Chemical Process

Technology
Chemical Process
Technology

Indra Deo Mall

phd fie (i) fiiche lm ippta

Former Professor and Head

Department of Chemical Engineering
Indian Institute of Technology, Roorkee
Uttrakhand, India
Distinguished Professor
Department of Chemical Engineering
University of Petroleum and Energy Studies, Dehradun
Uttrakhand, India

CBS Publishers & Distributors Pvt Ltd

New Delhi • Bengaluru • Chennai • Kochi • Kolkata • Lucknow • Mumbai
Hyderabad • Jharkhand • Nagpur • Patna • Pune • Uttarakhand
Disclaimer
Science and technology are constantly changing fields. New research and experience broaden the scope of
information and knowledge. The authors have tried their best in giving information available to them while
preparing the material for this book. Although, all efforts have been made to ensure optimum accuracy of the
material, yet it is quite possible some errors might have been left uncorrected. The publisher, the printer and
the authors will not be held responsible for any inadvertent errors, omissions or inaccuracies.

eISBN: 978-93-546-6730-5
Copyright © Authors and Publisher

First eBook Edition: 2024

All rights reserved. No part of this eBook may be reproduced or transmitted in any form or by any means,
electronic or mechanical, including photocopying, recording, or any information storage and retrieval system
without permission, in writing, from the authors and the publisher.

Published by Satish Kumar Jain and produced by Varun Jain for

CBS Publishers & Distributors Pvt. Ltd.
Corporate Office: 204 FIE, Industrial Area, Patparganj, New Delhi-110092
Ph: +91-11-49344934; Fax: +91-11-49344935; Website: [Link]; [Link];
E-mail: eresources@[Link]; marketing@[Link]

Head Office: CBS PLAZA, 4819/XI Prahlad Street, 24 Ansari Road, Daryaganj, New Delhi-110002, India.
Ph: +91-11-23289259, 23266861, 23266867; Fax: 011-23243014; Website: [Link];
E-mail: publishing@[Link]; eduportglobal@[Link].

Branches

Bengaluru: Seema House 2975, 17th Cross, K.R. Road, Banasankari 2nd Stage, Bengaluru - 560070,
Kamataka Ph: +91-80-26771678/79; Fax: +91-80-26771680; E-mail: bangalore@[Link]
Chennai: No.7, Subbaraya Street Shenoy Nagar Chennai - 600030, Tamil Nadu
Ph: +91-44-26680620, 26681266; E-mail: chennai@[Link]
Kochi: 36/14 Kalluvilakam, Lissie Hospital Road, Kochi - 682018, Kerala
Ph: +91-484-4059061-65; Fax: +91-484-4059065; E-mail: kochi@[Link]
Mumbai: 83-C, 1st floor, Dr. E. Moses Road, Worli, Mumbai - 400018, Maharashtra
Ph: +91-22-24902340 - 41; Fax: +91-22-24902342; E-mail: mumbai@[Link]
Kolkata: No. 6/B, Ground Floor, Rameswar Shaw Road, Kolkata - 700014
Ph: +91-33-22891126 - 28; E-mail: kolkata@[Link]

Representatives
Hyderabad
Pune
Nagpur
Manipal
Vijayawada
Patna
to
my parents, teachers and students
Foreword

T he developing nations, in their quest for economic growth, have been revamping,
modernizing and expanding the chemical industry. However, thesedays, the
industry has been facing various challenges, including the wide variation in the raw
materials and its costs, besides complying with stringent environmental standards and
enhanced quality of products required. To remain competitive, the chemical industry
has to look at various cost cutting and conservation measures including those for raw
materials, energy, and other utilities.
The book Chemical Process Technology by Prof ID Mall covers various inorganic and
organic chemical industries including fertilizers, pulp and paper, soap and detergents,
sugar and alcohol, cement, glass and refractory, dyes and paints, pharmaceutical
and metallurgical industries. Prof Mall has also discussed some details of petroleum
and petrochemical processes. The issues of specific energy consumption, corrosion,
environment and safety also have been widely covered in the last few chapters.
I congratulate Prof Mall for his efforts in detailing various aspects of chemical
process industries, and I am sure this compilation will help the students, faculty and
practicing engineers and scientists.
I wish Prof Mall all success in his future endeavors.

SJ Chopra
Chancellor
University of Petroleum and
Energy Studies (UPES)
Dehradun
Preface

C hemical industry is one of the most important sectors of economy and plays vital
role in the industrialization and urbanization which meet basic needs of mankind
through supplying fertilizers, synthetic fiber, synthetic rubber, polymers, sugar and
alcohol, paper dyes and intermediates, explosives, agrochemicals, dyes, paints, etc.
Globally, it processes more material than any other industry. With expected population of
7.6 billion by 2020, huge increase in demand for chemicals in various forms is expected
and offers the huge scope for the growth. The chemical industry in India accounts for
about 2.11% of gross domestic product (GDP) and is the third largest producer in Asia
and sixth largest in the world in terms of volume. Indian chemical industry has been
expected to grow from $118 billion in 2014 to $214 billion in [Link] diversification
within chemical industry is very large, as it includes more than eighty thousand
commercial products. The size of Indian chemical industry in terms of value of output
in year 2013–14 was 839,460 crore. The production of total major chemicals and
petrochemicals in 2014–15 was 21,226 kilo tons. Due to present epidemic all predicted
figures are going to change in spite of steps which are being taken globally.
Chemical technology is the one of the important courses in chemical engineering
curriculum. Chemical industry is knowledge intensive as well as capital intensive
industry. Knowledge of chemical process industries is of great importance to chemical
engineers. The book contains 28 Chapters. Chapter 1 deals with introduction to chemical
process industries dealing with technological development, major challenges, issues
and weakness of Indian chemical industry, global and Indian scenario. Chapter 2
deals with basic principles for chemical processes, unit processes and unit operations
in chemical industries. Chapter 3 deals with industrial gases. Chapter 4 deals with
chlor-caustic and soda ash industry while Chapter 5 discusses sulfur and sulfuric
acid. Chapter 6 deals with introduction to fertilizer industry, nitric acid and ammonia.
Chapters 7 and 8 describe nitrogenous and phosphorous and phosphatic fertilizer
industry. Chapter 9 describes cement and lime industries while Chapter 10 deals with
glass and refractories. Chapter 11 describes oils and fats industries while Chapter
12 describes explosives and miscellaneous chemicals. Chapter 13 describes about
metallurgical industry. Chapter 14 describes leather industries while in Chapter 15,
coal and coal as chemical feedstock has been discussed. Chapter 16 describes pulp
and paper industries. Chapter 17 describes about sugar and alcohol industries
while Chapter 18 describes about soap and detergent. Chapters 19 and 20 deal with
petroleum and petrochemical industries. Chapter 21 describes polymer, elastomer and
x Chemical Process Technology

synthetic fiber. Chapter 22 deals with agrochemicals while Chapters 23 and 24 deal
with dyestuff industry and paint, varnish and lacquers, respectively. Chapter 25
deals with pharmaceutical industry. Chapter 26 describes corrosion and material of
construction in chemical industries. Chapters 27 and 28 deal with energy management
in chemical industry and environment, health and safety in chemical process industry.
In appendices, a list of various petroleum, petrochemical, chemical and fertilizer
industry has been given. Cost of some important chemicals and utility is also given.
A list of commmonly used abbreviations in chemcial process industries is also provided
in the begining of the book.
Indra Deo Mall
Acknowledgments

would like to express my sincere thanks to Dr SJ Chopra, Chancellor, University

of Petroleum and Energy Studies for his encouragement, inspiration and valuable
comments, as well as for providing foreword in this book. I am greatly indebted
to Dr SN Upadhyaya, Former Director, Indian Institute of Technology, Banaras
Hindu University who has always a source of inspiration and encouragement.
I would like to offer my sincere gratitude to Dr Prem Vrat, Former Director,
Indian Institute of Technology, Roorkee, and Vice Chancellor, UP Technical
University and Dr SC Saxena, Former Director, Indian Institute of Technology,
Roorkee and Vice Chancellor, JP University. I would like to offer my sincere gratitude
to Prof MM Sharma and Dr RA Mashelkar who are source of inspiration to chemical
engineers. I would also like to pay my sincere gratitude to all my teachers at IIT, BHU,
Varanasi and rich tribute to those who are not with us for their inspiration and guidance.
I am thankful to my friend IM Mishra, Ex-Professor and Head, Chemical Engineering
IIT Roorkee, and Emeritus Professor, ISM Dhanbad, for his help and support. Thanks
are also due to Dr Vimal Chandra Srivastava, Head, Chemical Engineering, IIT Roorkee
for his support and sincere efforts and contribution.
The author pays rich tribute to late Shri Dhiru Bhai Ambani, great visionary who
has brought India on the world petroleum and petrochemical map and revolutionized
petroleum and petrochemical sector.
The author also pays rich tribute to late Prof AP Mall and Prof YD Upadhyay who
had been a source of inspiration and moral support.
I would like to offer my sincere gratitude to NPTEL, Reliance Industries Ltd., Indian
Oil Corporation Ltd, Panipat Refinery, Gas Authority of India Ltd, New Delhi; Indian
Petrochemical Corporation Ltd (Now Reliance Industries), Vadodara, and CPCL
for providing important technical information and Dr RP Verma, Former Executive
Director, IOC, R&D Centre, Faridabad, Dr SN Kaul, Former Acting Director, NERI,
Mr RK Ghosh, Former Director, Refineries, IOCL, Mr Sanjeev Singh, Director Refineries,
Former Chairman and MD, IOCL and Paradip Refinery, Mr A Basu, Former CMD, CPCL,
Chennai and presently, Head, Refineries HPCL, Dr MO Garg, Former Director General,
CSIR, late Sri Anand Kumar, Director Petrotech, Mr NP Rao DGM IFFCO Bareilly,
Dr Karuna, Head, Chemical Engineering Rohilkhand University, and Late Sri DK
Karwal, Former DGM, IOC Panipat Refinery, and Dr Sushil Kumar, Former President,
Reliance Industries. I would like to express my sincere thanks to Dr Chandrakant Thakur,
Assistant Professor, NIT, Raipur, for his untiring efforts in preparation of manuscript.
Sincere thanks are due to Dr V Subaramaiah, Assistant Professor, MNIT, Jaipur,
xii Chemical Process Technology

Dr SK Nanda, Professor, UPES, Dr M Gopinath, Assistant Professor, UPES, Dr Murali

Pujari, Assistant Professor, UPES, Dehradun. I also acknowledge the contribution of
my student, Saurabh Singh, Bokaro Steel Plant and some of my other students Anang
Swapnesh, Nitin Kumar, Dr Seema, Bhawna Bajpai, Dr Priyanka, Sanjay Gautam,
Shailendra, Karthikeyan Shukla, Rohit, Anirudh Jindal, Shamira Khatoon, Shrey Jain
and Rudraksh Rai and Sumit Shrma for designing cover page and flow diagram and
other computational work.
Last but not the least, I sincerely acknowledge the patience, support and
understanding of my wife Indira who is standing behind me during ups and down of
my life. I also acknowledge the support of Vishal and Pallavi, Kavim, Gunjan and
Sanjay, Priyansh and Shagun.
Indra Deo Mall
Contents

Foreword vii
Preface ix
Acknowledgments xi
Abbreviations xv
1. Chemical Process Industries 1
2. Basic Principles of Chemical Processes and Unit Operations in 16
Chemical Industries
3. Industrial Gases 46
4. Chlor-caustic and Soda Ash Industry 57
5. Sulfur and Sulfuric Acid 82
6. Fertilizer Industry 93
7. Nitrogenous Fertilizer and Nitric Acid 110
8. Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 133
9. Cement and Lime Industries 148
10. Glass and Refractories 162
11. Oil and Fats 176
12. Explosives and Miscellaneous Chemicals 186
13. Metallurgical Industry in India 195
14. Leather Industries 206
15. Coal and Coal as Chemical Feedstock 210
16. Pulp and Paper Industry 231
17. Sugar and Alcohol Industry 262
18. Soap and Detergent 276
19. Petroleum Refining 289
20. Petrochemical Industry 349
21. Polymer, Elastomer and Synthetic Fiber 422
22. Agrochemicals 475
23. Dyestuff Industry 484
24. Paint, Varnish and Lacquers 497
xiv Chemical Process Technology

25. Pharmaceutical Industry 504

26. Corrosion and Material of Construction in Chemical Industries 514
27. Energy Management in Chemical Industry 536
28. Environment, Health and Safety in Chemical Process Industry 550
Appendices
Appendix 1: Quantities and SI Unit 577
Appendix 2: Physical and Chemical Characteristics of Major Inorganic and 582
Organic Chemicals
Appendix 3: Major Petroleum, Petrochemical, Fertilizer and Chemical 597
Industries in India
Appendix 4: Major Manufacturing Associations 622
Appendix 5: Cost of Various Crude Oils and Petroleum Products 626
Index 629
Abbreviations

ACGIH American Congress of Governmental Industrial Hygienists

ADU Atmospheric Distillation Unit
AIHA American Industrial Hygiene Association
ANGM Association of Natural Gasoline Manufacturers
API American Petroleum Institute
Aq. Aqueous
ARCO Atlantic Richfield Co
ASTM American Society for Testing and Materials
Atm. Atmospheric Pressure
BMCI Bureau of Mines Correlation Index
BP British Petroleum; Boiling Point
BRPL Bongaigaon Refinery and Petrochemicals Limited
BTX Benzene, Toluene, Xylene
CCR Continuous Catalyst Regeneration
CCRU Continuous Catalytic Reforming Unit
CEL Shell Corrected Energy and Loss Index
CF Combustion Factor
CFC Continuous Film Contractor
CFR Compagnie Fransaus Deraffinage
CLO Clarified Light Oil
CNG Compressed Natural Gas
Co. Corporation
Conc. Concentration
CPCL Chennai Petroleum Corporation Limited
CPW Chlorinated Paraffins Wax
CR Catalytic Reforming
CSD Critical Solvent Dewaxing
DAO Deasphalted Oil
DCC Deep Catalytic Cracking
DEA Diethanol Amine
xvi Chemical Process Technology

DEG Diethylene Glycol

DGA Diglycol Amine
Dil. Dilute
DIPE Di-isopropyl Ether
DMF Dimethyl Formamide
DMSO Dimethyl Sulfoxide
EIA Environmental Impact Assessment
EII Energy Intensity Index
EOR Enhance Oil Recovery
EPA Environmental Protection Agency
EPDM Ethylene Propylene Diene Rubber
ETBA Ethyl Tertiary Butyl Alcohol
FCC Fluid Catalytic Cracking
FEP Fluorinated Ethylene Propylene
FO Fuel Oil
FP Freezing Point
FTT Furnace Transfer Temperature
GAIL Gas Authority of India Limited
GTL Gas to Liquids
GIS Geographic Information System
GPS Global Positioning System
IPA Isopropyl Alcohol
GTBA Gasoline Grade Tertiary Butyl Alcohol
HAZOP Hazard Operability Study
HCO Heavy Cycle Oil
H: HC Hydrogen to Hydrocarbon Ratio
HSD High Speed Diesel Oil
HTSD High Temperature Simulated Distillation
IBP Initial Boiling Point
ICI Imperial Chemical Industries
IFP Institut Français du Pétrole
LAB Linear Alkyl Benzene
LCO Light Cycle Oil
LD50 Lethal Dose
LDO Light Diesel Oil
LEL Lower Explosive Limit
LFL Lower Flammability Limit
LHSV Liquid Hourly Space Velocity
LNG Liquefied Natural Gas Liquid
LPG Liquefied Petroleum Gas
Abbreviations xvii

Ltd. Limited
LWD Logging While-Drilling Technologies
MAT Micro Activity Test
MBK Methyl Butyl Ketone
MCP Molecular Collision Parameter
MDD Maximum Drilling Depth
MDDW Mobil Distillate Dewaxing
MDEA Methyldiethanol Amine
MEA Monoethanol Amine
MEK Methyl Ethyl Ketone
MHC Mild Hydro Cracking
MLTD Mobil Low Temperature Disproportionation
MOGD Mobil Olefin to Gasoline and Distillate
MON Motor Octane Number
MP Melting Point
MSCC Milli Second Catalytic Crackings
MTBE Methyl Tertiary Butyl Ether
MVPI Mobil Vapor Phase Isomerization
MWD Measurement While Drilling
NA Naphthenic Acid
NAC Naphthenic Acid Corrosion
N+2A Naphthene + Two Times Aromatic Content
NGHS Natural Gas Hydrates
NIOSH National Institute for Occupational Safety and Health Services
NMP N-Methyl Pyrrolidone
NRCC Non-regenerative Catalytic Cracking
OH&S Occupational Health and Safety
OISD Oil Industry Safety Directorate
ONGC Oil and Natural Gas Corporation
OSA Oil Spill Authority
OSHA Occupational Safety and Health Administration
OSMA Oil Spill Management Authority
OSW Österreichische Stickstoff Werke
PDM Positive Displacement Motor
PRMC Project Review and Monitoring Committee for Oil Spill Management
PSA Pressure Swing Adsorption
QRA Quantified Risk Assessment
RFBD Residue Fluidized Bed Cracking
RFCC Residue Fluid Catalytic Cracking
RFG Reformulated Gasoline
xviii Chemical Process Technology

(R+M)/2 (RON+MON)/2
RON Research Octane Number
RVP Reid Vapor Pressure
SAC Solid Acid Alkylation Catalyst
SOP Super Oil Cracking
SCC Stress Corrosion Cracking
SEC Specific Energy Consumption
SHE Safety, Health and Environmental Management
SYDC Selective Yield Delayed Coking
TAA Tertiary Amyl Alcohol
TAEE Tertiary Amyl Ethyl Ether
TAN Total Acid Number
TAME Tertiary Amyl Methyl Ether
TBA Tertiary Butyl Alcohol
TBP True Boiling Point
TEA Triethanol Amine
TEG Tri Ethylene Glycol
TEL Tetra Ethyl Lead
TFE Tetrafluoroethylene
THEME Tertiary Hexyl Methyl Ether
THD Thermal Hydro Dealkylation
Tm Melting Point Temperature
TPR Throughput Ratio
TSA Temperature Swing Adsorption
UCC Union Carbide Co
UDEX Universal Dow Extraction
UEL Upper Explosive Limit
UOP Universal Oil Product
VDS Vortex Disengager Strippers
VGC Viscosity Gravity Correlation
VGO Vacuum Gas Oil
VI Viscosity Index
VLI Vapour Lock Index
VSS Vortex Separation System
WABT Weighted Average Bed Temperature
WAIT Weighted Average Inlet Temperature
WHSV Weight Hourly Space Velocity
ZMS High Silica/Alumina Ratio Zeolite
1
Chemical
Process Industries

1.1 INTRODUCTION
Chemical industry is one of the oldest industries and plays an important role in the social,
cultural and economic growth of a nation in providing basic needs of humankind—
food, shelter and clothing that have become an indispensable part of our life. It is
knowledge intensive as well as capital intensive industry. It is an integral constituent
of the growing Indian Industry (Annual Report 2016–17, Ministry of chemical and
fertilizer, Government of India). Figure 1.1 illustrates the role of chemical industry in
daily life. It is one of the most diversified of all industrial sectors covering thousands of
products. Chemical industry includes basic chemicals and its product, petrochemicals,
fertilizers, paints and varnishes, gases, soap and detergent, perfumes, pharma­-
ceuticals and covers thousands of products, which are finding use in our daily life
from industrial to household goods. Structure of organic chemical industry is shown
in Table 1.1. Various products are finding use in various fields like packaging to
agriculture, automobiles to telecommunication, construction to home appliances,
health care to personal care, explosive, pesticides to fertilizer, textile to tire cord,
chemicals to pharmaceuticals (Table 1.2). Indian chemical industry plays an important
role in the overall development of Indian economy and contributes significantly in
the GDP growth of the country. It comprises large scale, medium scale and small scale
units.

Fig. 1.1: Role of chemical industry (Sources: Mall, 2007, 2013, 2017)

1
2 Chemical Process Technology

Table 1.1: Structure of chemical industry

Inorganic chemical industry
Industrial gases: Syn. gases, hydrogen Phosphatic and potassium industries:
Nitro­genous industries: Ammonia, urea, nitric acid Rock phosphate, phosphoric acid, phos­
phatic fertilizers,
Marine chemicals: Salt, bromine iodine, sodium salts Electrothermal industries: Calcium carbide
Chloralkali industries, soda ash, bleaching powder, Sulfur and sulfuric acid
poly aluminum chloride
Ceramic industries: Cement, refractory and glass Nuclear industries
Metallurgical industry; ferrous and nonferrous metals
Organic chemical industry
Coal and coal chemicals Petroleum and petrochemicals
Pulp and paper Polymers, elastomers, synthetic rubbers
Soap and detergent Agrichemicals
Sugar and alcohol Pesticides
Explosives Dyes and intermediates
Surface coating industries: Paints, varnishes and Pharmaceutical industries
lacquers

Table 1.2: Major products of chemical industries and their area of application
Group of product Areas
Plastics and polymers Agricultural water management, packaging, automobiles,
telecommunications, health and hygiene, education
Synthetic rubber Transportation industry, textile, Industrial equipment lining
Synthetic fiber Non-woven and woven fiber in automobile, hosiery, textile
Soap and synthetic detergents Health and hygiene domestic as well as industrial
Industrial chemicals Drugs and pharmaceuticals, pesticides, explosives, surface
loading, dyes, lube additives, adhesive oil field, antioxidants,
chemicals, metal extraction, printing ink, paints
Sugar and alcohol Food, alcoholic breverages, chemical feed stock, ethoxylate,
biofuel
Pulp and paper Writing and printing paper, culture paper, news printing
paper, tissue paper, packaging paper
Fertilizer Agriculture, Chemical industry (ammonia and urea)
Agrochemicals Pesticides
Mineral acids and organic acid Chemical industry—organic and inorganic
Sources: Mall, 2007, 2013, 2017.

The chemical industry is a key contributor to the world economy and produces more
than 8000 products. Chemical industry is very important to the economic growth and
wealth of a country and the world as a whole. Production/consumption of chemicals
in the world rapidly accelerated from $1.45 trillion in 2003 to $4.1 trillion in 2013
Chemical Process Industries 3

with the rapid accelerated global GDP which increased from $39 trillion to 77 trillion
(Ganesan, 2017). According to Word Trade Statics Review 2016 the global exports in chemicals
is around $1750 billion (Ganesan, 2017). Chemical industry is a vital part of agricultural
and industrial development in India and has key linkages with several other down­-
stream industries such as automotive, consumer durables, engineering and food
processing (Chemical Engineering World, 2004). Organic chemicals are one of the
important sectors of the Indian chemical industry, which provide a vital development
role by providing petroleum products, chemical feedstock, basic chemicals,
intermediates, and important products like polymer, synthetic fiber, synthetic rubber,
paints, varnish, pesticides and explosives, dyes, specialty chemicals. Major feed stocks
for chemical industries are petroleum feed stock like naphtha, natural gas, kerosene,
etc. coal, biomass, oils and fats, sulfur, salt, limestone, rock phosphate, etc.

1.2 CHEMICAL INDUSTRY AND TECHNOLOGICAL DEVELOPMENT

Chemical process industry has evolved considerably over the last century largely in
response to changing societal requirements and changing raw material availability
and environmental issues. Some of the major technological developments in chemical
industry are (Mall 2017):
• Leblanc process to Solvay and modified Solvay process
• Lead chamber to contact process (single absorption) and double contact double
absorption (DCAA)
• Diaphragm process to mercury and mercury to membrane
• Wet to dry cement process
• Coal chemicals to alcohol-based chemicals to petroleum-based chemicals and vice
versa
• Acetylene-based chemicals to alcohol and petrochemical
• Claus to super claus process
• Wood-based paper to agro-based and waste paper-based
• Pulping to bio-pulping
• Stone ground wood pulping to refiner mechanical pulping (RMP), thermomechanical
pulping (TMP)
• Chlorine to oxygen bleaching and enzymatic bleaching
• Sulfur to pyrite-based sulfuric acid plant
• Conventional aluminum and iron-based catalyst to zeolite-based catalyst
• Coal-based fertilizer to natural gas and naphtha-based fertilizers
• Coal- and alcohol-based chemicals to petroleum-based chemicals
• Thermal cracking to catalytic cracking
• FCC to deep catalytic cracking for olefin and hydrocracking for processing heavier
crude
• Naphtha reforming to isomerization
• Acid catalyst to solid acid catalyst in alkylation process
• Naphtha steam cracking to gas cracking
• Conventional petroleum fuel to biofuel
• Coal as fuel to coal as chemical
• Coal gasification to petrocoke and biomass gasification
4 Chemical Process Technology

• Chemical pesticide to biopesticide

• Chemical fertilizer to biofertilizer
• Soap to detergent, liquid soap, non-biodegradable detergent to biodegradable
detergent
• Natural gas to coal bed methane, shale gas, gas hydrate
• Dimethyl terephthalate (DMT) to purified terephthalic acid (PTA)
• Conventional caprolactam to ammonium sulfate free caprolactam
• Natural fiber to synthetic fiber
• Natural rubber to synthetic rubber
• Petroleum refinery to natural gas refinery and biorefinery
• Petroleum refinery to petrochemical refinery
• Conventional gasification to underground gasification
• Conventional drilling to horizontal drilling and hydrofracturing
• Gas to liquid and methanol to olefin technology
• Coal to methanol and olefin
• Conventional desulfurization to ultradesulfurization processes and bio-
desulfurization
• Polymer to biopolymer
• Conventional Ziegler–Natta catalyst to metallocene catalyst

1.3 STRUCTURE OF CHEMICAL INDUSTRY

Chemical industry can be broadly divided into inorganic and organic chemical industry.
Structure of chemical Industry is given in Table 1.1.
Revolutionary innovations in chemical process industries are given in Table 1.3.

Table 1.3: Revolutionary innovations in chemical process industries

Year Revolutionary innovations
1914 Dubba cracking process
1935 First catalytic process
1938 High octane gasoline
First fluid catalytic cracking process
1949 First reformer, PlatformingTM Process
1953 Synthetic zeolites
1957 Biodegradable detergents
1958 Technologies for lead removal from gasoline
1950–60 Steam cracking of naphtha
1960s Automotive catalytic converter
1970s ParexTM Process
1971 CCR platforming commercialization
1978 Etherification of isobutylene
1990 OlexTM process
1990 Olex propane dehydrogenation process
1994 Detal solid bed detergent alkylation
Contd...
Chemical Process Industries 5

Table 1.3: Revolutionary innovations in chemical process industries (Contd...)

Year Revolutionary innovations
2000 onward Coal to chemicals, coal to methanol, DME, coal to natural gas
developments Coal liquefaction and coal based syn oil, gasification of coal and petrcoke
GTL technology, Shale gas by horizontal drilling
Low CAT proess, oxygen enriched sulfur recovery
Oxidative coupling of methane to olefin
2000 onward Biofuel, lingo biomass hydrolysis an fermentation
older technologies Algae biofuel
revived
GTL technologies
Nano particles for energy and environmental management
Application of nano catalyst
Resid FCC technology for maximum distillate yield
CO2 capture technology
LC fining
KBR Technology for Phenol
BenzOUT technology
Biobased Chemicals
Electrolysis of water
Single step process for hydrogen—CNG Production from natural gas
Developing feed stock in Naphtha-based hydrogen generation units
2010 onwards Synthetic fuel, dimethyl ether, gas to liquid technologies for gasoline,
diesel, methanol to gasoline (MTG), syn gas to gasoline (STG plus)
Advances in depolymerization of nylons
First indigenous Indalin technology for upgradation of low value streams
to Petrochemicals
First indigenous diesel hydrotreating technology in India
Addition of Bharat 6 norms
Digitalization of chemical industry and adoption of industry 4.0

1.4 GLOBAL AND INDIAN CHEMICAL INDUSTRIES

The chemical industry is one of the world largest sectors of economy and has impact on
many other industries. There has been continuous development in chemical industry
with age. Technology commercialization with age of chemical industry is given in
Figure 1.2. The global chemical industries consists of a very diverse range of product
and global market size. As per Hindu Business Line (2017), global chemical industry is
estimated at $4.3 and is expected to grow in future. Global chemical industry is expected
to grow at a CGR of 3.9% from 2015 to 2030. Faster big row will be seen in Asia rather
than Europe and USA (Chemical News April 2018, p.18). Global chemical production
especially petrochemical-based organic chemical based and fertilizer industry is likely
to show significant growth with evolution of shale gas, and utilization of more and more
natural gas. Global market for cosmetic and toiletry ingredient to reach $24.5 billion
6 Chemical Process Technology

Fig. 1.2: Technology commercialization of chemical industry with age.

Source: Vora BV. International conference organized by Chemtech during CHEMTECH World Expo 2011.

in 2018 from $18 billion in 2011 and $19.6 billion in 2013 (Chemical Industry Digest
December 2012, p.30).
Evolution of the Indian chemical industry and technological commercialization with
age of industry and age of product is given in Figure 1.3. Revolutionary innovations in
chemical process industries are given in Table 1.3.
Indian chemical industry is an important constituent of the Indian economy. As per the
Hindu Business Line (March 24, 2017), the Indian chemical industry is expected to grow
to $226 billion by 2020. In terms of volume it is 12th largest in the world and 3rd largest
in Asia. According to ICC president, Indian chemical industry ranked 7th globally
and likely to move 5th position by 2025. Indian chemical industry will be reaching a
size of $370 billion by 2025. The specialty chemicals industry has the potential to be
a $150 billion market by 2025. High demand supply gap for petrochemical would
be by 2025 (Chemical News, April 2018, p.12). Currently, per capita consumption of
products of chemical industry in India is about 1/10th of the world average. Over the

Fig. 1.3: Evolution of the Indian chemical industry and technological commercialization with
age of industry and age of product
Chemical Process Industries 7

last decade, the Indian chemical industry has evolved from being a basic chemical
producer to becoming and innovative industry. India is the fourth largest producer of
agrochemicals. Evolution of the Indian chemical industry and technological driving
force for development of chemical industry is given in Table 1.4. With investments in
R&D, the industry is registering significant growth in the knowledge sector comprising
of specialty chemicals, fine chemicals, and pharmaceuticals with higher annual growth
rate.
The chemical industry R&D spends would need to go up from current levels of less
than 0.5% to reach closer to global benchmarks of 4% of sales. Industry is expected to
grow much more in future due to high end demand based on increasing per capita
consumption and population growth, improved export competiveness and resultant
growth impact. Indian chemical industry can achieve accelerated growth phase with a
strategic roadmap.
Some of the critical issue now Indian chemical industries are facing are availability
of feedstock, rising cost of raw material including energy and ease of doing business,
availability of indigenous technology, poor infrastructure, small capacity plants, etc.
The total production of organic chemicals during 2008–09 works out to 1.25 million
with value of 0.9717 billion. The size of the petrochemicals segment was estimated
as 13.96 billion. Total size of dyestuff industry is estimated as $4 billion. There are 50
organized industries and over 900 small-scale industries. India has 8.5–9% global market
share. The India pharmaceutical industry is the fourth largest volume terms and 15th
largest market in value terms. The market will reach $30 billion by 2020. The size of the
agrochemicals industry estimated at over $1 billion. Consumption of various chemical
ingredients for cosmetic and toiletry is increasing due to increased population. Global
market for cosmetic and toiletry ingredients is increasing.
As a result, the annual consumption of chemical fertilizers has increased in nutrient
terms (N, P, K) has increased from 0.7 lakh tons in 1951–52 to 277.39 lakh tons in 2011–
12). Per hectare consumption of fertilizer which was less than 1 kg in 1951–52 has risen
to a level of 141.30 in 2011–12 (Ministry of Chemicals and Fertilizer Annual Report,
2012–13).
Segments of the Indian chemical industry are given in Table 1.5. Details of major
chemical production and growth are shown in Table 1.6. Product-wise production of
major chemicals is given in Table 1.7. Value output of different product groups in the
chemical and chemical products is given Table 1.8. As per the European Chemical
Council, world chemicals (excluding pharmaceuticals) sales in 2012 are valued at
3127 billion. India ranks 10th in world chemical market with chemical 61.1 Euro billon
in 2012. As per UN Comrade Data base for 2014, India ranks 14th in the world exports
of chemicals (excluding pharmaceutical products) and ranks 8th in the world imports of
chemicals (excluding pharmaceutical products). India’s export of chemicals (excluding
pharmaceuticals) was $29.76 billion in 2014.
Chemical industry is one of the world’s largest industry and has significant influence
on many other industries. Total global chemical shipments are worth 5 billion dollars.
Global chemical industries consists of a very diverse range of products. Global market
size was estimated at 3.9 trillion US dollars and is expected to grow at 3–4% per annum
over the next five years to reach 4.7 trillion US dollars (Source: Global Investors Summit
(March 7–8, 2016) Gurugram, India’s chemical market to grow $139 billion in FY 2014 to
$214 billion by FY2019. With market size of $139 billion the industry accounts for 3.3%
8 Chemical Process Technology

of global market (Table 1.9). Globally India ranks 3rd in terms of volume and 14th in
terms of value (Source: Global Investors Summit, March 7–8, 2016, Gurugram). India is
the second largest producer of cement in the world.
As per the Annual Report of 2017, Ministry of Chemicals and Fertilizer Industry,
Department of Chemicals and Petrochemicals, National accounts statistics 2016 chemical
and chemical products sector accounted for 2.33 of the GVA in 2014–15 compared to
2.34 5 in 2013–14. The size of the Indian chemical Industry in terms of value of output
in the year 2014–15 was 8,33,046 crores.

Table 1.4: Driving force for Indian chemical industry

Surface area 3.287 million km2
Population 1.2 billion
Coastline 6,000 km
Port traffic Over 350 million TPA
Road length Over 3 million km
Railways 100,000 Track km
(Largest in Asia, 2nd in the World)
Growth of population 1951 36 crore to present 130 crore
Growth in vehicle population More than fivefolds
India’s passager vehicle production projections In 2010—2.6 million vehicles
By 2015—5.1 million vehicles
By 2020—9.7 million vehicles
Contribution of GDP: Agriculture: 25%, Industry: 24% Services: 51%

Table 1.5: Segments of the Indian chemical industry

Basic chemicals (49.05%): Market value: US$32.78
• Inorganic chemicals (Caustic chlorine, soda ash, sodium bicarbonate, carbon black, titanium
oxide, sulfuric acid, hydrochloric acid, etc.)
• Organic chemicals (acetic acid, acetic anhydride, acetone, phenol, methanol, formaldehyde,
nitrobenzene, malice anhydride, aniline, chloromethane, acetaldehyde, ethanol amines, ethyl
acetate, etc.
• Petrochemicals (Olefins, aromatics-benzene, toluene, xylene, fiber intermediates MEG, PTA,
acrylonitrile, propylene, caprolactam, adipic acid, hexamethylenediamine, phthalic anhydride,
methanol, LAB, polymers, synthetic fiber, etc.)
• Fertilizers (Nitrogenous and phosphatic)
• Other industrial chemicals
Specialty chemicals (24.69%): Market value: US$16.50
• Paints and varnishes, Textile chemicals, Dyestuffs and intermediates, Catalysts, Plastic additives,
Adhesive sealants, Industrial gases
Knowledge chemicals (26.6%): Market value: US$17.55
• Pharmaceuticals
• Biotechnology
• Agrochemicals
Source: Lokhapare, 2011.
Chemical Process Industries 9

Table 1.6: Production of major chemicals and petrochemicals, production 1000 tons
Group Production/Growth rate 2011–12 2015–16 2018–19
Production 6478 6802 8043
Alkali chemicals
Growth (%) 3.3 2.7
Production 881 1002 1064
Inorganic chemicals
Growth (%) –1.9 6.1
Production 1640 1589 1884
Organic chemicals
Growth (%) 5.8 –1.9
Production 156 188 217
Pesticides technical
Growth (%) 8.5 0.6
Production 241 304 382
Dyes and pigments
Growth (%) –1.6 6.6
Production 9396 9884
Total major chemicals
Growth (%) 3.2 2.3
Production 3105 2362 36071
Synthetic fiber
Growth (%) –0.6 12.2
Production 6211 8839 100400
Polymers
Growth (%) 17.4 17.0
Production 100 242 351
Elastomers
Growth (%) –4.7 40.8
Production 623 566 687
Synthetic detergents intermediates
Growth (%) –2.4 –5.1
Production 969 1700 1589
Performance plastics
Growth (%) –0.7 6.9
Production 11008 14900 16269
Total basic major petrochemicals
Growth (%) 8.6 10.8
Total major chemicals and Production 20404 24783 27858
petrochemicals Growth (%) 6.0 7.3
Source: Annual Report 2015–16, 2016–17, 2019–2020 Government of India Ministry of Chemicals
and Fertilizer, Dept. of Chemicals and Petrochemicals.

Table1.7: Product-wise production of major chemicals

Production 2014–15 2018–19
Major chemical products
in 1000 MT
Alkali chemicals 8043
Caustic soda 2439.5
Liquid chlorine 1717.97
2462.00
Total alkali chemicals 6619.47
Contd...
10 Chemical Process Technology

Table1.7: Product-wise production of major chemicals (Contd...)

Production 2014–15 2018–19
Major chemical products
in 1000 MT
Inorganic chemicals 1064
Aluminum chloride, calcium carbide, carbon black, 921.60
Potassium chlorate, Titanium oxide, Red phosphorous,
Hydrogen peroxide, Calcium carbonate
Organic chemicals (Acetic acid, Acetic anhydride, 1619.11 1884
Acetone, Phenol, Methanol, Formaldehyde, Nitro­
benzene, Maleic anhydride, Pentaerythritol, Aniline,
Chloromethanes, Isobutylene, MEK, ONCB, PNCB,
Acetaldehyde, Ethanol amines, Ethyl acetate, Nitro­
toluene)
Pesticides and Insecticides 186.63 217
Dyes and Pigment 285.23 382
Synthetic fibers (Acrylic, Polyester, Nylon, Polypropylene, 3527 3601
Fiber
Polymers (Polyethylene, Polypropylene, Polystyrene, 6523 10040
Polyvinyl chloride)
Synthetic rubber (Styrene butadiene rubber, Poly­ 94 351
butadiene rubber, Ethyl propylene dimmers, Ethyl vinyl
acetate, Nitrile rubber)
Synthetic detergent intermediates 687
LAB 475
Ethylene oxide 164
Performance plastics (ABS resin, Polymethylmetha- 766 1589
acrylate (PMMA), Styrene acrylonitrile (SAN), Nylon
Fiber intermediates (Acrylonitrile, Caprolactam, Dime­ 4877
thyl terephthalate, Monoethylene glycol, Purified
terephthalic acid)
Olefins (Ethylene, Propylene, Butadiene) 6276
Aromatics (Benzene, Toluene, Mixed xylene, Orthoxylene, 4638
Paraxylene)
Other petro-based chemicals (Butanol, C4 raffinate, 1962
diethylene glycol, Diacetone alcohol, 2-ethyl hexanol,
methyl methacrylate, Phthalic anhydride, Propylene
oxide, Propylene glycol, polyvinyl acetate resin, vinyl
acetate monomer)
Total basic major petrochemicals 14905 16269
Total basic major chemicals and petrochemicals 24788 27858
Source: Annual Report 2015–16, 2019–20, Government of India, Ministry of Chemicals and Fertilizer,
Department of Chemicals and Petrochemicals.
Chemical Process Industries 11

Table 1.8: Global and Indian chemical Industry

Global industry revenue US $3.9 trillion
Industry revenue in India US $144 billion
Estimated revenue in India 2020 US $300 billion
Total production of Indian chemical 19,308 × 1000 tons
industry (Fy 2014)
Contribution to India’s GDP 2013 2.5%
CAGR of Revenue in India 2013 13% (Chemicals)
Direct and Indirect Employment 1 million
(Fy 2012)
Indian chemical industry • Eighth largest producer in India, third largest in Asia
• Fourth largest of agrochemicals
• 16% of word production of dye stuff and dye intermediates
Source: Global Investors Summit, Gurugram, March 7–8, 2016.

Table 1.9: Market size Breakdown of Indian Chemical industry (Market size in $139 billion)
Agrochemicals (Pesticides, fertilizers) 20%
Bulk chemicals (Organic and inorganic chemicals) 39%
Biotechnology 4
Pharma 17
Specialty chemicals 20

1.5 CHANGING SCENARIO IN CHEMICAL PROCESS INDUSTRY

There has been continuous change in capacity and size of the plant in chemical industry
due to development of process technology, equipment and requirement of products.
Changing scenario in chemical industry is given in Table 1.10.

Table 1.10: Changing scenarios in chemical process industry

Capacity
Sector
Past Present and future
Petroleum refinery 0.4 million tons 34 million tons
Naphtha cracker 20,000 tons/year >8 lakh tons
Ammonia plant >500 TPD >1500 TPD
Urea 300 TPD >1500 TPD
Sulfuric acid 0.018 million tons/year 0.7 million tons/year
Caustic chlorine 10 TPD >100 TPD
Cement 0.06–-0.07 million tons >3 million tons

1.6 CHEMICAL FEEDSTOCKS

With increasing demand of raw material there has been continuous search for new
and alternative feedstocks past, present and future, for chemical industry is given in
Table 1.11 and in Figure 1.4 (Mall, 2016).
12 Chemical Process Technology

Table 1.11: Chemical feedstocks: Past, present and future

Past Present and future
Coal, Salt, Biomass, Natural • Gaseous: Natural gas, Condensate, Refinery gases, Coal bed
rubber, Cotton Methane, Gas hydrate, Shale gas
• Liquids: Naphtha, Solvent extracts, Middle distillates
• Solids: Coal, Coke, Wax, Residues
• Biomass: Agriculture residue, Algae
• Sea Chemicals: Salt, Bromine, Iodine, Titanium, Zirconium, etc.
More 64 elements

Fig. 1.4: Past, present, and future of chemical feedstocks

1.7 CHARACTERISTICS OF THE INDIAN CHEMICAL INDUSTRY

Characteristics of Indian chemical industry is given below (Lokhapare, 2011):
• High domestic demand potential as the Indian markets develops and per capita
consumption levels increases
• High degree of fragmentation and small scale of operations
• Limited emphasis on exports due to domestic market focus
• Low-cost competitiveness as compared to other countries due to the high cost of
feed stocks and power
• Low focus on R&D despite initiatives to innovate processes to synthesis products
effectively.

1.7.1 INDIAN CHEMICAL INDUSTRY WEAKNESSES

Although Indian chemical industry has made consistent growth during last six decades,
however, compare to global level there is lot of scope for further development. Some
of the weaknesses are
• Sizes of older units well below global levels
• High-cost structures
• Higher cost of raw materials
• Long gestation periods
• Integration and infrastructure inadequacies
• Process development, low R&D investment
• Mindset.
Chemical Process Industries 13

Diversification, globalization, emerging technologies, etc. has affected the practice

of Engineering. Major issues are:
1. Raw material cost reduction, waste minimization and waste utilization and
conservation of natural resources
2. Capital investment reduction
3. Energy use reduction and alternate sources of energy
4. Increased process flexibility and inventory reduction
5. Ever greater emphasis on process safety
6. Increase attention to quality
7. Better environmental performance
8. Advance personalized learning and innovative idea
9. Discontinuing certain low value-added products/inefficient technologies
10. Provide access to clean water
11. Better health and safety management strategies.

1.7.2 TYPICAL ISSUES FOR CHEMICAL INDUSTRIES

Due to various technological and engineering developments, chemical industry has
been able to reduce the cost of production. Changes in technology and raw materials
have shifted regularly and frequently toward lower costs and more competitive­-
ness, better conversion efficiency, high productivity, less energy consumption, and
broader spectrum of product grades. However, due to increasing cost of raw materials
and stringent environment issues, chemical industry is facing major challenges in
future. Typical issues in chemical industry to meet the future challenges are shown
in Figure 1.5.
Due to various technological and engineering developments, chemical industry has
been able to reduce the cost of production. Changes in technology and raw materials
have shifted regularly and frequently to technological development in chemical industry
(Fig. 1.6).

Fig. 1.5: Typical issues in chemical industry (Source: Invited talk

National conference on Innovation and development in Chemical
technology IDCT 2014, Feb. 28–March 1, 2014)
14 Chemical Process Technology

Fig. 1.6: Technological development in chemical industry

Over the next few years, we can expect major shifts in three areas: Organizational
structure, talent management and corporate culture (Joshi, 2019). Digitalization has
become part of our life. With effect of industry 4.0 is likely to have impact in areas
of production and supply chain (Durani, 2019). Adoption of industry 4.0 will bring
significant strategic advantage and boom the chemical process industry (Shenoy, 2019)

BIBLIOGRAPHY
1. Annual reports 2010–11, 2013–14, 2015–16, 2016–17, 2019–20, Department of Chemicals and
Petrochemicals, Ministry of Chemicals and Fertilizer, Government of India.
2. Banerjee RB, Tuli DK, Mukhopadhya, Kalia A. Lignocellulosics for 2nd generation Bioethanol
production. Journal of Petrotech, July–Sep. 2011, p.55.
3. Chemical Engineering World, 2004, p.74.
4. Chemical Industry Digest, December 2012, p.30.
5. Chemical News April 2018, p.18.
6. Duchesne E. Coal to plastic technology Methane to Olefins (MTO) and olefin cracking process
(OCP) case study of total’s pilot research to commercialization”, Chemical Industry Digest April,
2011, p.68.
7. Durani AR. How new industry captains view Industry 4.0, Chemical Industry Digest, April 2019,
p.28.
8. Dutta I. Hurdles to maintaining output. The Hindu Survey of Indian Industry, 2011, p.157.
9. Dutta NC. Chemical from renewable resources, Chemical Industry Digest, August 2011, p.75.
10. Energy Outlook, 2003.
11. Furimsky E. Gasification in Petroleum refinery of 21st century. Oil and Gas Science Technology
Rev, IFP vol 54, 1999.
12. Global Investors Summit, March 7–8, 2016, Gurugram, Haryana, India.
13. Handa SK, Ganesh C. “Feed stock choice in Petrochemicals Industry”, Chemical Industry Digest,
August, 2010, p.60.
14. Hefler P. International Fertilizer Association, June 2013.
15. Hindu Business Line, 2017.
16. Joshi R. How new industry captains view Industry 4.0. Chemical industry April 2019 p.28.
17. Journal of the Petrotech Society, January 2007, p.37–38.
18. Kapoor R. Chemical News April 2018, p.12
19. Lo. Simultaneous saccharification and fermentation and co-fermentation of lignocellulosic
biomass from ethanol production, Methods Mol Biol, 581, 2009, 263–280.
20. Lokhapare SR. Indian chemical industry–current status. Chemical News July 2010, p.11.
21. Mall ID Invited talk National conference on Innovation and development in Chemical technology
Indraprastha university IDCT 2014, Feb 28–March 1 2014.
Chemical Process Industries 15

22. Mall ID. Petrochemical Process Technology, First edition, Macmillan, New Delhi, India, 2007.
Reprint 2015, Second edition 2017, Trinity Press: Laxmi Publication.
23. Mall ID. NTPEL (Nation Programming on Technology Enhanced Learning) Lectures on Organic
Chemical Technology, 2013.
24. Mall ID. Workshop on—Advances in Petroleum ands Petrochemicals” April 16, 2016, Organized
by Department of Chemical Engg, R&D Centre, University of Petroleum and Energy Studies
and IICHE Regional centre, Dehradun.
25. Mark E Reno, Monique Streff, Andrew Hird, Anjan Ray. Conversion of biomass to fuel as
an environmental impact reduction opportunity for the pulp and paper industry. In paper
International, April–June 2011.
26. Masood R. Role of raw material in petrochemical industry. Chemical Industry News, July 2002.
27. Mukherji D, Reddy BM, Raghvan KV. Advanced catalysis for sustainable development. Chemical
Industry Digest May 2015, p.50.
28. Patil A. Methanol from coal: an emerging alternate feedstock, Chemical Industry digest July
2009, p.69.
29. Rappaport H. Plyolefins “Feed stocks and market by Howard Rappaport” CMAI. Plast. India-
Feb-2009.
30. Shenoy, SR. How new industry captains view Industry 4.0. Chemical industry April 2019 p.28.
31. Singh MP, Tuli DK, Malhotra RK, Kumar A. Ethanol from lignolcellosic biomas: prospects and
challenges. J of the Petrotech society, June 2008, p.39.
32. Tuil HD, Reith JH, Zenson EV, Westmann M, Baker RR, Elberson, HW. Lignocellulosic Ethanol
a second option.
33. Vora BV. International conference organized by during CHEMTECH World Expo 2011.
34. World Trade Statistic Review, 2016.
2
Basic Principles of Chemical
Processes and Unit Operations in
Chemical Industries

INTRODUCTION
Chemical processes usually have three interrelated elementary processes, namely transfer
of reactants to the reaction zone, chemical reactions involving various unit processes,
and separation of the products from the reaction zone using various unit operations.
Processes may involve homogeneous or heterogeneous systems. In homogeneous
system, reactants are in same phase—liquid, gas or solid; while heterogeneous system
has two or more phases—gas–liquid, gas–solid, gas–gas, liquid–liquid, liquid–solid,
solid–solid, etc. Reactions may be reversible or irreversible, endothermic or exothermic,
catalytic or noncatalytic. Various variables affecting chemical reactions are temperature,
pressure, composition; catalyst activity, selectivity and stability; the rate of heat and
mass transfer. The reaction may be carried out in batch, semi-batch or continuous mode.
Reactors may be batch, plug flow or continuous stirred tank reactor (CSTR) type. It
may be isothermal or adiabatic. Catalytic reactors may be packed bed, moving bed or
fluidized bed.
Along with knowledge of various unit processes and unit operation, following
information are very important for the development of a process and its commerciali­
zation (Austin, 1984):
• Material and energy balance, raw material and energy consumption per ton of
product, energy changes.
• Batch versus continuous process flow diagram.
• Chemical process selection: design and operation, pilot plant data, equipment
required, material of construction.
• Chemical process control and instrumentation.
• Chemical process economics: competing processes, material and energy cost, labor,
overall cost of production.
• Market evaluation: purity of product and uniformity of product for further processing.
• Plant Location.
• Environment, health, safety and hazard issues.
• Construction, erection and commissioning.
• Management for productivity and creativity: training of plant personals and
motivation at all levels.
• Research, development and patient.
• Process intensification.
16
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 17

In order to improve the productivity and for making the process cost-effective and
improving overall economy, compact, safe, energy efficient and environmentally
sustainable plant, process intensification has become very important and industry is
looking beyond the traditional chemical engineering. Teaching the priciple of chemical
engineering to produce the ultimate product—the well rounded chemical engineer—is
one of the most innovative and continually evolving challenges (Ziemlewski, J CEP
February 2009, p.6). Chemical engineering always incorporats the new developments
in biotechnology and nanotechnology. Safety, health and environment, productivity
through conservation of raw material, better energy mangment through incorporating
various developments, and incorporating software computational and and modeling
capabilities have become imporatant theme of chemical engineering curricuum. Now
chemical engieering environment has become global and mutidisciplinary and demands
both technical competencies and soft skills. Five essential soft skills that an engineer
needs are teamwork, leadership, communication, cultural diversity organisational
development and performance (Ziemlewski, 2009). Today ‘s world is full of challenges
and the enire world is witnessing turmoil due to growing energy crisis, food shortage,
absence of clean water and rapant acts of terror growing world population. Chemical
engineeing is boundary less (Yadav, 2009). The chemical engineering is uniquely placed
to solve many of the buisiness, economic and social challenges of 21st century (Liveris,
2007). In the follwing text some basic concepts of chemical engineeing is discussed.

2.1 HEAT TRANSFER

Heat transfer (or heat) is thermal energy in transit due to a spatial temperature difference.
There are three modes of heat transfer, i.e. conduction, convection and radiation.
1. Conduction
Conduction is the transfer of energy from the more energetic particles of a substance to
the adjacent less energetic ones as a result of interactions between the particles.
(Area) (Temperature difference)
Fourier’s Law: Rate of heat conduction ∝
Thickness
or
Qcond = – KA DT (K= W/mK)
Dx
2. Convection
Convection is the mode of energy transfer between a solid surface and the adjacent
liquid or gas that is in motion, and it involves the combined effects of conduction and
fluid motion. Convection is called forced convection if the fluid is forced to flow over
the surface by external means such as a fan, pump, or the wind. In contrast, convection
is called natural (or free) convection if the fluid motion is caused by buoyancy forces
that are induced by density differences due to the variation of temperature in the fluid.
Newton’s law of cooling:
Qconv = hAs (Ts–T) (h = W/m2K)
3. Radiation
Radiation is the energy emitted by matter in the form of electromagnetic waves (or
photons) as a result of the changes in the electronic configurations of the atoms or
molecules. A blackbody is defined as a perfect emitter and absorber of radiation.
18 Chemical Process Technology

Emissivity of a surface represents the ratio of the radiation emitted by the surface at a
given temperature to the radiation emitted by a blackbody at the same temperature.
The fraction of irradiation absorbed by the surface is called the absorptivity, the fraction
reflected by the surface is called the reflectivity, and the fraction transmitted is called
the transmissivity.
Stefan–Boltzmann law: Qemit, max = es AsT4 (e = 1 for black body)
C1
Planck’s law: Ebl (l, T) =
5
l [exp (C2/lT) –1]
C1 = 2phc 20 = 3.742 × 108W.mm4/m2
Where, C2 = hc0/k = 1.439 × 104 mm.K
Wien’s displacement law: (lT)max power = 2897.8 mm.K

Critical Radius of Insulation

It is the outer radius of the insulation at which the rate of heat transfer is maximum.
It depends on thermal conductivity of the material and outer surface’s heat transfer
coefficient.

Fins
These are extended surfaces, made of highly conductive materials such as aluminum,
commonly used in practice to enhance heat transfer, and they often increase the rate
of heat transfer from a surface several folds.

Boiling and Condensation

When the temperature of a liquid at a specified pressure is raised to the saturation
temperature Tsat at that pressure, boiling occurs. Likewise, when the temperature of a
vapor is lowered to Tsat, condensation occurs. Typical boiling curve for water at 1 atm
pressure is shown in Figure 2.1.

Fig. 2.1: Boiling curve for water at 1 atm pressure

Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 19

Evaporation occurs at the liquid–vapor interface when the vapor pressure is less
than the saturation pressure of the liquid at a given temperature. Boiling, on the other
hand, occurs at the solid–liquid interface when a liquid is brought into contact with a
surface maintained at a temperature Ts sufficiently above the saturation temperature
Tsat of the liquid.
Two distinct forms of condensation are observed—film condensation and dropwise
condensation.
In film condensation, the condensate wets the surface and forms a liquid film on
the surface that slides down under the influence of gravity. The thickness of the liquid
film increases in the flow direction as more vapors condenses on the film. This is how
condensation normally occurs in practice. In dropwise condensation, the condensed
vapor forms droplets on the surface instead of a continuous film, and the surface is
covered by countless droplets of varying diameters.
A heat pipe is a simple device with no moving parts that can transfer large quantities
of heat over fairly large distances essentially at a constant temperature without requiring
any power input.

Heat Exchangers
They are devices that facilitate the exchange of heat between two fluids that are at
different temperatures while keeping them from mixing with each other. Logarithmic
mean temperature difference (LMTD), which is an equivalent mean temperature
difference between the two fluids for the entire heat exchanger.

Steam Economy
Steam economy is the ratio between total steam evaporated and steam consumed.

2.2 THERMODYNAMICS
There are three types of systems. Open system which can exchange matter and energy
with surroundings, closed system, which can exchange energy but not matter with
surroundings, isolated system, which can exchange neither energy nor matter with
surroundings.

Properties of System
Intensive Properties
An intensive property is a bulk property, meaning that it is a physical property of a
system that does not depend on the system size or the amount of material in the system.
Extensive Properties
An extensive property is additive for subsystems. This means the system could be
divided into any number of subsystems, and the extensive property is measured for
each subsystem; the value of the property for the system would be the sum of the
property for each subsystem.

Types of Thermodynamic Processes

Isothermal
The process in which no change in temperature occurs is termed to be isothermal process.
20 Chemical Process Technology

Isobaric: The process in which no change in pressure occurs is termed to be isobaric

process.
Isochoric: An isochoric process, also called a constant-volume process, and is volumetric
process, or an isometric process, is a thermodynamic process during which the volume
of the closed system undergoing such a process remains constant.
Adiabatic
The process in which no transfer of heat takes place is called adiabatic process.
Cyclic
A cyclic process is the underlying principle for an engine. If the cycle goes counter
clockwise, work is done on the system every cycle.

Zeroth Law of Thermodynamics

If two systems are in thermal equilibrium with a third system, they must be in thermal
equilibrium with each other.
First Law of Thermodynamics
Energy can be changed from one form to another, but it cannot be created or destroyed.
The total amount of energy and matter in the universe remains constant, merely changing
from one form to another.
Second Law of Thermodynamics
The entropy of any isolated system not in thermal equilibrium almost always increases.
It states that “in all energy exchanges, if no energy enters or leaves the system, the
potential energy of the state will always be less than that of the initial state.” This is
also commonly referred to as law of entropy.

Heat Engines
A device that can produce work at the cost of heat input and rejecting the waste heat
to low temperature sink.

Refrigerators
The transfer of heat from a low-temperature medium to a high-temperature one requires
special devices called refrigerators. The objective of a refrigerator is to maintain the
refrigerated space at a low temperature by removing heat from it.

Heat Pumps
Transfers heat from a low-temperature medium to a high-temperature one to maintain
a heated space at a high temperature.

Other Common Terms Frequently Used in Thermodynamics

Enthalpy
Heat content of a system at constant pressure is known as enthalpy. It is denoted by H.
Heat capacity: Amount of heat required to raise the temperature of system by 1°C.
Entropy: Entropy is a measure of the “disorder” of a system. What “disorder” refers to
is really the number of different microscopic states a system can be in, given that the
system has a particular fixed composition, volume, energy, pressure, and temperature.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 21

Gibbs free energy: Gibbs free energy is a measure of the amount of energy available to do
work in an isothermal and isobaric (constant temperature and pressure) thermodynamic
system. This is where the term “free” comes from; it refers to the amount of energy in
a system that is easily available for usage.
Helmholtz free energy: In thermodynamics, the Helmholtz free energy is a thermodynamic
potential that measures the “useful” work obtainable from a closed thermodynamic
system at a constant temperature and volume.
Joule Thomson Effect
The pressure drop in the fluid accompanied by a large drop in temperature is called
Joule–Thomson effect. Due to this reason throttling devices (based on this effect) are
commonly used in refrigeration and air-conditioning applications. The magnitude
of the temperature drop (or, sometimes, the temperature rise) during a throttling
process is governed by a property called the Joule–Thomson coefficient. It is
isenthalpic process.
Fugacity
It is the fictitious pressure term used for real gases so as to retain simple form of equation
applicable for ideal gases.
Activity Coefficient
An activity coefficient is a factor used in thermodynamics to account for deviations
from ideal behavior in a mixture of chemical substances.
Degree of Freedom
It gives the number of independent variables that should be specified in order to specify
a system completely.

2.3 MASS TRANSFER

The mass transfer operation includes the following techniques:

Diffusion
It is a spontaneous mixing process aiming at homogenization of the fluid mixture.
Gases and liquids are all associated with mass transfer. Diffusion is caused by a random
molecular motion being the consequence of thermally induced agitation of molecules,
which finally tends to complete homogenization of the mixture.
• Adsorption: It is the adhesion of atoms, ions, or molecules from a gas, liquid, or
dissolved solid to a surface. This process creates a film of the adsorbate on the
surface of the adsorbent. This process differs from absorption, in which a fluid
(the adsorbate) is dissolved by or permeates a liquid or solid (the adsorbent),
respectively.
• Absorption: It is a physical or chemical phenomenon or a process in which atoms,
molecules or ions enter some bulk phase—gas, liquid or solid material.
• Drying: It is a mass transfer process consisting of the removal of water or another
solvent by evaporation from a solid, semi-solid or liquid.
• Humidification and dehumidification: Humidification is the process of constituting the
water-vapor content in a gas. The reverse of the operation is called dehumidification.
22 Chemical Process Technology

Both are important for many industrial operations, such as air conditioning, gas
cooling, controlled drying of wet solids, comfort heating, etc. When a gas is brought
in contact with a pure liquid in which it is essentially insoluble, interphase mass and
heat transfer takes place.
• Distillation: The process of separation of two or more liquids on the basis of their
boiling points is termed to be distillation.
• Liquid–liquid extraction: Liquid–liquid extraction also known as solvent extraction
and partitioning, is a method to separate compounds based on their relative
solubilities in two different immiscible liquids, usually water and an organic solvent.
It is an extraction of a substance from one liquid into another liquid phase.
Molecular Diffusion
Molecular diffusion is concerned with the movement of individual molecules through
a substance by virtue of their thermal energy. It is governed by Fick’s first law.
dCA
Fick’s first law: JAB = –  CDAB dz

NA CDAB NAC – CA (NA + NB)
2
Diffusion in gases: NA = In
NA + NB Z NAC – CA1 (NA + NB)
DABPt – –
Steady state diffusion of A by nondiffusing B: NAZ = – (PA –PA )
RTzP 1 2
BM
DAB – –
Equimolar counter diffusion: NAZ = (PA –PA )
RTz 1 2

Diffusion coefficient
Gases: DAB ∝ T 3/2, P–1
Liquid: DAB ∝ T, m–1, M0.5
B

Film Theory
The film theory postulates that the concentration will follow such that the entire
concentration difference (CA –CA ) is attributed to molecular diffusion within an effective
1 2
film of thickness Zf.
K ∝ DAB

√
D
AB
Penetration theory: K=2
pq

Surface renewal theory: K= √SD AB

Distillation
Distillation is a unit operation in which the constituents of a liquid mixture are separated
using thermal energy on the basis of their relative volatility.
Relative volatility (a): This is the ratio of the concentration ratio of any A and B compo­
nents in one phase to that in the other phase and is a measure of the separa­bility.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 23

y*/(1–y*) y* (1–x)
a= =
x/(1–x) x(1–y*)
Raoult’s Law
For an ideal solution, the equilibrium partial pressure p* of a constituent at a fixed
temperature equals the product of its vapor pressure P when pure at this temperature
and its mole fraction in the liquid.
–*
pA = pAx
Minimum boiling azeotropes: When the positive deviations from ideality are
sufficiently large and the vapor pressures of the two components are not too far apart,
the total-pressure curves at constant temperature may rise through a maximum at
some concentration.
Maximum boiling azeotropes: When the difference in vapor pressures of the compo­
nents is not too great and in addition the negative deviations are large, the curve for
total pressure against composition may pass through a minimum.
Relative Volatility
For a liquid mixture of two components (called a binary mixture) at a given temperature
and pressure, the relative volatility is defined as
(yi/xi)
a= = Ki/Kj
(yj/xj)
where:
a = the relative volatility of the more volatile component i to the less volatile
component j
yi = the vapor-liquid equilibrium concentration of component i in the vapor phase
xi = the vapor-liquid equilibrium concentration of component i in the liquid phase
yj = the vapor-liquid equilibrium concentration of component j in the vapor phase
xj = the vapor-liquid equilibrium concentration of component j in the liquid phase
(y/x) = K commonly called the K value or vapor-liquid distribution ratio of a component

Types of Distillation
• Simple distillation
• Steam distillation
• Flash distillation
• Molecular distillation
• Extractive distillation
• Azeotropic distillation
Mccabe Thiele method: It is commonly used to calculate number of theoretical trays
in a distillation tower.
Reflux ratio, R = Ratio of flow returned as reflux to flow of top product
Total reflux ratio implies:
• No product out
• High purity
• Maximum reboiler heat and condenser cooling capacity.
24 Chemical Process Technology

Minimum reflux ratio implies:

• Infinite no. of trays
• Minimum reboiler heat and condenser cooling capacity.
Overall Efficiency
It is the ratio of number of theoretical plates and number of actual trays in a column.
It pertains to entire column.
Murphree Efficiency
Murphree tray efficiency is based on a semi-theoretical model that assumes that the
vapor between trays is well-mixed, that the liquid in the downcomers is well-mixed,
and that the liquid on the tray is well mixed and is of the same composition as the liquid
in the down comer leaving the tray. It pertains to single point on given plate.
Absorption
Absorption involves the selective dissolution of one or more components of a gas or
vapor into liquid. Stripping involves transfer of a component from liquid phase in
which it is dissolved to a gas phase.
Henry’s law: It states that the solubility of a gas in liquid is dependent on its partial
pressure in the gas phase.
p = Hx
Extraction
Separations involving the contact of two insoluble liquid phases are known as liquid-
extraction operations. In all such operations, the solution which is to be extracted is
called the feed, and the liquid with which the feed is contacted is the solvent. The
solvent-rich product of the operation is called the extract, and the residual liquid from
which solute has been removed is the raffinate.
Distribution coefficient: The ratio of the concentration of the solute in the extract phase
to raffinate phase.
K = y*/x
Selectivity
The ratio of the ratios, the separation factor or selectivity (b) is analogous to relative
volatility of distillation.
(weight fraction of C in E)/(weight fraction A in E) y*E
b= =
(weight fraction of C in R)/(weight fraction A in R) x*R
Leaching
Leaching is the preferential solution of one or more constituents of a solid mixture by
contact with a liquid solvent.
Equipments used:
• Bollman extractor
• Ratocel extractor
• Dorr thickner
Humidification
Humidification involves interphase of mass and energy which results when a gas is
brought into contact with a pure liquid in which it is essentially soluble.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 25

Dehumidification is the removal of moisture from air and is opposite to humidification

process.
Humidity
The ratio mass of vapor/mass of gas is the absolute humidity (Y’). If the quantities are
expressed in moles, the ratio is the molal absolute humidity (Y).
yA PA PA
Y= = =
yB PB 1–pA

MApA
Y'=
MB(1–pA)

Psat
A
Saturated absolute humidity: YS =
P – Psat
1 A

Dry-bulb temperature: This is the temperature of a vapor-gas mixture as ordinarily

determined by immersion of a thermometer in the mixture.
Wet-bulb temperature: It is the steady state, nonequilibrium temperature reached
by a small mass of liquid immersed under adiabatic conditions in a continuous stream
of gas.
Dew point: It is the temperature at which a vapor–gas mixture becomes saturated when
cooled at constant total pressure out of contact with a liquid.
Humid volume (VH) of a vapor–gas mixture is the volume of unit mass of dry gas and its
accompanying vapor at the prevailing temperature and pressure.

υH = 8315 ( 1
MB
+
Y'
MA )( tG + 273
Pt )
Humid heat (Cs) is the heat required to raise the temperature of unit mass of gas and
its accompanying vapor one degree at constant pressure.
Cs = CD + Y'CA
Adiabatic Saturation Temperature: The adiabatic saturation temperature (sometimes
referred to as the thermodynamic wet-bulb temperature) is defined as the temperature
obtained by an air-water vapor mixture if it becomes saturated with water vapor in an
adiabatic process
las
tG1 – tas = (Y’as –Y’1)
CS1
Drying
It refers to the separation of volatile liquids from solid materials by vaporizing the
liquid and removing the vapor.
Moisture content (wet basis): The moisture content of a solid or solution is usually
described in terms of weight percent moisture, and unless otherwise qualified this is
ordinarily understood to be expressed on the wet basis, i.e. as (kg moisture/kg wet
solid) 100 = [kg moisture/(kg dry solid + kg moisture)] 100 = 100X/(1 + X).
Moisture content (dry basis): This is expressed as kg moisture/kg dry solid.
26 Chemical Process Technology

Equilibrium moisture X*: This is the moisture content of a substance when at equilibrium
with a given partial pressure of the vapor.
Bound moisture: This refers to the moisture contained by a substance which exerts an
equilibrium vapor pressure less than that of the pure liquid at the same temperature.
Unbound moisture: This refers to the moisture contained by a substance which exerts
an equilibrium vapor pressure equal to that of the pure liquid at the same temperature.
Free moisture: Free moisture is that moisture contained by a substance in excess of
the equilibrium moisture: X – X*. Only free moisture can be evaporated, and the free-
moisture content of a solid depends upon the vapor concentration in the gas.
Constant-rate period: It is called when the drying takes place entirely within the constant-
rate period, so that X1 and Xf > XC and N = NC.
Ss (X1–X2)
q=
ANc
Falling rate: If X1 and X2, are both less than XC, so that drying occurs under conditions
of changing N.

2.4 REACTION ENGINEERING

Residence time: Residence time (also known as removal time) is the average amount
of time that a particle spends in a particular system. This measurement varies directly
with the amount of substance that is present in the system.
V
t=
q
Where t is used as the variable for residence time, V is the capacity of the system, and
q is the flow for the system.
Liquid Hourly Space Velocity (LHSV)
It is a method for relating the reactant liquid flow rate to the reactor volume at a standard
temperature. Usually, this temperature ranges from 60°F to 75°F (15.6°C to 23.9°C). The
volumetric flow rate is treated as a liquid at these conditions, even though the actual
material may be a gas under normal operating conditions
LHSV = Reactant liquid flow rate/Reactor volume
Weight Hourly Space Velocity (WHSV)
WHSV is defined as the weight of feed flowing per unit weight of the catalyst per hour.
Since weight of the catalyst charged in to the reactor is not varied and always same, so
any variation in flow of liquid per hour will change the WHSV.

Conversion
The conversion XA is the number of moles of A that have reacted per mole of A fed to
the system.

Yield
It is the amount of product obtained in a chemical reaction. The absolute yield can be
given as the weight in grams or in moles (molar yield). The fractional yield, relative yield,
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 27

or percentage yield, which serves to measure the effectiveness of a synthetic procedure,

is calculated by dividing the amount of the obtained product by the theoretical yield
(the unit of measure for both must be the same).

Continuously Stirred Tank Reactor (CSTR)

As the name suggests, it is perfectly mixed reactor where concentration is same at all
the places in the reactor.

Plug Flow Reactor

The plug flow reactor (PFR, sometimes called continuous tubular reactor, CTR, or piston
flow reactors) is a model used to describe chemical reactions in continuous, flowing
systems of cylindrical geometry.
Fluid going through a PFR may be modeled as flowing through the reactor as a
series of infinitely thin coherent “plugs”, each with a uniform composition, traveling in
the axial direction of the reactor, with each plug having a different composition
from the ones before and after it. The key assumption is that as a plug flows through
a PFR, the fluid is perfectly mixed in the radial direction but not in the axial direction
(forward or backward).

Moving Bed Reactor

Moving bed reactors are catalytic reactors in which the catalyst moves through the
reactor along with the reactants. They are open systems and operate at steady state.

Recycle Reactor
If one desire to promote back mixing or intermediate mixing in a system, it is then
desirable to use recycle reactor.
Volume of fluid returned to the reactor enetrance
Recyle ratio (R) =
Volume of fluid leaving the system
Space Velocity
Space velocity refers to the quotient of the entering volumetric flow rate of the reactants
divided by the reactor volume (or the catalyst bed volume) which indicates how many
reactor volumes of feed can be treated in a unit time.

Conversion
The fracssstional conversion of a reactant is the ratio moles reacted
Moles reacted
f=
Moles fed
Selectivity
The terms yield and selectivity are used to describe the degree to which a desired
reaction predominates over competing side reactions.
Moles of desired product formed
Yield:
Moles that would have been formed if there were no side
reactions and the limiting reactant had reacted completely
28 Chemical Process Technology

Moles of desired product formed

Selectivity:
moles of undesired product formed
Arrhenius Equation
The Arrhenius equation is a simple, but remarkably accurate, formula for the temperature
dependence of the reaction rate constant, and therefore, rate of a chemical reaction.
The Arrhenius equation gives “the dependence of the rate constant k of chemical
reactions on the temperature T (in absolute temperature Kelvin) and activation energy
Ea”, as shown below:
–E /RT
k = Ae a
Where A is the pre-exponential factor or simply the prefactor and R is the universal
gas constant.

First-order Reaction
A first-order reaction depends on the concentration of only one reactant (a unimolecular
reaction). Other reactants can be present, but each will be zero-order. The rate law for
an elementary reaction that is first order with respect to a reactant A is
d[A]
r= – = k[A]
dt
Second-order Reaction
A second-order reaction depends on the concentrations of one second-order reactant,
or two first-order reactants. For a second order reaction, its reaction rate is given by:
d[A] d[A] d[A]
– = 2k[A]2 or – = k[A] [B] or – = 2k[B]2
dt dt dt
Reversible Reaction
A reversible reaction is a chemical reaction that results in an equilibrium mixture of
reactants and products. For a reaction involving two reactants and two products this
can be expressed symbolically as
aA + bB  cC + dD
Autocatalytic Reactions
Reactions in which the product formed itself acts a catalyst for the reaction are called
autocatalytic reactions.
Heterogeneous Reactions
These are the chemical reactions in which the reactants are components of two or more
phases.

2.5 FLUID MECHANICS (Fig. 2.2)

Newton’s Law of Viscosity

It states that the shear stress between adjacent fluid layers is proportional to the negative
value of the velocity gradient between the two layers.
du
t=m
dy
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 29

Fig. 2.2: Fluid mechanics

Newtonian Fluid
A fluid which has a linear relationship between shear stress and velocity gradient, i.e.
follows Newton’s law of viscosity.

Non-Newtonian Fluid
Fluids which do not follow the linear law and are treated in books on rheology.
Dilatants, or shear-thickening, fluid increases resistance with increasing applied
stress.
Pseudo-plastic, or shear-thinning, fluid decreases resistance with increasing stress.
If the thinning effect is very strong, as with the dashed-line curve, the fluid is termed
plastic. The limiting case of a plastic substance is one which requires a finite yield stress
before it begins to flow.
The linear-flow Bingham plastic idealization is shown, but the flow behavior after
yield may also be nonlinear. An example of a yielding fluid is toothpaste, which will
not flow out of the tube until a finite stress is applied by squeezing.
Some fluids require a gradually increasing shear stress to maintain a constant strain
rate and are called rheopectic. The opposite case of a fluid which thins out with time
and requires decreasing stress is termed thixotropic.

Fluid Kinematics
It deals with describing the motion of fluids without necessarily considering the forces
and moments that cause the motion.
A streamline is a curve that is everywhere tangent to the instantaneous local velocity
vector.
A path line is the actual path traveled by an individual fluid particle over some time
period.
Continuity Equation
r1A1V1 = r1A1V1
30 Chemical Process Technology

f)
Velocity Potential Function (f
In an irrotational region of flow, the velocity vector can be expressed as the gradient of
a scalar function called the velocity potential function.
y)
Velocity Stream Function (y
It is the scalar function of space and time in such a way that its derivative in a given
direction is equal to the velocity component of the fluid along perpendicular to that
direction.

Fluid Dynamics
Euler’s Equation dp
r + gdz + ndn = 0

p n2
Bernoulli’s Equation +z+ = const.
rg 2g

Various Flow Meters

Venturimeter
A venturimeter is a device used for measuring the rate of flow of a fluid flowing through
a pipe. It mainly consists of:
• A short converging part: It is that portion of the venturi where the fluid gets converges.
• A Throat: It is the portion that lies in between the converging and diverging part of
the venturi. The cross section of the throat is much less than the cross section of the
converging and diverging parts. As the fluid enters in the throat, its velocity increases
and pressure decreases.
• Diverging part: It is the portion of the venturimeter (venturi) where the fluid gets
diverges.
Orifice Meter
The principle of the orifice meter is identical with that of the venturi meter. The reduction
of the cross section of the flowing stream in passing through the orifice increases
the velocity head at the expense of the pressure head, and the reduction in pressure
between the taps is measured by a manometer. Bernoulli’s equation provides a basis
for correlating the increase in velocity head with the decrease in pressure head.
Pitot Tube
A pitot tube is a pressure measurement instrument used to measure fluid flow velocity.
The pitot tube was invented by the French engineer Henri Pitot in the early 18th century
and was modified to its modern form in the mid-19th century by French scientist Henry
Darcy. It is widely used to determine the airspeed of an aircraft, water speed of a boat,
and to measure liquid, air and gas flow velocities in industrial applications.

Mechanical Operations
Ritinger’s Law
The work required in crushing is proportional to the new surface created. This is
equivalent to the statement that the crushing efficiency is constant and, for a giving
machine and material, is independent of the sizes of feed and product. If the sphericities
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 31

(before size reduction) and (after size reduction) are equal and the machine efficiency
is constant, the Rittinger’s law can be written as
P
∙ = Kr
m
( D–1
x1
– –
Dx2
1
)
where P is the power required, ∙ is the feed rate to crusher, D
­–
–­
m x2 is the average particle
diameter before crushing, Dx1 is the average particle diameter after crushing, and Kr is
Rittinger’s coefficient.
Power Law
A Power-law fluid, or the Ostwald–de Waale relationship, is a type of generalized
Newtonian fluid for which the shear stress, t, is given by

t=K (
∂u n
∂y )
where K is the flow consistency index (SI units Pa∙sn), ∂u/∂y is the shear rate or the
velocity gradient perpendicular to the plane of shear (SI unit s–1), and “n” is the flow
behavior index (dimensionless). If ‘n’ were less than one, the power law predicts that
the effective viscosity would decrease with increasing shear rate indefinitely, requiring
a fluid with infinite viscosity at rest and zero viscosity as the shear rate approaches
infinity, but a real fluid has both a minimum and a maximum effective viscosity that
depend on the physical chemistry at the molecular level. Therefore, the power law is
only a good description of fluid behavior across the range of shear rates to which the
coefficients were fitted.
Fluids: Fluid which obeys Newton’s law of viscosity and other are non-Newtonian fluids
(paints, tooth paste, jellies, gels, slurryies, polymer solution). Non-Newtonian fluids
may be Bingham fluid, pseudoplastic fluids, dialatant fluids. If fluid flos at Reynolds
number <2100 the it is laminar flow.
Bernoulli Equation
Incompressible flow equation of liquids and of gases at low Mach number, the mass
density of a fluid parcel can be considered to be constant, regardless of pressure
variations in the flow. For this reason, the fluid in such flows can be considered to be
incompressible and these flows can be described as incompressible flow.
v2 p
+ gz + = constant (A)
2 ρ
where:
v Is the fluid flow speed at a point on a streamline?
g Is the acceleration due to gravity,
z Is the elevation of the point above a reference plane, with the positive z-direction
pointing upward—so in the direction opposite to the gravitational acceleration,
p Is the pressure at the chosen point, and
ρ Is the density of the fluid at all points in the fluid.
Pumps
The purpose of a pump is to add energy to a fluid, resulting in an increase in fluid
pressure, not necessarily an increase of fluid speed across the pump.
32 Chemical Process Technology

Volume flow rate (capacity): V = m ∙ /ρ

( )( )
p ν2 p ν2
Net head: H= +z+ – +z+
ρg 2g out ρg 2g
in

Various type of pumps are centrifugal pump which operate on centrifugal forces,
reciprocating pumps which deliver fixed volume of fluids on each stroke; rotary pumps
deliver a fixed quantity of fluid per revolution. Priming, cavitation and NPSH (net
positive suction head) are commonly used terms. Characteristics of centrifugal pump
is the plot of volumetric flow rate vs head, efficiency, power input.

Dimensionless Numbers
Reynolds Number (Re)
The Reynolds number, Re, is arguably the most commonly used dimensionless group
in chemical engineering. It gives a measure of the ratio of inertial and viscous forces in
fluid flow. It is often used to determine if the flow is either laminar or turbulent.
In laminar flow, viscous forces dominate. The flow paths are smooth, streamline and
constant.
In turbulent flow, inertial forces dominate. The flow regime is unstable, generating
eddies and vortices.
The Reynolds number can be calculated using the following equation:
ρ.u.L
Re =
m
Where
r Fluid density (kg/m3)
u Fluid velocity (m/s)
L Characteristic dimension (m)
m Dynamic viscosity (Pa.s)
The units used to calculate Reynolds number are unimportant—provided that they
are consistent.
In pipes (or circular cross-section) the characteristic dimension can be taken as the
pipe diameter. For pipe flow, laminar flow is usually found at Reynolds numbers
below about 2000, and turbulent flow is found above about 4000. At Reynolds number
between about 2000 and 4000, the flow regime is transitional, i.e. rapidly changing
between laminar and transitional flow.
Prandtl Number (Pr)
The Prandtl number, Pr, is the ratio of kinematic viscosity to the thermal diffusivity.
It is used in many calculations involving heat transfer in flowing fluids, as it gives a
measure of the relative thickness of the thermal and momentum boundary layers. It
can be calculated using the following equation:
Cp.m
Pr =
k
Where
Cp Fluid specific heat capacity (J/kg.K)
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 33

m Dynamic viscosity (Pa/s)

k Thermal conductivity (W/m.K)
It should be noted that the Prandtl number is dependent on the fluid physical
properties alone. Consequently, it is often found in physical properties. For many gases
(with the notable exception of hydrogen), the Prandtl number has a value of 0.6–0.8
over a wide range of conditions.
Nusselt Number (Nu)
The Nusselt number, Nu, is the ratio of convective to conductive heat transfer in a fluid
over a given length, l:
h.l
Nu =
k
Where
h Heat transfer coefficient (W/m2.K)
l Characteristic length (m)
k Thermal conductivity (W/m.K)
For heat transfer in pipes, the characteristic length is the pipe diameter.
At a Nusselt number of around one means that convection and conduction are about
equal. Typically, this occurs in laminar conditions. As the Nusselt number becomes
larger, convective heat transfer becomes relatively more important. This occurs as the
flow becomes more turbulent. The mass transfer equivalent of the Nusselt number is
the Sherwood number.
Sherwood Number (Sh)
The Sherwood number, Sh, is a measure of the ratio of convective and diffusive mass
transfer in a fluid. It is analogous to the Nusselt number in heat transfer:
hD.l
Sh =
D
Where
hD Mass transfer coefficient (m/s)
l Characteristic length (m)
k Molecular diffusivity (m2/s)
Froude Number (Fr)
The Froude number, Fr, is a measure of the ratio of the inertial and gravitational forces
and can be expressed as:

Fr = ν
(g.l)½
Where
v Velocity (m/s)
g Acceleration due to gravity (m/s2)
l Characteristic length (m)
It is often used to analyze fluid flow problems where there is a free surface. For
example, in agitated vessels, Fr governs the formation of free surface vortices.
34 Chemical Process Technology

Grashoff Number (Gr)

Grashoff number, Gr, is a ratio of the buoyancy and viscous forces. It can be expressed as:
[Link].l 3.ρ  2
Gr =
m2
  
Where
b Volumetric coefficient of thermal expansion (–)
g Acceleration due to gravity (m/s2)
ΔT Temperature difference (K)
l Characteristic length (m)
ρ Fluid density (kg/m3)
µ Dynamic viscosity (Pa.s)
It is used to calculate heat transfer in natural convection, where fluid velocity depends
on buoyancy.
Mach Number (Ma)
The Mach number, Ma, is the ratio of the fluid velocity to the velocity of sound in that
medium. It can be expressed as:

Ma = u
a
Where
u Fluid velocity (m/s)
a Speed of sound in fluid medium
In chemical engineering, the Mach number is commonly used in calculations involving
high velocity gas flow.
Schmidt Number (Sc)
Schmidt number, Sc, is the ratio of kinematic viscosity to the diffusivity. It can be
expressed as:
m
Sc =
ρ.D
Where
m Dynamic viscosity (Pa/s)
r Fluid Density (kg/m3)
D Diffusivity (m2/s)
It characterizes mass transfer in a flowing fluid.

2.6 UNIT PROCESSES AND UNIT OPERATIONS IN CHEMICAL PROCESS TECHNOLOGY

Chemical process is combination of unit processes and unit operation. Unit process
involves principal chemical conversions leading to synthesis of various useful product
and provides basic information regarding the reaction temperature and pressure,
extent of chemical conversions and yield of product of reaction nature of reaction
whether endothermic or exothermic, type of catalyst used. Unit operations involve the
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 35

physical separation of the products obtained during various unit processes. Various
unit processes in chemical industries are given in Table 2.1.
Nitration involves the introduction of one or more nitro groups into reacting molecules
using various nitrating agents like fuming, concentrated, aqueous nitric acid mixture
of nitric acid and sulfuric acid in batch or continuous process. Nitration products find
wide application in chemical industry as solvent, dyestuff, pharmaceuticals, explosive,
chemical intermediates.
Typical products: TNT, Nitrobenzene, m-dinitrobenzene, nitroacetanilide, alpha
nitronaphthalene, nitroparaffins.

Table 2.1: Unit processes in chemical process industries

Alkylation and hydrodealkylation Decomposition
Acylation Fermentation
Ammoxidation Halogenation
Amination by reduction Hydrogenation
Amination Hydrogenolysis
Aromatization Hydroformylation
Amination by ammonolysis Hydrolysis
Calcination Hydration
Carbonation Hydroammonalysis
Causticisation Isomerization
Chlorination and oxychlorination Neutralization
Condensation Nitration
Biomethanation Methanation
Carbonization
Disproportionation Oxidation and partial oxidation
Cracking; Thermal, steam cracking, catalytic Pyrolysis
cracking
Dehydration Polymerization: Addition and condensation
Chain growth and step growth, bulk, emulsion,
suspension, solution, radical and coordination
polymerization
Dehydrogenation Reduction
Digitization and coupling Reforming: Steam reforming
Catalytic reforming
Gasification of coal and biomass Sulfidation
Desulfurization and hydrodesulfurization Sulfonation
Electrolysis Sulfation
Etherification Xanthation
Estertification and transestrerificartion
36 Chemical Process Technology

Unit Operations in Chemical Industries

Unit operations are very important in chemical industries for separation of various
products formed during the reaction. Table 2.2 gives the details of unit operation in
chemical process industries. Typical unit operations are shown in the Figure 2.3.

Table 2.2: Unit operations in vhemical process industries

Absorption and stripping Membrane process: Reverse osmosis, ultrafiltration,
dialysis, electrodialysis, pervaporation
Adsorption and desorption Crushing, grinding, pulverizing and screening
Pressure swing adsorption
Chromatography
Distillation: Batch distillation Solid–liquid extraction
Flash distillation, azeotropic distillation,
extractive distillation
Reactive distillation
Evaporation Striping
Fluidization Sublimation
Crystallization Solvent extraction
Liquid–liquid extraction

Distillation
Distillation has been the king of all the separation processes and most widely used
separation technology and will continue as an important process for the foreseeable
future (Olujie, et al. 2003). Distillation process is used for separation of two or more
component present in the feed into various components. The process of distillation
involves vaporization and subsequent separation by condensation. Separation is based
on the difference in the vapor pressure of different components at a given temperature.
Distillation is used in petroleum refining and petrochemical manufacture. Distillation
is the heart of petroleum refining and all processes require distillation at various stages
of operations.

Membrane Processes
Membrane processes have emerged one of the major separation processes during the
recent years and finding increasing application in desalination, waste water treatment
and gas separation and product purification. Membrane technology is vital to the process
intensification strategy and has continued to advance rapidly with the development of
membrane reactors, catalytic membrane reactor, membrane distillation, and membrane
bioreactors for wide and varied application (Sridhar, 2009).
Membrane process classified based on driving force. Various types of membrane
process and driving force are given in Table 2.3.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 37

Fig. 2.3: Contd...

38 Chemical Process Technology

Fig. 2.3: Contd...

Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 39

Fig. 2.3: Contd...

40 Chemical Process Technology

Fig. 2.3: Typical unit operations in chemical industries

Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 41

Table 2.3: various types of membrane processes based upon driving force
Membrane process Driving force
Reverse osmosis Pressure difference
Ultrafiltration Pressure difference
Microfiltration Pressure difference
Nanofiltration Pressure difference
Dialysis Concentration difference
Pervaporation Concentration difference
Liquid membrane Concentration difference
Electrodialysis Electrical potential
Gas permeation Concentration difference
Thermo-osmosis Temperature difference

Based on lower operating costs, comparable capital cost and only slightly product
loss (including fuel), membranes have demonstrated a flexible, cost, effective alternative
to amine treating for some natural gas processing applications (Cook and Losin, 1995).
Membrane distillation is a membrane separation process, which can overcome the
limitation of more traditional membrane process. Membrane distillation has significant
advantage over other processes, including low sensitivity to feed concentration and the
ability to operate at low temperature (Patil and Patil, 2012). Various type of membrane
processes are mention in Table 2.4.

Table 2.4: Various types of membrane processes based upon separation mechanisms
Separation process Separation mechanisms Feed stream
Microfiltration Sieving Liquid or gas
Ultrafiltration Sieving Liquid
Dialysis Sieving and sorption–diffusion Liquid
Reverse osmosis Sorption-diffusion Liquid
Evaporation Sorption-diffusion Liquid
Gas and vapor permeation Sorption-diffusion Liquid or vapor

Absorption
Absorption is the one of the most commonly used separation techniques for the gas
cleaning purpose for removal of various gases like H2S, CO2, SO2 and ammonia. Cleaning
of solute gases is achieved by transferring into a liquid solvent by contacting the gas
stream with liquids that offers specific or selectivity for the gases to be recovered. Unit
operation and is mass transfer phenomena where the solute of a gas is removed from
being placed in contact with a nonvolatile liquid solvent that removes the components
from the gas.
• Solvent: Liquid applied to remove the solute from a gas stream.
• Solute: Components to be removed from entering streams.
42 Chemical Process Technology

Some of the Commonly Used Solvents

Amine processes: Mono-ethanol amine (MEA), di-ethanol amine (DEA), tri-ethanol
amine (TEA), diglycol amine (DGA), methyl diethanol amine (MDEA)
• Carbonate process: K2CO3, K2CO3 + MEA, K2CO3 + DEA, K2CO3 + arsenic trioxide
• Physical absorption: Polyethylene glycol dimethyl ether (Selexol), N-methyl
pyrrolidine, NMP (Purisol), Methanol (Rectisol), Sulfonane mixed with an
alkanolamine and water (sulfinol).
Adsorption
Adsorption technology is now used very effectively in the separation and purification
of many gas and liquid mixtures in chemical, petrochemical, biochemical and
environmental industries and is often a much cheaper and easier option than distillation,
absorption or extraction. Some of the major applications of adsorption are gas bulk
separation, gas purifications, liquid bulk separation, liquid purifications (Keller II, 1995).
One of the most effective method for recovering and controlling emissions of volatile
organic compounds is adsorption. Some of the commercial adsorbents are silica gel,
activated carbon, carbon molecular sieve, charcoal, zeolites molecular sieves, polymer
and resins, clays, biosorbents. Some of the key properties of adsorbents are capacity,
selectivity, regenerability, kinetics, compatibility and cast (Knaebel, 1995). Some of the
methods used for regeneration of adsorbent are thermal swing, pressure swing, vacuum
(special case of pressure swing), purge and gas stripping, steam stripping (Crittenden,
1988). Commercial adsorption processes is given in Table 2.5 (Keller II, 1995). Some of
the important criteria of good adsorbent are:
• It must selectivity concentrate one or more components called adsorbate to form
their fluid phase levels.
• The ability to release adsorbate so that adsorbent can be reused.
• As high as possible delta loading the change of weight of adsorbate per unit weight
of adsorbent between adsorbing and desorbing steps over a reasonable range of
pressure and temperature.

Table 2.5: Commercial adsorption processes

Sorbex process Application
Parex Separation of paraxylene from mixed C8 aromatics isomers
MX sorbex Meta xylene from mixed C8 aromatics isomers
Molex Linear paraffins from branched and cyclic hydrocarbons
Olex Olefins from paraffins
Crsex Para cresol or meta cresol isomers
Cymex Para cymene or meta cymene from cymene isomers
Sarex Fructose from mixed sugar
UOP ISOSIV processor Separation of normal paraffins from hydrocarbon mixture
Kerosene Isoiv process For separation of straight chain normal paraffins from the kerosene
range (C10–C18) used for detergent industry

Pressure swing adsorption (PSA): It is based on the principle of relative adsorption strength,
and is a milestone in the science of gas separation (Shiv Kiran and Chakravarty, 2002).
Some of the commercial applications of PSA are air drying, hydrogen purification, bulk
separation of paraffins, air separation for oxygen and nitrogen production.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 43

Chromatography: It is a sorptive separation process. In chromatography feed is introduce

in column containing a selective adsorbent (stationary phase) and separated over
the length of the column by the action of a carrier fluid (mobile phase) that is conti­nually
supplied to the column following the introduction of the feed. The separation occurs as
a result of the different partitioning of the feed solutes between the stationary phase.
The separated solutes are recovered at different time in the effluent from the column
(Rangrajan, 2010).

Crystallization Process
Crystallization processes are used in the petroleum industry for separation of wax.
The process involves nucleation, growth, and agglomeration and gelling. Some of the
applications of crystallization is in the separation of wax, separation of p-xylene from
xylenes stream. Typical process of separation of p-xylene involves cooling the mixed
xylene feedstock to a slightly higher than that of eutectic followed by separation of
crystal by centrifugation or filtration.

Liquid–Liquid Extraction
Liquid–liquid extraction has been commonly used in petroleum and petrochemical
industry for separation of close boiling hydrocarbons. Some of the major applications are:
• Removal of sulfur compound from liquid hydrocarbons
• Recovery of aromatics from liquid hydrocarbon
• Separation of butadiene from C4 hydrocarbons
• Extraction of caprolactam
• Separation of homogeneous aqueous azeotropes
• Extraction of acetic acid
• Removal of phenolic compounds from waste water
• Manufacture of rare earths
• Separation of asphaltic compounds from oil
• Recovery of copper from leach liquor
• Extraction of glycerides from vegetable oil
Some of the important properties of good solvents are summarized below:
• High solvent power/capacity
• High selectivity for desired component
• Sufficient difference in boiling points of the solvent and the feed for effective
separation
• Low latent heat of evaporation a specific heat to reduce utility requirement
• High thermal a chemical stability
• Low melting point
• Relatively inexpensive
• Nontoxic and non-corrosive
• Low viscosity low interfacial tension.

Technological Development in Unit Operations

• Distillation, azeotropic, extractive distillation, reactive distillation, membrane
distillation
• Random packing to structured packing
44 Chemical Process Technology

• Single and two pass to multiple down comer

• Rasching rings and berl saddles to Intalox saddles, pall rings, nutter rings, half rings,
super rings, Fleximax
• Pan Park to wire gauge packing, Goodloe, Mellpark, Flexipack, Gempack, Intalox
• Fixed bed to Fluidized bed reactor
• Conventional reactor to microreactor
• Ball mill grinding to vertical roller mill and press roll mill
• Open circuit grinding to closed circuit grinding
• Batch digester to continuous digester
• Low speed and low-capacity chipper to high-speed chipper and high-capacity chipper
• Low speed paper machine to high-speed machine
• Drum displacer, pressure diffuser, displacement presses, combined deknotting and
fine screening,
• High temperature screening before washing, reverse cleaners
• Adsorption (Olex, Parex and Molex), crystallization and membrane separation
processes
• Solvent extraction processes and new solvents
• Conventional distillation short path distillation, divided wall column
• Conventional bubble cap, sieve plate to valve tray
• Random packing to structured packing
• Axial flow reactor to radial flow reactor
• Conventional instrumentation to smart (intelligent) instrumentation.

Nanotechnology and Biotechnology

Nanomaterials in chemical process industries are very important and rapidly
developing. The potential of nanomaterials in genetic engineering, catalysis, nanofluids,
nanobiotechnology are being explored extensively.
Biotechnology in chemical process industries is being used in various areas such
as biopuling, biobleaching, bioextraction, biodesulfurization, bio-fuels, biopolymers,
environmental engineering, etc.
Biorefinery is new concept emerging in petroleum refining industry. Industrial
biotechnology is real cross-sectorial technology providing a common basis to energy
carriers, bulk, specialty and fine chemicals as well as pharmaceuticals (Kircher,
2013). Chemical rngineers have important role in developing and utilization of
nanotechnology and biotechnolgy in chemical process industries. Fermentative
production is already playing an important role in many areas. Enzymatic catalysis
is also going to play an important role in future. Biorefinery is also going to play an
important role in future by utilizing biological raw materials especially alcohol, biodiesel,
furfural, etc. (Kamm, 2013).

BIBLIOGRAPHY
1. Austin GT. Shreve’s Chemical Process Industries, (5th ed.), McGraw Hill Publication, 1975.
2. Cook PJ, Losin MS. Membranes provide cost effective natural gas processing, Hydrocarbon
processing, April 1995, p.80.
3. Crittenden B. Selective adsorption, Chemical engineer, September, 1988, p.21.
Basic Principles of Chemical Processes and Unit Operations in Chemical Industries 45

4. Groggins PH. Unit processes in organic synthesis, Tata McGraw Hill Education Private Limited
(5th ed.) 1995.
5. Kamm B. “The LCF-Biorefinery” Chemical Industry Digest September 2013, p.62.
6. Keller II GE. Adsorption: building upon a solid foundation, Chemical engineering progress
October, 1995, p.56.
7. Kircher, M “Industrial biotechnology status and future trend”, Chemical Industry Digest, Sept.
2013, p.55.
8. Knaebel KS. For your next separation consider adsorption, Chemical Engineering November
1995, p.92.
9. Leveris A. The rebuilding of chemical engineers, Chemical News, April 2007, p.61.
10. Olujie Z, Kaibel B, Jansen H, Rietfort T, Zich E, Frey G. Distillation column internals/configurations
for process intensification”, Chem Biochem Eng Vol. 7, No. 4, 2003, 301–9.
11. Patil N, Patil VS. Chemical Industry Digest, April 2012, p.75.
12. Rangarajan S. Adsorption, Chemical Business, May 2010, p.33.
13. Shiv Kiran T, Chakravarty M. Pressure swing adsorption—principles, processes and application,
Chemical Engineering world, September 2002, p.98.
14. Spillman RW. Economics of gas separation membranes, Chemical engineering progress, January,
1989, p.41.
15. Sridhar S. Membrane technology in process intensification, Chemical Industry Digest, February
2009, p.62.
16. Stankiewicz AI, Moulijn JA. Process intensification: transforming chemical engineering. Chemical
Engineering Progress, Jan, 2000, p.22. Ziemlewski, J Cep February 2009, p.6.
17. Yaday GD. Is there any beauty, charm and challenge left in Chemical Engineering. Indian
Chemical Engineer, Vol No.1 January–March 2009, p.9.
18. Ziemlewski J. Designing the new global Chemical Engineer, Chemial Engg Progress (CEP)
February 2009.
3
Industrial Gases

3.1 INTRODUCTION
Industrial gases are considered to be those gases used in their pure form by industry,
medicinal industry in large quantities. According to Nasdaq research, industrial gases
in India is projected to cross $2 billion by 2020. Industrial gases are known as specialty
gases, fuel gases, medical gases and refrigerant gases. Growing demand from various
industries, such as metallurgy and petrochemical industries, healthcare sector, packaged
food, refrigeration industry, etc. are projected to grow in future and are the major
driving force of growth.
They are used as gases, liquids or cryogenic liquids. Fuel gases are those gases which
are used as fuel, e.g. producer gas, water gas, coke oven gas, natural gas. Synthesis gas:
Mixture of CO and H2 or H2 and N2. Industrial gases are finding application.
The industrial and medical gases industry serves a very large number of customers.
Industrial gases are essential for almost all manufacturing. Large quantities of oxygen,
nitrogen and argon are used in the steel and metal industry. Shipyards and the
automotive industries use acetylene, propane, mixtures of fuel gases and oxygen for
cutting and welding. Some of the important fuel gases are producer gas, water gas,
coke oven gas, LPG, etc.

3.2 PROFILE OF GLOBAL AND INDIAN GAS COMPANY

According to the Freedonia group, inc., a Cleveland-based industry research firm, world
demand for industrial gases is forecast to increase 6.9% annually to $36.8 billion in
2011, with volume exceeding 300 billion cubic meters (bcm). Asia/pacific is the largest
consuming region because of rapid growth in developing industrial markets, especially
those of China and India.
In India, there are presently over 300 small and medium sized plants and
approximately 25 large tonnage plants all over the country. These gases are supplied
through pipelines to captive customers in adjacent factories; in cryogenic transport tanks
for bulk deliveries to long distance customers; or filled in cylinders (http;//[Link].
org/projects/industrial-gases/z,39,0,64/[Link]).
Major players in India include BOC India, INOX Air Products Ltd., Jindal Praxair
Oxygen Co. Ltd., Air Liquid India Holding P. Ltd., Aims Industries Ltd., etc. The Indian
gas industry is growing at an average rate of 12% per annum during the last couple of
46
Industrial Gases 47

years, with the industrial oxygen growing consistently at 15–17% per annum. Natural
gas comprises 9% of India’s primary energy consumption and it will be 14% of energy
mix by 2010.
The present annual turnover of the gas industry, excluding captive production is
about ` 3,000 crore ($650 million). With increased industrialization, the demand pattern
of industrial gases is also changing fast. Modern application in the food processing
industry, agro industries, healthcare and technology are growing at a tremendous pace.
This has driven the industry to adopt stringent quality control systems and an efficient
distribution network.
Growth of liquified natural gas (LNG) trade has significantly contributed to the
increasing share of LNG in total global energy mix and decarbonisation of global energy
and to achieve low CO2 emissions (Mathew and Francics, 2020).

3.3 TYPES OF INDUSTRIAL GASES

The most common industrial gases are given in Table 3.1. Various types of natural gas
and refinery gases are given in Table 3.2. Heating value of these gases varies and is
given in Table 3.3.

Table 3.1: Common industrial gases

Air gases Oxygen (O2), nitrogen (N2), and argon (Ar)
Rare gases Helium (He), krypton (Kr), xenon (Xe) and neon (Ne)
Fuel gases and industrial gases as • Water gas, producer gases, town gases, natural and shale
chemical feedstock gas, LPG, Refinery gases, Coal bed methane
• Synthesis gases (CO + H2 and H2 + N2), Coke oven gases,
natural gas, shale gas, chlorine gas, CO and CO2, SO2, LPG
(methane, propane), acetylene, ethylene, propylene

Table 3.2: Natural gas and refinery gases

Sour natural gas Natural gas containing appreciable amount of hydrogen
sulfide and carbon dioxide
Natural gas condensate and natural Condensable hydrocarbon present in the natural gas having
gas liquid (NGL) heavy hydrocarbon. NGL are removed from natural gas by
cooling and the uncondensed gas is mainly methane.
Liquefied natural gas (LNG) LNG consists of mixture of methane, ethane, propane, small
amount of higher hydrocarbons and possibly nitrogen.
LNG is a natural gas cooled to –260ºF to a liquid which
occupies 1/600 the volume of gas. Transport is safe and is
at atmospheric pressure.
Compressed natural gas (CNG gas) Compressed natural gas is pressurized natural gas stored
at very high pressure 200 bar
Natural gas hydrates (NGHs) • Natural gas hydrates are ice like crystals composed of
water and natural gas and are characterized as the natural
gas trapped in cage like structure formed by ice.
• Natural gas hydrates can be considered modified ice
structure enclosing methane and other hydrocarbons,
but they can melt at temperatures well above normal ice.
Contd...
48 Chemical Process Technology

Table 3.2: Natural gas and refinery gases (Contd...)

• There are three types of methane hydrate structure. They
all include pentagonal dodecahedra of water molecules
enclosing methane.
Coal bed methane • Coal bed methane is a form of natural gas extracted from
coal beds and has become important source of energy all
over the world. CXBM is the methane adsorbed into solid
matrix of the coal.
• Unlike much natural from conventional reservoirs, coal
bed methane contains very little heavier hydrocarbons
such as propane or butane, and no natural gas condensate.
Porosity plays an important role in building up methane
gas reserves in the coal bed.
Liquefied petroleum gas (LPG) • LPG is domestic fuel and consist propane and butane.
LPG is used as domestic fuel and for the manufacture of
petrochemicals
• Industrial grade LPG (80% butane and 20% propane)
CV 29275% kcal/Nm3
• Domestic LPG: 70% butane and 30% propane) CV 25775%
kcal/Nm3
• At atmospheric pressure and temp. 1.5-pressure and
temp. heavier than air
Sources: Crude oil distillation, FCC, Catalytic Reforming, Hydro­
cracker and other thermal refinery processes
Refinery gases Gas obtained from during distillation, cracking and other
process in processes in Refinery containing methane, ethane,
propane and butane, olefins (ethylene, propylene and
butane), Hydrogen sulfide and Methane: 8–10%, Ethylene
and Ethane: 8–12%, Propane and Propylene 40–55% Butane
and Butene up to 30%, CV 20500 kcal/Nm3
Source: Mall ID. Petroleum Refining Technology”, CBS Publishers 2016.

Table 3.3: Gross heating value of some of the industrial fuel gases

Composition of air
Gases % by volume Boiling point (ºC)
Nitrogen 78.08 –196
Oxygen 20.95 –183
Argon 0.93 –186
Carbon monoxide 0.035 –78 (sublimation point)
Neon 0.00182 –246
Helium 0.00052 –269
Krypton 0.00011 –152
Xenon 0.00009 –108
Contd...
Industrial Gases 49

Table 3.3: Gross heating value of some of the industrial fuel gases (Contd...)
Composition of air
Gases % by volume Boiling point (ºC)
Hydrogen 0.00005 –25.3
Nitrous oxide 0.00005 –88
Water (H2O) Up to 4.0 100
Gross heating value
Kcal/m3 Kcal/kg
Acetylene 13,332 11,983
Blast furnace gas 818 654
Blue water gas NA 3,639
Carbon monoxide 2,875 2,427
Carburetted water gas 4,895 6,356
Coal gas 1,326 9,167
Coke oven gas 5,109 9,471
Digester gas 6,141 6,287
Natural gas 8,455 10,833

Carbon Monoxide
It is used in the manufacture of acetic acid, formic acid, polycarbonates, toluene
di-isocynate, methanol. Major source of CO is from synthasis gas. It is also obtained as
by-product during alcohol prodution (Table 3.4).

Table 3.4: Hydrogen, CO and synthesis gas consumer

Hydrogen Ammonia, anline, 1,4 butanediol, caprolactam, 2-ethylhexanol, hexamethylene
diamine, hydrogen peroxide, isononyl alcohol, toluene diamine, fuel cell, as fuel
Carbon monoxide Acetic acid, formic acid, polycarbonates, toluene di-isocynate, methanol
Synthesis gas Methanol, oxo alcohol

3.4 OXYGEN AND NITROGEN

Oxygen and nitrogen are two very important gas and are very crucial life supporting
substance (Patwarhan, 2017). Oxygen and nitrogen are very reactive nonmetallic
elements; however, industrially, the gases are very important for the manufacture of
various chemicals. Although these gases are available in abundant in nature but their
industrial production is very important for industrial uses and production of various
chemicals. Oxygen is not only life sustaingting element and is very important for
human and aquatic and marine life. Nitrogen in the form of ammonia is very important
part of fertilizer as urea, ammonium chloride ammonium nitrate, nitrophophate, and
diammonium phosphate. It is also very important in the manufacture of explosives,
caprolactam and large number of chemicals.
Oxygen and nitrogen produced either by liquefaction process and subsequent
fractionation of air or by pressure swing adsorption. Liquefaction is based on either by
Linder cycle or Joule Thomson cooling.
50 Chemical Process Technology

• Linde cycles: uses refrigeration by Joules Thomson cooling which involve expansion
of gas through a throttle valve. This is constant enthalpy process.
• Claude cycles: Refrigeration by adiabatic expansion of compressed air in a turbo-
reciprocating or rotating expansion machine to expand the gas. This is constant
entropy process.
Oxygen and Nitrogen by Pressure Swing adsorption: Oxygen and nitrogen can be produced
from air by pressure swing adsorption or liquefaction process.
Pressure Swing adsorption: The use of the pressure swing adsorption (PSA) process has
seen tremendous growth during the last decades mainly due to its simplicity and low
operating costs. Major applications have been the recovery of high purity hydrogen,
methane and carbon dioxide as well as the generation of nitrogen and oxygen (Linde).
Linde as the world leader in adsorption technology and supplied more than 500 PSA
plants. The A series comprises fully tailored nitrogen PSA generators, having high
capacity and purity range. The product purity for A-series Nitrogen purity (N2+Ar
97–99.99). Thew major advantage of Linde N2 PSA units are high purity nitrogen, low
nitrogen product cost, higher reliability, easy turn down, fully automatic operation,
and easy maintenance.

Pressurization/Adsorption vs Depressurization/Desorption
• The separation of nitrogen and oxygen from air takes place in an adsorber vessel
filled with carbon molecular sieve.
• This is based on the fact of faster kinetic diffusion of oxygen molecules into the pore
structure of the carbon molecular sieve than for nitrogen molecules.
Compressed air alternately pressurizes each of two identical adsorber beds.
Beginning at a point in the cycle where one adsorber bed (A) is being pressurized
and the other adsorber bed (B) is undergoing depressurization. Process flow diagram
for the production of oxygen and nitrogen by pressure swing adsorption is given in
Figure 3.1.

Fig. 3.1: Oxygen and nitrogen by pressure swing adsorption

Membrane Process: Based on the principle of differential velocity with which the various
gas mixtures components permeate the membrane. The driving force in the gas
separation process is the difference in partial pressures on different membrane sides.
Industrial Gases 51

Oxygen and Nitrogen Production by Liquefaction Process

Conventional Linde Frankl Cycle Process: Uses regenerative exchangers where product
stream and incoming impurities CO2 and H2O air come in contact.
Low Purity Oxygen and Nitrogen
Kellogg process: It uses recuperative-reversing heat exchanger. These are built in a
concentric triple-tube design with high purity oxygen moving the inner tube, never
contacting the incoming air. The reversing system is used to remove CO2 and H2O from
the incoming air stream by switching the flow of oxygen and nitrogen.
High Purity Oxygen and Nitrogen
Oxygen and nitrogen were produced by air fractionation at low temperature; however,
with development of pressure swing, adsorption it is possible to produced oxygen and
nitrogen by PSA at even lower capacity.
Air Separation Unit
Product: Oxygen, Nitrogen, Air Argon
Air which is mixture of oxygen, nitrogen, argon and rare gases are separated at low
temperature by use of low temperature distillation. Air contains impurities like dust,
water, carbon dioxide and hydrocarbons which are removed to ensure safe and efficient
operation.
Process steps involved in production of oxygen and nitrogen by air fractionation
process are:
• Compression of air by multistage compressing having intercooler
• Cooling and purification filtration for removal of foreign material, CO, water vapor
and hydrocarbon if any, by molecular sieve adsorbers
• Low temperature heat exchange and cooling to liquid temperature by means of
nitorgen
• Separation into oxygen, nitrogen, argon by low temperature distillation
• Rewarming of separated components.
Process flow diagram is given in Figure 3.1.
Air separation: Compressed air after cooling to 20ºC enters a set of reversing heat
exchanger where air is cooled by outgoing product nitrogen and oxygen. Carbon oxide
and moisture are also removed consequently from the air during cooling process.
Compressed air leaves the cold end of reversing heat exchanger slightly above its dew
point.
Cooled air from the reversing heat exchanger is fed in to the bottom of medium
pressure column containing number of trays. Air is bubbled through a rich liquid at the
bottom of column. Air streams become poorer in oxygen by contact with descending
flow of liquid stream on the trays. Pure nitrogen is produced from the medium pressure
column.
Rich liquid containing 40% oxygen from the bottom of the high pressure column
is passed through expansion valve to low pressure column. Pure oxygen is produced
after fractionation in the low pressure column. Pure oxygen from the bottom of the
low-pressure column send to oxygen turbo compressor through reversing heat
exchanger. Waste nitrogen coming from top of the L>P column goes to atmosphere via
subcooler, reversing heat exchanger.
52 Chemical Process Technology

Medium pressure nitrogen is used in the expansion turbine after passing through
cold section of reversing heat exchanger as low pressure nitrogen.
Argon separation: Argon having purity of about 97% is separated from the top of the
crude argon column.

3.5 METHANE AND SYNTHESIS GAS DERIVATIVES

Methane and synthesis gas are important petrochemical feedstock for manufacture of
large number of chemicals, which are used directly or as intermediates, number of which
are finding use in plastic, synthetic fiber, rubber, pharmaceutical and other industries.
‘Synthesis gas’ is commonly used to describe two basic gas mixtures—synthesis gas
containing CO and hydrogen, and synthesis gas containing hydrogen and nitrogen for
production of ammonia.
Petrochemical derivatives based on synthesis gas and carbon monoxide have
experienced steady growth due to large scale utilization of methanol and development
of carbonylation process for acetic acid and oxo synthesis process for detergents,
plasticizers, and alcohols.
Synthesis gas and carbon monoxide have experienced steady growth due to large
scale utilization of methanol and development of carbonylation process for acetic acid
and oxo synthesis process for detergents, plasticizers, and alcohols.
Various raw materials for synthesis gas production are natural gas, refinery gases,
naphtha, fuel oil/residual heavy hydrocarbons and coal. Although coal was earlier
used for production of synthesis gas, it has now been replaced by petroleum fractions
and natural gas. Petrocoke is the emerging source for synthesis gas. Coal is getting
importance alone or with combination of petroleum.
Detail of production of synthesis gas is discussed in Chapter 7.

3.6 HYDROGEN

Hydrogen is the most abundant and lightest element in the universe (Chemical Industry
Digest vol. 30, October 2017) and has wide application in chemical process industry,
i.e. aviation fuel, rocket fuel, hydrogen bomb. It is also used in the manufacture
of ammonia, anline, 1,4 butanediol, caprolactam, 2-ethylhexanol, hexamethylene
diamine, hydrogen peroxide, isononyl alcohol, toluene diamine, fuel cell, as fuel.
Hydrgen is going to be bridge between renewable energy and fossil fuels. Hydrogen is
alternate fuel to meet the energy needs of industry, transport, and residential buildings
(Sonde, 2020).

Raw Material
Major raw materials for production of hydrogen are water, natural gas, naphtha and
coal. Although hydrogen was available since 1671, in 1800, Nicholson and Crustal
followed by Ritter succeeded in decomposing water in to hydrogen and oxygen gas
(Patwardhan, 2017). This method was stared earlier by nangal fertilizer unit of National
Fertilizer. With rising cost of electricity, the electrolysis technology is not being used
at industrial scale. Production of hydrogen from electrolysis of water using catalyst is
again getting importance.
Industrial Gases 53

Hydrogen Producing Technology

• Thermal
• Electrochemical
• Biological

Hydrogen Separation Processes

• Adsorption
• Membrane
• Cryogenic

Electrolysis of Water
• The splitting of water is accomplished by passing a DC electric current through
water.
• The electricity enters the water at the cathode, a negatively charged terminal, passes
through the water and exists via the anode, the positively charged terminal.
• The hydrogen is collected at the cathode and the oxygen is collected at the anode.
Electrolysis produces very pure hydrogen for use in the electronics, pharmaceutical
and food industries.

Photobiological
• This method involves using sunlight, a biological component, catalysts and an
engineered system.
• Specific organisms, algae and bacteria, produce hydrogen as a byproduct of their
metabolic processes.
• These organisms generally live in water and therefore are biologically splitting the
water into its component elements.
• Currently, this technology is still in the research and development stage and the
theoretical sunlight conversion efficiencies have been estimated up to 24%.

Hydrogen from Steam reforming and Partial oxidation, catalytic reforming, by gasification:
Hydrogen is produced in chemical industries, synthesis gas and hydrogen are
produced either by steam reforming of natural gas/naphtha or partial oxidation of
Fuel oil, Petro coke. Details of the steam reforming and partial oxidation is given in
Chapter 7. Hydrogen produced in different refinery processes; catalytic reforming is
one of the major sources. The amount of hydrogen rich gas produced depends on feed
composition and process conditions in the reactor section (Polovina, 2014). The purity
of gas is around 73–75%. Gas is further purifying to 99.99% by absorption followed
by pressure swing adsorption. Hydrogen gas in refinery and petrochemical is used in
hydrotreating, hydrocracking, catalytic reforming, and isomerization.
In petroleum industry, hydrogen is conventionally produced by steam reforming
of naphtha; however, because of availability of large amount of coke from refineries
due to use of heavier crude. Integrating the gasification of liquid residue into a refinery
balances the hydrogen demand for various processes using hydrogen. Now some of the
refineries, petrochemical complexes and fertilizer industry are producing or planned
for gasification process for production of synthesis gas and hydrogen. Various process
54 Chemical Process Technology

used for gasification are Lurgi Fixed bed technology, Kopper-Totzek and Texaco process
(entrained bed) and Winkler process using fluidized bed reactor.
Honey well technology used for hydrogen plant at CNPC Guangxi Petrochemical
Company in China. This is based on PSA and will produce 99.9% purity of hydrogen
and with increased hydrogen recovery (Patwardhan, 2017).
Small Hydrogen generation Plants: Many manufacturing processes require hydrogen gas in
small quantities with high purity. Modular hydrogen plant with capacity 300–16,500 m3/
hr from Linde Engg India using large variety of feedstocks like natural gas, methanol,
LPG and naphtha (Jell and Mamtani, 2012).
Uses of Hydrogen: Hydrogen is a versatile and clean fuel (Sonde, 2020). Hydrogen has
wide application in chemical process industry, aviation fuel, rocket fuel, hydrogen
bomb. Hydrogen is the highly reactive and is commonly used as reducing agent.
Some of the major uses of hydrogen are as intermediate feedstock in the manufacture
of large chemical, in hydrogenation reaction, for hydrogenation of unsaturated fats
and oil. Hydrogen has gained importance as fuel and in fuel cell. Hydrogen is used
in huge amount for the manufacture of ammonia. Hydrogen is used in refinery
and petrochemical industry in various process. However, its use has increased
in the refinery due to increasing use of hydrotreatment, hydrocracking, catalytic
reforming process, and isomerization. Hydrogen can be used as industrial fuel and
for generating electricity using fuel cell or microturbines. Hydrogen fueled mobility
is one of the most important emerging options because of its lowest CO2 emitting
system (Sonde, 2020).

3.7 ACETYLENE (C2H2)

Significant role in the metal industry for cutting and welding. Acetylene is one of the
most versatile chemical which was used as a chemical feedstock for the manufacture
of large number of chemicals which are used to manufacture wide range of products
including plastic, synthetic rubber, dyestuffs, solvents, pharmaceuticals and carbon
black. Acetylene is the only organic building block which can be derived from inorganic
raw material—lime, coal, and water. With coming of cracker plant now acetylene
as raw material for production of petrochemical has been replaced by ethylene and
propylene. Oxyacetylene-blown torch is widely used in welding and cutting metals.
It can be produced in small quantity from calcium carbide for many welding works.
Acetylene is commonly made by reaction of calcium carbide with water.
CaC2 + 2H2O C2H2 + Ca (OH)2

However, the above process is now replaced with electric arc process or parial
combustion of natural gas for large scale production.
Acetylene is also made from methane by electric arc furnace where energy requirement
is very large.
2CH4 C2H2 + 3H2

Acytelene can be also produced from partial oxidation of natural gas.

During cracking of ethane and propane acetylene is also obtained as by product and
some of the gas based plants in India is recovering acetylene.
Industrial Gases 55

3.8 CARBON DIOXIDE

Research efforts are going on for sequestration of CO2 and utilize it as useful feedstock.
At present, the emissions of CO2 are 24 billion tons, and it will reach 57 billion tons
in 2050. Developing CO2 to produce chemicals has good potential (presently only 120
million tons only utilized for production of chemicals) due to relative abundance,
renewable nature, low cost and can lower global warming.
Conversion of CO2 into various industrial products involves application of an
appropriate catalyst system that promotes reaction rates, directs the selectivity path way
and minimizes the energy of the reaction. Synthesis of urea, soda ash, as blowing agent,
supercritical extraction fluid, as cryogenic fluid, carbonation of soft drinks for recycling
of waters from acid mines drainage, as cooling media, making calcium carbonate, fire
extinguisher, cyclic carbonates for polycarbonate, electrolytes in lithium ion batteries,
green solvent, copolymerization of CO2 and epoxide aliphatic polycarbonate, acetic
acid and large number of chemicals from catalytic hydrogenative, photochemical,
electrochemical process, photochemical, catalytic nonhydrogenative. Some of the
important CO2 derivatives are:
• Acetic acid
• Synthesis of formic acid , carbamate synthesis
• As soft oxidant: selective oxidation of ethyl benzene
• Production of synthesis gas from CO2 reforming
• Methanol synthesis
• Catalytic nonhydrogenative process: Lactone, dimethyl carbonates, salicylic acid,
formaldehyde, polycarbonates, cyclic carbonate, ethylbenzene and alkanes.
Argon
Argon is produced from air fractionation process where is preset as less than one percent
in atmosphere. Measure uses of argon are in steel, stainless steel production, welding
shielding gases, in light bulbs, fluorescent tubes, fiber optics and some lasers. Because
of its highly unreactive nature like nitrogen it is used a protective blanket to prevent
substances from oxidizing. Argon is also commonly use as carrier gas in research and
laboratory operation due to its inert nature.
Noble (or rare) gases (Helium, neon, krypton, xenon): These gases are present in very small
quantity less than two thousandths of one percent of air.
Helium is one of the most abundant elements in the universe. Apart from air where
it is present in very small quantity, it occurs on earth in presence of natural gas. Helium
is recovered from natural gas also. It is very inert having low boiling point. It is very
inert and is used for helium-based shielding gases in welding application. It is also used
for medicinal and research purposes in many specialized instruments.
The main uses of neon are in lighting, display signals and electronics tubes. Krypton
is used in eximer lasers, particulary in surgery. Xeon is used in lighting application. It
is also used in the field of medicine.
Producer gas and water gas (Blue gas): Producer gas is produced by passing air and steam
through bed of coal or coke. Earlier many plants were using producer gas, however
due low heating value and high energy consumption of energy now producer gas is
not being used by many of the industry due to high heat value gases.
56 Chemical Process Technology

Water gas is also called blue gases because color of the flame is blue and has low
heating value.
Coke oven gas: During process of coke production by coal carbonization, coke oven
gas is produced as by-product which is purified for separation of ammonia. Coke
oven gases are largely used as fuel in steel plant. Ammonia and sulfur gases in
coke oven gases are used for fertilizer manufacture in the steel plants.

BIBLIOGRAPHY
1. http;//[Link]/projects/industrial-gases/z,39,0,64/[Link]
2. Austin George T. Shreve’s chemical process technology. McGraw-Hill International edition
(5th ed.) 1984.
3. Expirit Associates. Uses of industrial gases Gases and intermediates. [Link]
4. Jell A, Mamtani M. Small Hydrogeneration Plants, Chemical Industry Digest, May 2012, p.55.
5. Mathew T, Francis A. LNG markets-A Global Perspective and future outlook. Chemical Industry
Digest Annual January 2020, p.56.
6. Patwardhan V. Chemical Industry Digest, July 2017, p.32.
7. Patwardhan V. Chemical Industry Digest, September 2017, p.11.
8. Patwardhan V. Chemical Industry Digest, December 2017 p.29.
9. Sonde RS. Hydrogen: Bridge between reneable energy and fossil Fuels. HFC-Hydrogen fuel cells
for stationary and mobility applications. Chemical Industry Digest Annual January 2020.
10. Veena Patwardhan. Chemical Industry Digest vol 30, October 2017.
11. Weiss Mac-michale, Heuric H, Roma D, Walter S. Gasification for hydrogen supply, PTQ 2013
p.91.
4
Chlor-caustic and
Soda Ash Industry

4.1 INTRODUCTION
The chlor-alkali industry is a very important part of the world of the chemical industry.
India is one of the major players in the chlor-alkali sector. It produces producing
three important chemicals namely caustic soda, soda ash and chlorine which find
wide application in manufacture of a large number of compounds which have
downstream applications in paper, textiles, aluminum, soaps and detergents, PVC,
chlorinated organics, pesticides, etc. Large quantities of gaseous, liquid and solid
pollutants are generated by the caustic soda industry. The chlor-caustic industry is
amongst the top highly polluting industries. Due to increasing public concern and
awareness, pressure on chlor-caustic industry for better environmental management
is expected to increase in the upcoming years. Elemental chlorine was discovered only
in the late 18th century (Patwardhan, 2018). The use of chlorine in many chlorine-based
industries is on downtrend. Several environmental protection laws and acts have been
enforced in India. Although some of the industries are already in process of phasing
out use of chlorine in the processes, e.g. CFCs manufacture and chlorine bleaching,
chlorine and its various compounds is finding application in disinfection and sanitation
and find application of large number of chemicals which are finding many industrial
applications. The chlor-alkali industry witness increased environmental regulatory
pressures due to toxicity of mercury, chlorine, hydrochloric acid, etc. The good news,
however, is that the industry is alive to the environment concerns. Polluting wastes and
effluents like mercury, gases like hydrogen, carbon monoxide, chlorine, etc. are now
being regulated to conform to limits as required by environment protection laws. But
the industry will have to conform to more stringent regulations in the near future. Out
of the chlor-alkali units in India, still some plants are based on mercury cell process,
while now lage number of plants have now changed membrane cell process, only one
is based on diaphragm cell process.
Chlor-alkali is an industrial process widely used to produce chlorine, caustic soda
and other chlorine and sodium derived/based products, such as sodium hypochlorite,
calcium hypochlorite, bleach liquor, chlorosulfonic acid, chlorine dioxide, hydrogen
gas, bleaching powder, polyaluminum chloride, chlorinated paraffins, PVC, chlor-
alkali with its three products caustic soda, soda ash, and chlorine form basis of the end
user. For every one ton of chlorine 1.1 ton of caustic soda is produced. This is a major
challenge for effective utilization of caustic soda and chlorine (Chemical Digest Annual
Jan 2018 p.103).
57
58 Chemical Process Technology

4.2 PROFILE OF CHLOR-ALKALI INDUSTRY (GUJARAT)

The present global capacity of caustic soda is estimated at 94 million MTPA
while India’s capacity is only 3.66 million tons, i.e. mere 3.9% of the world capacity
(Chemical Industry Digest Annual Jan 2018). There are 37 manufacturing units of
caustic soda and chlorine having installed capacity of about 3.246 million tons caustic
soda. Chlorine production is in the ratio of 1:0.89. Today 95% plants are running on
membrane cell technology which are energy efficient and environmentally friendly.
Rest 5% are based on mercury cell process which will be shifting to membrane cell
process. Gujarat is the largest producer. Caustic soda industry is highly energy
consuming process and consumes 2.5 MW per metric ton of caustic soda. Demands
for alumina, paper, textiles are major drivers for caustic which consumes 60% of total
demand of caustic soda. As growth of these industries is growing fast, consumption
of caustic soda will be also increased. Installed capacity, production and capacity
utilization of caustic soda units are given in Table 4.1. Major consuming sectors of
chlorine are vinyl chloride, chlorinated paraffin wax, pulp and paper and chemicals.
The production scenario of caustic chlorine in India is given in Tables 4.2 and 4.3.
India has more than adequate capacity to meet the domestic demand of both caustic
soda and chlorine (Indian Chemical Industry XIIth Five-year plan 2012–17) (Table
4.4). The major raw material for caustic chlorine is salt which is obtained mainly from
sea water and India has adequate volumes of this resource. Chlorine which is the
main byproduct, demand of which is not well developed in India unlike the global
chlorine market.

Table 4.1: Capacity, production and capacity utilization of caustic soda units
Year Installed capacity Production Capacity utilization (%)
2013–14 3,308.7 2,618.3 79.1
2014–15 3,390.0 2,761.8 81.5
2015–16 3,370 2,871.0 85.2
2016–17 3,661.9 3,022.5 82.5
Source: Chemical Industry Digest Annual Jan. 2018, p.104.

Table 4.2: India’s caustic consumption industry wise

Industry Percentage
Textile 13.7
Pulp and paper 11.2
Alumina 10.2
Organics 7.7
Soap and detergent 6.5
Inorganics 6.0
Pesticides 5.2
Pharma 4.2
Others 35.2
Source: Indian Chemical Industry, XIIth Five-year plan 2012–17.
Chlor-caustic and Soda Ash Industry 59

Table 4.3: Production scenario of caustic and chlorine in India (thousand tons)
Year Installed capacity Production of caustic soda Production of chlorine
2006–2007 2,547.8 1,993.1 1,765.9
2007–2008 2,741.8 2,160.3 1,914.0
2008–2009 2,923.0 2,198.8 1,948.1
2009–2010 3,202.4 2,326.0 2,060.6
2010–2011 3,246.3 2,457.6 2,177.4
Source: Indian Chemical Industry, XIIth Five-year plan 2012–17.

Table 4.4: Per capita consumption of chlorine

Country Per capita consumption of chlorine in kg
Germany 55
USA 45
Japan 29
France 23
China 13
Brazil 7.80
India 1.85

Major global caustic soda and chlorine players: Dow Chemicals (US), Occidental Chemical
Corporation (USA), Bayers AG (Germany), PPG Industries (US), Tata Chemicals, Ltd.,
Shin Eisu Chemical Co. (Japan), Formosa Plastics Corp (Taiwan), Solvay Chemicals
(Belgium), Ineos Chlor Limited, (UK) FMC, Corp., Shandong Halhua Group (China),
Clech SA (Poland).
Status of Indian chlor-alkali industry as on 31.03.2013 is given in Table 4.5.

Table 4.5: Status of Indian chlor-alkali industry as on 31.03.2013

No. of chlor-alkali units in India—34
Total operating capacity of caustic soda— 31.34 lakh MTPA
Expected caustic soda capacity by March 2015— 34.5 lakh MTPA
During the year 2012–13
Caustic soda production— 25.4 lakh MTPA
Caustic soda demand— 28.1 lakh MTPA
Caustic soda capacity utilization— 81%
Caustic soda demand CAGR during last five years—4.98%
Chlorine production— 22.5 lakh MTPA
Chlorine demand— 22.5 lakh MTPA
Chlorine demand CAGR during last five years—3.67%
India has sufficient caustic soda capacity to meet increasing demand of the country; Due to dumping
of cheap caustic soda in India by other countries capacity utilization is low.
Source: Gilra, 2013.
60 Chemical Process Technology

4.3 ISSUES AND CHALLENGES BEFORE CHLOR-CAUSTIC INDUSTRY

Some of the major issues and challenges before chlor-caustic industry are:
• Increasing price of energy.
• Lack of integrated plants, and downstream chlorine utilization projects.
• Poor infrastructure and high transportation costs.
• Inadequate opportunity for chlorine utilization; PVC, isocyanides, etc.
• Industry not fully developed.
• Long distance transportation of chlorine due to non-integrated plants.
• Increasing regulatory standards and compliances.
• Reducing energy input cost and making operations much more energy efficient
process.
• Increasing salt prices and transportation costs.
• Achieving zero effluent discharge and effective water management.

4.4 SEA WATER

Sea water is rich source of large number of minerals. Six most abundant ions of sea
water are chloride, sodium, sulfate, magnesium, potassium, calcium, bromine. The
amount of these salts varies. Apart from above constituents sea water contain large
number of precious elements.

4.5 COMMON SALT

Common salt is one of the major raw materials for caustic chlorine apart from its use
as edible purpose (Table 4.6).
Per capita
Consumption of salt
India 14 kg
USA 180 kg
UK 135 kg
Japan 65 kg
Presence of iodine in common salt
10 mg/kg of salt.
Prevents endemic goiter (morbid enlargement of thyroid gland).
Main sources of salt and their availability
• Sea water: Sea salt 90% of total production containing 241,900 km3 of salt
• Lake water, Subsoil brine: 9.07%
• Rock salt: 0.017%
Sea water: Vast coastal line of about 5600 km including states of Maharashtra, Gujarat,
Tamil Nadu, Kerala, Andhra Pradesh, Karnataka, Orissa, West Bengal.
Salt lakes: Sambhar lake in Rajasthan, Chilka lake in Odisha.

Subsoil water: Dhrangadhru, Didwanu, Pachbadra, Tuticorin, Kharagodu.

Rock salt: Mandi mines in Himachal Pradesh.

Chlor-caustic and Soda Ash Industry 61

Table 4.6: World salt demand (million metric tons)

Annual growth (%)
Item
2005 2010 2015 2005–2010 2010–2015
World salt demand 245.0 283.5 327.0 3.0 2.9
North America 65.8 67.4 71.5 0.5 1.2
Western Europe 44.0 44.0 43.1 – –0.4
Asia/Pacific 88.7 118.0 152.0 5.9 5.2
Central and South America 10.8 12.3 13.6 2.6 2.1
Eastern Europe 24.5 28.0 30.8 2.7 1.9
Africa/Mideast 11.2 13.9 16.1 4.4 2.9
Source: Chemical Industry Digest July 2012, p.30.

4.5.1 Processes for Salt Manufacture

Various methods used for production of salt are:
• Solar evaporation (for sea water and lake)
• Artificial (open pan evaporation), vacuum evaporation
• Mining of rock salt either by dry or saturated brine by injecting water
• Freezing of sea water.
Solar evaporation of sea water is the major source of salt, although some salt is also
manufactured by solar evaporation of lake water which is rich in NaCl content.

4.5.2 Factors Affecting Solar Evaporation

Various factors affecting solar evaporation are temperature of air, pressure, direction
and velocity of wind, relative humidity.

4.5.3 Causes Which Influence the Rate of Evaporation of Water from

Open Surfaces
Various factors which influence the rate of evaporation from open surfaces are
temperature of liquid surface, the quantity of water vapor in the surrounding atmos­
phere, renewal of this atmosphere extent of the surface evaporation.

4.5.4 Design Consideration of Solar Salt Works

Various design consideration for locating solar salt works are proximity to sea,
topography of land, quality of soil, safeguard against floods, surface of exposure, initial
density of brine.

4.5.5 Sea Chemicals

Sea is rich source of many chemicals apart from salt. Sea contains about 35 parts per
1000 (3.5%) dissolved salt. Some of the important minerals are also present in the sea
sand. Composition of sea water varies widely and is influenced by a wide variety of
chemical transport. Recovery of minerals from sea water and sand present big challenge.
It offers enormous scope for chemical process industries and Chemical engineering
which involves a large number of unit processes and unit operations. Around
60 elements are found in sea water. Some of the important minerals present in sea water
are given in Table 4.7.
62 Chemical Process Technology

Table: 4.7 Important minerals found in sea water

Elements Concentration (ppm) Elements Concentration (ppm)
Chlorine 19000 Strontium 8
Sodium 10500 Boron 4.6
Magnesium 1350 Lithium 0.17
Sulfur 885 Iodine 0.06
Calcium 400 Titanium 0.001
Potassium 380 Uranium 0.003
Bromine 65
Source: Seetharaman and Srinivasan, 1978; Gopala Rao, Sitting M, 1997; Cruickshank, 2006.

About 30% of the salt produced throughout world is from sea water. Salt itself is
source of large number of chemicals like caustic soda, soda ash, hydrochloric acid
magnesium compounds. Apart from salt, bromine and potassium recovery is also very
important activity. Presence of large number of important minerals from sea floor is also
going to open new opening for chemical engineers. Much of the world magnesium is
recovered from sea water. Large quantities of bromine is also recovered from sea water
([Link] Bcheckedd/topic/531121/sea water). Magnesium
ion is the third abundant element present sea water. Magnesium is produced from sea
water. After separation of salt by evaporation and crystallization the mother liquor is
called britten which is source of many chemicals.
Sea water has normally 4.176 mg/L of MgCl2 and 0.076 g/L of MBr2 (Gopala Rao,
Sitting, 1997). Magnesium compounds are manufactured from sea water using lime.
MgCl2 + Ca(OH)2 Mg(OH)2 +CaCl2

MgSO4 + Ca(OH)2 +H2O Mg(OH)2 + CaSO4 2H2O

Potassium from sea water is recovered from sea bitterns by fractional crystallization
in the form of caranallite (KCl.MgCl2.6H2O) from which potassium can be recovered.
Bromine recovery from sea water is by vaporizing of chlorinated water and then by
passing SO2.
– –
Cl2 +2Br 2Cl = Br2

SO2 + Br2 + H2O 2HBR +H2SO2

2HBr + Cl2 2HCl + Br2

Oil and gas exploration and drilling in ocean for oil and gas has already find attention
of chemical engineers, geologists and geophysists. Gas hydrate is rich source of methane.
Gas hydrates which are ice like substance composed of water and natural gas are already
getting importance in oil and gas sector. Gas hydrates are present in ocean sediments.
One cubic meter of gas hydrates yield about 160 m3 of methane (Cruickshank, 2006)
and may be potential source of energy and petrochemicals. Sea water is also providing
water through reverse osmosis for drinking purposes and chemical and petroleum,
petrochemical industry.
Sea/ocean beaches contains many precious minerals like platinum, gold, diamonds,
limonite, magnetite, zircon, rutile, columbite, chromite, quartz, etc.
Chlor-caustic and Soda Ash Industry 63

4.6 COMMON TERMS USED IN ELECTROLYTIC PROCESS

Energy consumed: Current flowing × Potential of the cell
Gibbs–Helmholtz Equation
JDH dE
E=– +T
nF dt
E = Theoretical decomposition voltage
DH = Enthalpy change of reaction for 1 g equivalent of product
J = Electrical equivalent of heat
T = Absolute temperature ºK
F = Faraday’s constant
n = Number of equivalent involved
NaCl + H2O → NaOH + 1
2 H2 + 1
2 Cl2

Na(s) + 1
2 Cl2(g) → NaCl aq. DH = 407 kJ

H2(g) + 1
2 O2(g) → H2O (l) DH = 286 kJ

Na(s) + 1
2 O2(g) + 1
2 H2 (g) → NaOH DH = 469 kJ

Net DH for overall reaction

407 + 286 – 469 = 224 kJ
dE
Neglecting T, E = 2.31 V
dt

Decomposition voltage
Voltage efficiency = 60–75%
Operating voltage
9650ºC of electricity produce 1 g equivalent product
1 amp h = 3600 Coulomb
Theoretical current
Current efficiency = 95–97%
Actual current
Current density = Current per unit area amp/cm2
Energy efficiency = Voltage efficiency × Current efficiency
Equivalent produced
Decomposition efficiency = 60–75%
Equivalent charged

4.7 CHLOR-CAUSTIC PRODUCTION

Various processes used for production of caustic and chlorine are:
• Mercury cell process (MRCP)
• Diaphragm process (DCP)
• Membrane cell process (MBCP)
During the manufacture of caustic and chlorine various major steps involved in
various processes are:
• Brine purification
64 Chemical Process Technology

• Electrolysis of brine by diaphragm cell, mercury cell or membrane process

• Chlorine processing
• Hydrogen processing
IS specification of salt for industrial purpose is given in Table 4.8.

Table 4.8: IS specification of salt for industrial purpose

NaCl 98% maximum
SO4 0.50% maximum
Ca 0.20% maximum
Mg 0.20% maximum
Na2CO3 0.60% maximum
Insoluble 0.50% maximum

4.7.1 Brine Purification

Brine purification is the integral part of various cell processes. However, in case of
membrane process additional dechlorination process is added because of sensitivity
of chlorine toward membrane. In case of membrane process for brine purification two
steps are involved, which consist of primary and secondary treatment of brine solution.
Waste brine mud obtained from brine purification has been one of the major sources
of mercury cell process (Fig. 4.1).
Requirement of treated brine
NaCl 310–315 g/L, SO4 1.5–2.0 g/L, Ca <3 mg/L, Mg <1 mg/L, pH 7.2–7.4, Temperature
48–50ºC.
Objective of purification
• To make pure caustic
• To avoid clogging of cell diaphragm with consequent voltage increase
• To avoid formation of Ca and Mg amalgams with subsequent loss of mercury
• To avoid sludge formation which results in loss of brine, higher pollution.
• For better cell operation.
Basic requirement of salt purification
Reduction in calcium salt, magnesium salt and sulfate content
Chemicals required for purification
• BaCl2 or barium carbonate for precipitation of sulfate
• Soda ash: For removing calcium.
• Caustic coda: For removing magnesium
• Lime: For controlling sulfate content.
Steps in salt purification
Various steps involved in salt purification are:
• Addition of BaCO3 to remove sulfate slight excess of BaCO3, retention time 1 hour.
• Addition of Na2CO3 to remove the remaining calcium slight excess of Na2CO3,
1 hour retention.
• Addition of NaOH or lime to remove magnesium.
Chlor-caustic and Soda Ash Industry 65

Raw material (per ton of caustic)

NaCl 1.8–2.2 T
Power 2800–3800 kWh
Soda ash, barium carbonate, lime, HCl, mercury graphite

Fig. 4.1: Process flow diagram for brine purification

4.7.2 Diaphragm Cell

In electrolytic cell process graphite is used as anode and the purified sodium chloride
solution is fed to the anodes chamber and percolates through to the cathode chamber.
During electrolysis Na ions migrate to the cathode chamber and react with molecules
to produce hydrogen and caustic soda. As caustic soda obtained from diaphragm cell
process of lower concentration about 12%. It is further evaporated to get caustic lye of
higher concentration (Fig. 4.2).

Fig. 4.2: Caustic-chlorine by diaphragm process

Overall reaction: NaCl + H2O → NaOH + 1

2 H2 + 1
2 Cl2
66 Chemical Process Technology

Operating voltage: 3.4–3.8 V

Anode: Graphite
Cathode: Steel wire netting
–
Anode reaction: Cl → 1
2 Cl2 + e
+
Cathode reaction: H + e → 1
2 H2

NaCl + H2O → NaOH + 1

2 H2 + 1
2 Cl2
–
Side reactions: 4OH → 2H2O + O2 + 4e
–
4OH + e → 2H2O + CO2 + 4e
– –
Cl2 + OH → HOCl + Cl
–
3ClO → ClO3 + 2Cl
– –
OH ions are about 2½ times faster than Cl ions.
These reactions contaminate the product, lowers the process efficiency and thus
results in disintegration of graphite anode, increase cell resistance.
Clogging of diaphragm results in higher voltage drop, higher hydrostatic pressure.
Secondary reactions occur when
• Concentration of brine is low.
• Temperature is low.
• pH is high.
• Electrolyte is stationary and undisturbed.
Evaporation of caustic from diaphragm cell: Caustic produced from diaphragm cell
process is of low concentration about 12% and it is to be concentrated to 50% caustic
soda generally called caustic lye which may be further concentrated in evaporator and
further concentrated for making caustic flakes.
Concentration of Caustic from diaphragm process: Caustic produced from diaphragm cell
process is of low concentration about 12% and it is to be concentrated to 50% caustic
soda generally called caustic lye which may be further concentrated in evapo­rator and
further concentrated for making caustic flakes.
Various steps involved in evaporation and concentration of caustic soda is given in
Figure 4.3.

Fig. 4.3: Evaporation and concentration of caustic soda

Chlor-caustic and Soda Ash Industry 67

4.7.3 Mercury Cell

Mercury cell process was later developed to have caustic soda of higher concentration
and high purity. However, it was phased out later because of environmental pollution
problem due to mercury and many of the countries have installed membrane cell process
for the production of caustic chlorine replacing the mercury cell process.
A typical mercury cell unit consists of:
• Brine house for
• Cell house
• HCL
• Liquid chlorine
Typical composition of salt used in a chlor-caustic plant are:
NaCl 97–98.5%, Ca 0.1–0.25%, Mg 0.1–0.5%, sulfate 0.2–0.75
Typical characteristics of mercury cell process is given in Table 4.9.

Table 4.9: Typical characteristics of mercury cell

Anode area 13.9 m2
Cathode dimensions 12 × 1.15 m2
Slope 180 mm
Rated current 108 KA
Current density 7.91 KA/m2
Cell voltage 3.18 V
Number of anodes per cell 24
Spacing between cathode and anode 2 mm

Characteristic of charged brine

• Specific gravity 1.174
• Temperature 69ºC
• pH 4–4.5
In electrolytic cell process purified sodium chloride acts as electrolyte. Sodium
combines with mercury to form sodium mercury amalgam which goes to denuder
where it reacts with pure water forming caustic soda and hydrogen, releasing mercury
for recirculation.
Mercury cell has two compartments, i.e. anode compartment and other decomposer
(secondary cell). They are separated except for the flowing of mercury and the connecting
piping for amalgam. The anodic compartment is a long narrow rectangular box installed
at slight incline of about 18 cm to permit gravity flow of mercury and the depleted brine
during the electrolysis sodium amalgam, and chlorine is generated. Sodium amalgam
is decomposed to NaOH and hydrogen gas (Fig. 4.4).
68 Chemical Process Technology

Fig. 4.4: Caustic by mercury cell process

Reactions in mercurry cell process

Anode Reaction:
–
Cl × Cl2 + e

Cathode Reaction:
+ 1
H +e 2 H2
+
Na + e Na
Na + Hg NaHg
1
NaHg + H2O NaOH + 2 H2 + Hg
1 1
NaCl + H2O NaOH + 2 H2 + 2 O2

Concentration of mercury cell caustic soda: Various steps invoved in solid cautic soda
from mercury process is given below:

Factors affecting the mercury cell are:

• Concentration of brine solution 300 gpl
• Anode assembly
• Distance between anode and cathode should be minimum but not to the extent that
any salt crystal formation causes short circuit current density
• Decomposition efficiency
• Brine flow rate and temperature
• Mercury loses
• Consumption of graphite.
Chlor-caustic and Soda Ash Industry 69

Decomposition voltage 4.3V–5V (operating) Theoretical 3.05 V

Factors influencing the efficiency of mercury cell process are:
• Concentration (310 g/L), purity of salt, temperature (60ºC) and pH (<5).
• Rate of flow of mercury 10 mL/min
Thickness 3 mm, Slope: 1 mm/meter
• Final concentration of amalgam (about 0.3% sodium). Brine density is not allowed
to fall below 270 kg/m3 to avoid evolution of hydrogen at the mercury and oxygen
at graphite.
• Gap between mercury and graphite about 3–5 mm.
• Higher concentration of NaOH has tendency to solidify in secondary cell.
• Hydrogen content of chlorine gas (conc. of H2 >4% H2 in Cl2–H2 mixture are explosive.
• Salt consumption 1.7–2.3 tons, average 1.9, target 1.8 tons, 1.4613 T NaCl (100% pure),
1582 (95% NaCl).
• Characteristic of typical mercury cell:
Voltage 4.4 V
Maximum current per cell 720,000 amp.
Current density amp/m2 400–900
Current efficiency 94.96
Energy efficiency 75
NaOH kg/kWh 0.50
Cl2 kg/kWh 0.97
Anode life 300–400
Operating temperature 60–70
Concentration of caustic 50%
Mercury loss kg/T Cl2 0%
Number of cells 50–60
Brine density % H2 in anode gas % CO2 in anode gas
260 0.23 0.30
240 0.36 0.35
220 0.53 0.43
200 0.73 0.47
180 0.90 0.60
Optimum condition for better cell operation
• pH 3–4, Temperature 60–80ºC
• To purify brine for removal of Ca++, Mg++, Fe++
• Caustic to withdraw continuously
• To keep electrolyte flowing from anode to cathode to counter the diffusion of OH–
ion toward anode.

4.7.4 Membrane Cell Process

Because of the mercury pollution in mercury cell process, membrane cell has replaced
the conventional mercury cell process. Electrolytic cell process membrane is made of
70 Chemical Process Technology

synthetic material from perfluorosulfonic or carboxylic acid. Only Na ions carrying

positive charge are allowed to pass through it.
Typical membrane cell process consists of:
Primary brine purification: Precipitation of impurities especially alkaline earth metals
and silica. This requires precipitation and filtration prior to secondary purifications
Secondary brine purification: Polishing filters using ion exchange columns are used
for removal of alkaline earth metals. Ion exchange resins are used in secondary brine
purification for removal of alkaline earth metals like Ca, Mg, Sr, Ba and Ni, Al, SiO2.
Brine dechlorination: As in membrane cell there is an increase of active chlorine content
in the brine which is an aggressive oxidizing agent to resin and must be removed
thoroughly. The chlorine limit in the feed brine to the ion exchange resin should be
<0.1 ppm, preferable <0.005 ppm. Dechlorination is done in two stages first by vacuum
dechlorination (pressure; approx. 20 kPa/9200 mbar, pH 1.7–2.0, temperature 70–85ºC)
followed by chemical dechlorination using sodium sulfite (Pressure ambient, pH 2–8,
Temp. 80ºC).
Brine purification in membrane process is given in Figure 4.5.

Fig. 4.5: Brine purification in membrane process

Cell house: Electrolysis cell consists of anolyte part, catholyte circulation. Purified
brine is electrolyzed in analytic compartments while chlorine gas is generated. OH, ion
migrated from catholytic compartment is continuously neutralized using hydrochloric
acid. Chlorine is separated from depleted brine and collected into main chlorine gas
header and sent to chlorine gas treatment plant. Depleted brine is fed to the purified
brine. Hydrogen and caustic soda are produced by electrolysis in the cathodic
compartment. Hydrogen gas is separated from caustic soda. Hydrogen is collected in
main hydrogen gas header
In order to keep the concentration of caustic soda concentration de-mineralized water
is fed to catholytic separator.
Caustic concentration plant: For concentration of caustic from 32% to 50% NaOH
Membrane: Some of the commonly used material for membrane are polyperfluorosulfonic
acid (Nafion) and polyperfluorocarboxylic acid (Flemion).
Chlor-caustic and Soda Ash Industry 71

Characteristics of membrane: Deflects negatively charged chlorination and provide

impermeable barriers to prevent mixing of H2 and Cl2. Only sodium ion is allowed to
pass (Fig. 4.6).

Fig. 4.6: Caustic soda by membrane cell process

Membrane: Polyperfluorosulfonic acid (Nafion), Polyperfluorocarboxylic acid (Flemion),

and Polytetra flux ethylene PTFE.
Product: About 28% NaOH, 0.02–0.2% NaCl

Brine consumption: In membrane process lower concentration of brine is there as compared

to other processes 1.65–1.8 ton/ton of caustic.
Feed brine quality: Brine feed quality is very critical in membrane process and need
additional steps in purification.
NaCl 300–310 g/L
Total hardness as Ca 10 ppb
Sodium sulfate 3.5–4.5 g/L
Silica <1 mg/L
Aluminum 20 ppm
pH 3–4
Temp. 55–60
Power per ton of caustic 2600 kWh
Concentration of dilute caustic from membrane process is shown in Figure 4.5.

Comparison of mercury, diaphragm and membrane cell: Comparison of mercury, diaphragm

and membrane cell is given in Table 4.10.
72 Chemical Process Technology

Table 4.10: Comparison of mercury, diaphragm and membrane cell

Parameters and Mercury cell Diaphragm cell Membrane cell
other details
Anode Metal or graphite Metal or graphite Titanium + coated SS
Cathode Mercury SS SS coated
Brine quality Purified brie (primary Purified brine (primary Highly purified brine
purification) purification) (primary and
secondary purification)
Brine consumption 1.9–2.1 2–2.1 1.8
per ton caustic
Caustic concen­ 50% 11–14% 28%
tration
Impurities like NaCl 0.04 1.5% 0.02%
Brine plant Contains free chlorine No chlorine No chlorine
Suitability for rayon Suitable Not suitable, need Suitable
further purification
Pollution problem High mercury No mercury pollution. No mercury pollution
pollution However, asbestos
pollution
Operational ease Easy to operate Slight troublesome, Easy operation,
more manpower less manpower
Handling of brine More brine circulation Less brine circulation Less brine circulation
Purity of hydrogen Contaminated with No contamination No contamination
mercury
Cell room Monitoring necessary Not required Not required
monitoring for mercury consump­
tion control
Energy consumption During electrolysis During electrolysis During electrolysis
3200 2450 2570
Total 3300 Total 3100 Total 2860
Cell voltage 4.5 3.4 3.5
Current efficiency 97 96 94

4.8 HYDROCHLORIC ACID

Some of the major uses of hydrochloric acid are demineralization of water, pickling
of metals, acid treatment of oil and gas wells, as neutralizer in organic and inorganic
chemistry, hydrolysis of proteins and carbohydrates, regeneration of ion exchangers,
chlorine dioxide manufacture, methyl and ethyl chloride manufacture, chlorosulfonic
acid manufacture. Some of the sources of HCl are:
• Caustic chlorine plant: Produced by reaction of hydrogen and chlorine
• Byproducts in EDC manufacture as by product of cracking of EDC
Typical equipment used in HCl manufacture are:
Combustion chamber: Water jacketed chamber where hydrogen and chlorine are burned.
In combustion chamber highly corrosive environment persists and it is made of carbate.
Chlor-caustic and Soda Ash Industry 73

Cooler or absorber: Absorption of HCl vapor in shell and tube type of absorption where
absorption takes place in the tube side while water is circulated in cell side to remove
heat of absorption.
Tail gas tower: Absorption of HCl from tail gases.
Scrubber: Scrubbing of gases coming from tail tower with water (waste fume scrubbers)
Mist eliminator: For elimination of acid mist.
Flame arrestor: For stopping the flame from spreading. Flame arrestor is filled with
water through which hydrogen is passed before being fed to combustion chamber.
Fusion house: For concentrating caustic soda to 96% concentration in series of furnaces.

4.9 POLYALUMINUM CHLORIDE

Polyaluminum chloride (PAC) is an inorganic, polyaluminum chloride based, flocculent
especially suitable for waste water treatment. Due to large volume and polymeric
structure of the hydroxide flocs produced by the PAC, the activity of the product covers
a wide pH range, also at very low water temperatures.
Specifications
Appearance : Amber liquid
Specific gravity : 1.37 ± 0.02
pH at 20ºC : 1.6 ± 0.2

4.9.1 Manufacturing Process

Specified amounts of alumina hydrate and hydrochloric acid directly taken in the reactor
where reaction is affected with agitation, temperature and pressure. After completion
of the reaction the crude product is cooled in a separate graphite heat exchanger and
then filtered to remove unreacted alumina hydride. The basic product obtained after
filtration is stored in storage tanks from where it is suitably diluted/formulated un the
final product as per specific requirement of the consumer.
Unreacted alumina hydride is taken back to the reactor and digested with waste
sulfuric acid resultant aluminum sulfated solution is added to the particular formation
of the final product.
Unloading: The product is taken out of the reactor through bottom. The unloading process
take time of 30 minutes.
The other important equipment in the process are:
• Graphite cooler: It is shell and tube type heat exchanger is used to cool the process
fluid.
• Filter press: It is used to filter the crude PAC.
• Scrubber: The fumes of HCl from the reactor are dissolved in the water to control
the air pollution.
Safety
The most important part of the plant is the glass line reactor. To prevent the crakes
and breaking of glass the heat and cooling processes are being done in steps. After
completion of every batch the reactor is checked for breakage.
PAC Powder: Transporting PAC in liquid form at far places is difficult and costlier as well.
To facilitate the transportation, handling and storage liquid PAC is dried to PAC powder.
74 Chemical Process Technology

The drying operation takes place in spray dryer. Liquid PAC is sprayed in form
of small droplets (to increase the heat transfer) by atomizer, where hot air with a
temperature of around 350ºC enters the drying chamber tangentially. Mass transfer
from the surface of droplets takes place due to contact with hot air and vaporization
takes place. The powder form of the PAC is obtained and packed. Characterstics of
liquid and powder forms of PAC are given in Table 4.11.

Table 4.11: Characteristics of liquid and powder PAC

Liquid PAC AC/100 S Water treatment
Arya PAC Water treatment
SAB-18/5 Paper sizing (acidic)
SAB Paper sizing (neutral) and effluent treatment
Powder PAC SAB-18 Water treatment and effluent treatment
AC-100 S Water treatment

Various forms of PAC and their uses: The liquid PAC produced is formulated into various
final products as per the consumer requirements. The different formulated forms are:
Reactor
The reactor is a jacketed tank with inside coating of glass. At various stages of a batch
the temperature is maintained by fluid in the jacket. The reactor is provided with an
educator for proper mixing and the baffles. A batch has the following stages of operation:
• Loading
• Heating
• Precooling
• Cooling
1. Loading: First of all, the reactor is loaded with raw materials. 6600 kg of HCl is fed in
the reactor in 15 minutes. Then 2900 kg of alumina hydrate is fed into 30 minutes.
In this way, load process takes time of 45 minutes.
2. Heating: The temperature required for the reaction is 160ºC. This temperature is
achieved in steps. The temperature is not increased directly dye to brittleness of glass.
Steam at lower pressure (about 3 kg/cm2) is passed to the jacket for 30 minutes which
brings the reactor to a temperature of 60ºC. It brings the reactor to the temperature
of 160ºC. Then isothermal conditions are maintained for two hours.
3. Precooling: Water at 90ºC is passed in jacket for one four which brings reactor fluid
PAC to a temperature of 135ºC.
4. Cooling: Temperature of reactor is further reduced to 90ºC by passing cooling water
with temperature 45ºC for 1½ hours.

4.10 CHLOROSULFONIC ACID

Product Specification
Name : Chlorosulfonic acid
Chemical formula : CISO3H
Popular name : Sulfuric chlorohydrins
Chlor-caustic and Soda Ash Industry 75

Physical state : Liquid, clear or cloudy fumes with heavy white vapors when
exposed to atmosphere
Odor : Sharp, acrid penetrating odor
Flammability: : Nonflammable, however, the acid may cause ignition by
contact with combustible material.

Manufacturing Process
Chlorosulfonic acid (CSA) plant consists of two sections: reaction section and hydrogen
chloride recovery section. Raw materials SO3 and HCl gas are charged to the reactor.
CSA is formed by the reaction of SO3 and HCl.
SO3 + HCl CISO3H

After condensed by cooling, CSA formed is send to product tank. Waste gas which
mainly contain HCl gas is sent to HCl recovery section. HCl gas is absorbed by process
water while cooling and 30% hydrochloric acid is obtained. This HCl acid is sent
to HCl recovery tank. After hydrochloric acid gas is removed, waste gas is discharged
into air.
Uses
Various end uses of chlorosulfonic acid are dyes, dyes and intermediate, vinyl sulfone,
drugs and pharmaceuticals, saccharin, etc.

4.11 STABLE BLEACHING POWDER

Stable bleaching powder (SBP) plant was commissioned on 23th August 1986. Present
capacity of the plant is 46 TPD. The annual capacity is 16,800 TPA, which is 10% of
total capacity of India.

Manufacturing Process
Stable bleaching powder is manufactured by the chlorination of dry lime powder
under vacuum in chlorination drum. This is a batch process. Known amount of slaked
lime is charged in the drum and liquid chlorine is injected till chlorination completes.
After completion of chlorination, the powder is dried by steam and dry powder is then
discharged to a hopper, from which it is packed in various sizes of drum or bags with
the help of a drum or bags with the help of a weighing balance.

Uses
Stable bleaching powder is of utmost important in water treatment, sanitation, bleaching
agent in textiles, papers, etc.

4.12 SODA ASH

The soda ash industry in India traces its origin to the 1930s when Dhrangadhra
Chemical works sets up its plant in Gujarat which was followed by Tata Chemicals
which started soda ash plant at Mithapur in Gujarat. Both processes were based on Solvay
process (Raghavan R. “Soda ash: Inventory pile up likely to be exacerbated” Chemical
Weekly Annual, 1998, Sept. 29, 1998, p.125). The much of the industry is presently
located in the western belt especially Saurashtra in Gujarat. The driving force for this
76 Chemical Process Technology

has been the availability of salt, chemical manufacture salt and availability of water.
Power consumption is about 30–35% of the cost of and the high costs have deterrent to
competitive production of soda ash. The fortune of the industry is intimately related to
the demand supply situation (“Soda ash: inventory pile up likely to be exacerbated”).
Global soda ash world capacity is 67 million tons per anuum, while India’s capacity
is is 3.4 million tons per anuum, i.e 5% of global capacity (Chemical Digest Annual
January 2018).
Soda ash (commercial name sodium carbonate) forms an important part of Indian
inorganic chemical industry. It accounts for 50–60% of chlor-alkali industry by turnover.
It is a high volume, low-value product and finds application mainly in the production
of detergents (42% light soda ash), glass (23% dense soda ash), chemicals (17% mainly
light soda ash), sodium silicate, pulp and paper and water treatment.

Soda Ash: Global Overview

Worldwide consumption of soda ash is estimated at 48 million tons. The US accounts
for over 92.3% of global natural soda ash production of 11.7 million tons. The country
has world’s lagest trona deposit in the green river basin. Global capacity of soda ash
is given in Table 4.12.

Table 4.12: Global capacity of soda ash

Capacity Production Demand
India 3.0 2.50 2.75
China 32.0 26.0 24.0
North America 12.50 12.0 5.30
Europe 12.0 11.0 10.50

Total capacity of Chitouching 32 million tons which is 10 times of India’s soda ash
capacity.
China and US are the biggest soda ash producing countries accounting for 40%
and 20% of the total global ash capacity respectively (Indian Chemical Industry
XIIth Five-year plan 2012–17). Globally majority of soda ash is used in glass industry
accounting for about 50% of global soda ash consumption.
Indian Scenario: There are five manufactures of soda ash in India having installed capcity
of 3.16 million tons.
Consumption pattern: Soda ash finds application in detergent, glass, sodium silicate and
chemical manufacture (Table 4.13). The biggest single application is as filler and builder
in low cost detergent manufacture. Another major consumer is glass industry
• Glass industry
• Soap and detergent industry
• Steel industry
• Non-ferrous metallurgy industry
• Chemical industry
• Sodium bicarbonate
Chlor-caustic and Soda Ash Industry 77

Table 4.13: Commercial form of soda ash

Light soda ash Na2CO3 510–560 General purpose

Dense phase Na2CO3 968–1075 Glass

Fused soda ash Na2CO3 1075–1100 Metal refining

Monohydrate Na2CO3H2O 300–330 General use

Soda cystal Na2CO310H2O 290–300 General use

• Sodium sesquicarbonate [Na3H(CO3)2]

• Chemically pure sodium carbonate
• Sodium bichromate
• Sodium per carbonate
• Sodium phosphates
• Sodium silicates
• Sodium sulfites
• Other applications
ƒ Production of various chemical fertilizers
ƒ Production of artificial sodium bentonites or activated bentonites
ƒ Manufacture of synthetic detergents
ƒ Organic and inorganic coloring industry
ƒ Enameling industry
ƒ Petroleum industry
• Fats, glue and gelatine industry, etc.
Soda ash plants in India: Some of the major soda ash producing plants in India and
their location are given in Table 4.14. Shahu Chemical which was producing soda ash
by Solvay process is closed. Installed capacity and production of soda ash is given in
Tables 4.15. to 4.17. Indian soda ash demand is expected to reach 3.6 million tons by 2017.
During the year of 2013–14 the imports and exports of soda ash are 7.0 lakh and
77.368 lakh MTA. The installed capacity of soda ash as on 31st March 2015 is 30.76 lakh
MTPA.

Table 4.14: Major Soda ash producing industry

Name of company Year Location
DCW Ltd. 1932 Dhrangadhra, Gujarat
Tata Chemicals 1944 Mithapur, Gujarat
Suarashtra Chemicals 1959 Porbandar, Gujarat
Tuticorin Alkalies and Chemicals 1982 Tuticorin, Tamil Nadu
Punjab National Fertilizers and Chemicals 1984 Nangal, Punjab
Gujarat Heavy Chemicals 1988 Sutrapada, Gujarat
Nirma Industries 1969 Ahmedabad, Gujarat
RSPL Jamnagar Green Field 2011 (Project stage) Jamnagar, Gujarat
78 Chemical Process Technology

Table 4.15: Soda ash capacity of Table 4.16: Domestic consumption of

Indian manufacturers soda ash in India
Name of the company Percentage share Consumption Percentage
of manufacturer Glass 26
Tata Chemicals 31% Detergent 37
Tuticorin Alkalies and 4% Others 37
Chemicals
Gujarat Heavy Chemicals 27%
DCW Ltd 3%
Nirma 35%

Table 4.17: Installed capacity and production of soda ash in India (thousand tons)
Year Installed capacity Production
2006–07 2993.7 2046.9
2007–08 3078.7 2024.7
2008–09 3078.7 2129.0
2009–10 3078.0 2147.2
2010–11 3161.0 2424.6

Soda ash is the common name for the technical grade anhydrous sodium carbonate
(Na2CO3). In the eighteenth-century, soda ash was produced by LeBlanc process based
on roasting salt cake with carbon and limestone. The following synthetic processes are
available:
• Leblanc process
• Solvay process
• Dual process (modification of Solvay process)
The raw materials and utility consumption by different process routes are as follows:
• Brine
• Limestone
• Carbon for the lime kiln
• Ammonia
• Additives
Leblanc process: Original process of soda ash manufacture was started with Leblanc
process which has more labor involvement, less product purity, and corrosion problem
due to HCl. The process involve reaction of NaCl with H2SO4 for production of sodium
sulfate which is reduced to sodium sulfide in presence of carbon. Sodium sulfide is
further reacted with calcium carbonate to produce sodium carbonate. Calcium sulfide
so formed is converted to calcium carbonate by reaction with carbon dioxide.
• Na Cl + H2SO4 NaHSO4 + HCl
• NaHSO4 + NaCl Na2SO4 = 2HCl
• Na2SO4 + C Na2S + CO
• Na2S + CaCO3 Na2CO3 + CaS
• CaS + H2O + CO2 CaCO3 + H2S
Chlor-caustic and Soda Ash Industry 79

4.12.1 Solvay Process

Solvay process, also known as ammonia soda process, uses salt (NaCl) and limestone
(CaCO3) as raw materials. Ammonia, which is also used in the process is almost totally
regenerated and recycled. Various steps involved in production of sodium carbonate
are (Fig. 4.7):
• Brine purification
• Lime kilns and milk of lime production
• Absorption of ammonia
• Precipitation of sodium bicarbonate
• Separation of sodium bicarbonate from mother liquor
• Sodium bicarbonate calcination
• Ammonia recovery
• Product storage and handling.
Raw material requirement
• Salt 1.55 T
• Lime stone 1.20 T
• Coke 0.09 T
• Ammonia losses 1.5 kg
• HP steam 1.35 T
• LP steam 1.60 T
• Power 210 KW

Fig. 4.7: Solvay process for manufacture of soda ash

80 Chemical Process Technology

Various steps involved in soda ash process are:

1. Purification of brine: The process involves the for removal of Ca, Mg and Fe using
precipitation process.
2. Ammonia absorption: Ammoniation of brine
NH3 conc. 75–85 g/L
NaCl 260–275 g/L
NH3 and weak CO2 in brine, cooled to 30ºC
Solubility of NH3 in brine-conc of brine,presence of CO2, temp.
3. Carbonation of Ammoniated brine: Ammoniated and partially carbonated with weak
CO2 (around 40% purity) and goes to cleaning tower. CO2 serves to carbonate the
liquor just below precipitation. The liquor from cleaning tower goes to forming tower.
High rate of reaction is favored high temp, high conc. of CO2 and intimate mixing.
High conversion of chloride to bicarbonate is favored by high CO2 pressure and
concentration. Optimum cooling of slurry exits 72–76% conversion with bicarbonate
slurry temp. of about 28ºC. An exit temp. too low gives mixed ammonia and sodium
bicarbonate crystals
Solvay tower 5–6 in number; 2.3–3 meters in diameter and 30 meters height.
Temp at both end 20–25ºC in middle 45–50ºC

Advantages
• Can use low-grade brine
• Less electric power consumption
• Less corrosion problems
• No co-products to dispose off
• Does not require ammonia plant investment

Disadvantages
• Higher salt consumption
• Higher investment in ammonia recovery unit versus crystallization units for
ammonium chloride
• Waste disposal of calcium chloride brine stream
• More steam consumption
• Higher capacity plant for economic break-even operation
• With current fertilizer shortage, all of the ammonium chloride will be used as a mixed
chemical fertilizer ingredient, so co-product disposal no problem

4.12.2 Modified Solvay Process (Dual Process)

Modified Solvay process which is also called dual process, ammonia recovery unit and
milk of lime section are replaced with an ammonium chloride section, where ammonium
chloride is crystallized and recovered. In this process ammonium chloride is produced
as a co-product in equivalent quantities and differs from the conventional solvay process
as it does not recycle ammonia. Process flow diagram for the manufacture of soda ash
by modified Ssolvay process is given in Figure 4.8.
Chlor-caustic and Soda Ash Industry 81

Fig. 4.8: Modified Solvay process

BIBLIOGRAPHY
1. Cruickshank MJ. Ocean raw material, Kirk othmer encyclopedia of Chemical Technology,
Vol 17 (5th edn) 2007 Willey-Interscience (a. Forest).
2. Ghosh PK, Kumar A. Chemical Industry Digest, April 2011, p.76.
3. Gilra BS. Seminar on operation and maintenance of Membrane Cell plants and Vendor Meet
cum Expo, November 21–2, 2013, Trident, Chennai.
4. Gopala Rao M, Sitting M. Dryden’s Outlines of Chemical Technology for the 21st century
(3rd edn) East west Press 1997.
5. [Link] opportunities-
2019/[Link]
6. [Link] Bcheckedd/topic/531121/sea water
7. Indian Chemical industry XIIth Five-year plan 2012–17.wg_chem0203.pdf
8. Majumdar AH. Hydrochloric acid, CEW Vol 27, No 11, November 1992, p.5.
9. Patwardhan V. Chemical Industry Digest, September 2018.
10. Ragavahn R. Chemical weekly, Annual, Sep 29, 1998, p.125.
11. Seethaaram B, Srinivasam D. Recovery of Minerals from sea water, CEW Vol. XIII No. 11, p.63.
12. Singh YR. Voluntary mercury cell phase out programme of India, Sockholm, Sweden,
June 6, 2010.
13. Technical EIA Guidance manual for Soda ash Ministry of Environment and Forest 2012.
14. Todi A. Chlorine-opportunity for India, Chemical News June 2010, p.2.
5
Sulfur and Sulfuric Acid

5.1 INTRODUCTION
Sulfur is an essential element for all life and is widely used in chemical and biochemical
processes. Primarily, sulfur is used in the manufacture of fertilizer, sulfuric acid and
industrial chemicals. In fertilizer industry, sulfur in the form of sulfuric acid is used for
the manufacture of phosphoric acid, SSP, ammonium sulfatic, potassium sulfate, and
elemental sulfur-based fertilizers. Nonfertilizer uses include metallurgical processing,
caprolactam, titanium oxide, industrial phosphates, petroleum refining, pulp and paper
industry and others. Elemental sulfur is also used in matches, insecticides, fungicides.
Elemental sulfur is an essential element for all lives and is widely used in biochemical
processes and medicines.
On earth, elemental sulfur can be found near hot springs and volcanic regions in many
parts of the world, especially along the pacific ring of fire. Common naturally occurring
sulfur compounds include the sulfide minerals, such as pyrite (iron sulfide), cinnabar
(mercury sulfide), galena (lead sulfide), sphalerite (zinc sulfide), and stibnite (antimony
sulfide); and the sulfates, such as gypsum (calcium sulfate), alunite (potassium aluminum
sulfate), and barite (barium sulfate) are found in Indonesia, Chile, and Japan.
Sources of Sulfur
Various sources of sulfur are:
• Elemental sulfur
• Metal sulfides: Iron pyrite (FeS2), copper pyrite (FeCuS2), copper glance (Cu2S2), zinc
blende (ZnS), PbS, COS, NiS.
• Sulfates: Gypsum (CaSO4.2H2O), anhydrite (CaSO4), Na2SO4, MgSO4, etc.
• Sulfur recovery from sulfur bearing gases
• Sulfur recovery unit consist of recovery of sulfur from H2S present in acid gas
from amine treating/regeneration unit and H2S from sour water stripper section.
Amine absorption and regeneration: Absorption of H2S bearing stream and
regeneration of amine. H2S rich stream from amine regeneration is sent to sulfur
recovery unit.

Elemental Sulfur
Elemental sulfur is present in some of the countries and it was obtained by mining.
sulfur mining is done by Frasch process. Mining of sulfur involves injection of hot water
82
Sulfur and Sulfuric Acid 83

at about 170ºC for melting sulfur in the underground deposit and passing pressurized
air for recovery of hot sulfur. The melted sulfur alongwith water is transferred to the
bins where the sulfur solidied. Process flow diagram for mining of sulfur from mines
is given in Figure 5.1. China is the largest importer of sulfur bulk of which is used in
fertilizer industry.

Fig. 5.1: Sulfur mining process

With increasing environmental stringent regulation and require ment ultralow sulfur
in fuels sour gas processing and oil refining are going to be major source of sulfur.
Abu Dhabi is top sulfur exporter.

Properties of Sulfur
Atomic mass 32.06
atomic number 16
MP 115.2ºC
BP 444.6ºC

Sulfur from pyrite ores: Sulfur in form of SO2 is recovered from pyrite ores during roasting
of ores to obtain metal oxides. SO2 bearing gas after removal of particulates is used for
manufacture of sulfuric acid. Sulfuric acid by pyrite process is made by some of the
units India processing pyrites for the manufacture of zinc and copper.
Sulfur Recovery from sulfur-bearing gases: Sulfur recovery unit consists of recovery of sulfur
from H2S present in acid gas from amine treating/regeneration unit and H2S from sour
84 Chemical Process Technology

water stripper section. H2S-bearing gases from refinery are absorbed in amine solution
and regenerated H2S gas is sent to sulfur recovery plant for recovering elemental sulfur
using Claus or modified Claus process. Sulfur recovery from H2S bearing gases and
from refinery gases are shown in Figures 5.2 to 5.4.

Fig. 5.2: Sulfur recovery from H2S

Fig. 5.3: Sulfur recovery from various sources from refinery

Sulfur and Sulfuric Acid 85

Fig. 5.4: Sulfur from sulfur recovery unit of refinery

5.2 SULFURIC ACID

It follows one of the oldest industrially applied processes discovered by a Persian
alchemist in the tenth century. Saltpeter and sulfur were mixed in a glass container
and burned in a moist atmosphere. Acid was collected from the condensed vapors.
In England, 1746, the lead chamber reactor was invented. This invention allowed for
higher production rates (<78%). In England, 1831, a patent was filed that described
the oxidation of sulfur dioxide over a platinum catalyst, the contact process. This new
process increased the yield of reaction from 70 to above 95%. In 1913, BASF was granted
a patent for the use of vanadium pentoxide as a catalyst for the contact process. By
the 1930s, vanadium pentoxide was becoming the dominant catalyst used because of
insensitivities to poisons and lower cost. In 1960, a patent application was filed by Bayer
using the so called double-catalyst process (double absorption).
Global sulfuric acid production surpassed 230.7 million tons. In 2012, the world
sulfuric acid capacity was estimated at more than 290.7 million tons with over 40% share
in Asia. In 2015 global production of sulfuric acid was expected to go beyond 257–257.6
million tons. China, US, India, Russia and Moroco are the top five major sulfuric acid
manufacturing counties ([[Link]
Global elemental sulfur potential demand for sulfuric acid and nonsulfuric acid is to
be 55,941,000 and 8,272,000 tons.
In India all sulfuric acid is manufactured from sulfur except Hindustan Copper,
Hindustan Zinc, Indogulf Corporation Ltd., Dahej and Sterlite Industries which are
based on smelter gases from zinc and copper. Dharmsi Morarji Chemicals Co. is a
leading sulfuric acid manufacturer unit. Some of the other sulfuric acid producing
plants are IFFCO, SAIL (Bhilai Steel Plant), GSFC, Vadodara, Coromandel Fertilizer,
Industries, Liberty Phosphate, East Coast Fertilizers and Chemicals, EID Parry (India),
Ganga Fertilizer, and Bharat Fertilizer. There are about 140 sulfuric acid plants out of
which 130 are based on sulfur and 10 smelter gas. Hindalco Acids and Fertilizers is one
of the major producers of sulfuric acid based on sulfur and DCDA process (Monsanto
Environment).
86 Chemical Process Technology

5.2.1 Uses of Sulfuric Acid

Sulfuric acid is one of the most widely used chemical in chemical process industries.
It is used in chemical, fertilizer, agrochemical, petroleum, petrochemical and
metal industries. Sulfuric acid was considered barometer of industrialization. Various
uses of sulfuric acid is given in Figure 5.5. Large tonnage of sulfuric acid is used
in fertilizer plants.

Fig. 5.5: Uses of sulfuric acid

5.2.2 Sulfuric Acid Manufacture

Earlier sulfuric acid was manufactured by lead chamber process. However, due to
low concentration and high emission of sulfur gases, this process is not being used
(Table 5.1). With development of catalyst like platinum or vanadium now sulfuric acid
is being manufactured by DCDA process using vanadium catalyst which has several
advantages over platinum catalyst.

5.2.3 Technological Development of Sulfuric Acid

Although sulfuric acid manufacture started with lead chamber process, before
introduction of single conversion single absorption process (SCSA), now DCDA process
has replaced the SCSA process except some plants based on smelter gases, which are
working on SCSA process. Apart from conversion efficiency stringent environment
regulation has been the major driving force for development. CPCB standard for SO2
(kg/metric tons of 100% acid), acid mist is 50 mg/Nm3, respectively.

Table 5.1: SO2 emission standards from different countries

Country SO2 (kg/metric tons of 100% acid)

Japan 1.0
USA 2.0
UK 3.0
India 4.0

To lower the emission SO2 and acid mist continuous development in converter and
absorber has taken place. Driving force for various development in sulfuric acid plants
is taking place. Now plants are coming with 5-stage converter, already two plants are
based on 5-stage converter.
Sulfur and Sulfuric Acid 87

5.2.4 Sulfuric Acid by Double Contact Double Absorption (DCDA) System Using Sulfur
as Raw Material
Product Specification
98.5% by weight minimum
Free iron 0.05% by weight maximum
Oleum 23% free SO3 by weight minimum
Free iron 80 ppm maximum
SO2 11% by weight minimum

Raw Material and Utilities per ton of Acid

Sulfur 0.34 MT (theoretical requirement: 0.3265)
DM water 1.5 MT
Power 75 KWH
Steam production 1.3 MT
Reactions
S + O2 SO2
1
SO2 + 2
O2 SO3

SO3 + H2O (97% H2SO4) H2SO4 + DH

H2SO4 + SO3 H2DO4SO3

(Oleum)

Process Steps Involved in Sulfuric Acid Manufacture

1. Sulfur handling and purification
2. Combustion air system
3. Sulfur burner and hot gas filter
4. SO2 converter
5. Intermediate absorption system
6. Oleum production system
7. Final absorption system
8. Product SO2
9. Process:
• Solid sulfur is melted in sulfur melter by passing steam in coils at 5–6 kg/cm2.
The melter consists of concrete walled tanks containing steam coils. Normally
one melter works as settling tank for removal of suspended impurities. Molten
sulfur is filtered through a steel mesh sieve which is fitted on hollow shaft closed
in a steam jacketed cylindrical vessel.
• Molten sulfur after removal of impurities in settling tank and filters is pumped to
sulfur burner by sulfur pumps where it is burned in presence of dry air to form
SO2. Molten sulfur is sprayed under pressure inside the sulfur burner using an
atomizer. Air used for combustion of sulfur is dried in air drying tower using
sulfuric acid.
88 Chemical Process Technology

• The combustion gases containing 9–10% SO2 at about 960–970ºC is cooled in

waste heat boiler for generation of steam. The cooled gases at 560–580ºC are
further cooled in a shell and tube heat exchanger to 430–440ºC.
• Clean hot gases after filtering in hot gas filter is fed to 4-bed catalytic oxidation
chamber for oxidation of SO2 to SO3 using vanadium pentoxide as catalyst.
The conversion achieved after 4th stage is about 99.6%. The oxidation process
is exothermic and cooled in each stage after each stage of the converter.
Temperature of gases after each stage is given in Table 5.2.

Table 5.2: Temperature of gases after each converte stage

SO2 converter stage Inlet (ºC) Outlet (ºC)
I 420 600
II 430 520
III 440 450
IV 420 430

Reactions
S + O2 SO2
1
SO2 + 2
O2 SO3

SO3 + H2O (97% H2SO4) H2SO4 + DH

H2SO4 + SO3 H2DO4SO3

As both oxidation reaction from sulfur to SO2 and SO2 to SO3 require oxygen excess
is used to burn sulfur.

Catalyst in Sulfuric Acid Manufacture (V2O5 vs Platinum)

Although platinum was used as catalyst in earlier stages of sulfuric acid manufacture
for oxidation of sulfur dioxide, however platinum is highly sensitive toward even
traces of arsenic, selenium, chlorine and other impurities. Now vanadium pentoxide
has replaced platinum as catalyst. Comparison of platinum and vanadium pentoxide
is given in Table 5.3.

Table 5.3: Comparison of vanadium pentoxide and platinum as catalyst

V2O5 Platinum
Higher conversion Lower conversion
Longer life with high efficiency Shorter life and highly fragile
Not affected by poison Poisoned by arsenic and other impurities
Can handle low SO2 gas Can handle only rich gas with 8–10% SO2

Variables in Catalytic Oxidation of SO2

• Reaction requires high activation energy
• Reaction uses porous carrier with large surface are and controlled pore size such as
alumina, silica gel, zeolite.
Sulfur and Sulfuric Acid 89

• The active component is either V2O5 or platinum

SO3 + O2 SO3
• Platinum is more prone to catalyst poisoning
• Multiple bed catalytic reactor with intermediate cooling is in each stage is provide
to maintain the temperature as the oxidation reaction is exothermic.
• Lower temperature limit: For vanadium catalyst it is 400­–440ºC. Kindling temp of
vanadium catalyst is 400–440ºC.
• Upper temperature limit: 600–650ºC. Above this limit catalyst gets fractured and
loses its activity.
• Temperature range of operation: 400–600ºC.
• Equilibrium conversion of SO2 decreases as temperature increases. The oxidation of
SO2 to SO3 is thermodynamically favored by low pressure.
• The conversion is almost complete at 427ºC.
• Although elevated pressure is favorable, but effect of pressure is small.

Absorption of SO3
SO3 produced in the converter is absorbed in concentrated sulfuric acid. The intermediate
absorption is carried out after the third stage conversion. The gases from the third stage
of the converter is cooled in economizer to 180ºC and absorbed in 98.4% sulfuric acid.
Final absorption is carried out after 4th stage conversion. The gases from fourth stage
converter are absorbed in final absorption tower.
SO3 +H2O H2SO4 (g)
SO3 + mH2SO4 + H2O (m+1) H2SO4 (g)

Variables in Absorption of SO3

Some of the major variables in absorption of SO3 are:
• Optimum temperature range for absorption is 60–70ºC.
• Too low acid concentration results in fine acid mist formation and subsequent loss
of acid in effluent gas.
• Very high concentration leads to poor absorption.
• Partial pressure of SO3 over 100% sulfuric acid is very high, so not all of SO3 would
be absorbed.
• Partial pressure of SO3 over the solution should be negligible to have high driving
force.
• Water vapor has high partial pressure. So SO3 and H2O in vapor phase combine to
form H2SO4 mist.
• Absorption operation is effective so that a single pass through system raises the
concentration of H2SO4 by not more that 1–1.5%

5.2.5 Sulfuric Acid from Pyrite Roaster Gases

Sulfuric acid is also produced from pyrite roasting plant where the roaster gases from
iron, copper and zinc pyrite roaster are used for the manufacture of sulfuric acid. The
process steps involved similar to DCDA process. Roaster gases containing sulfur dioxide
90 Chemical Process Technology

from the roaster are send for cleaning to cyclone and ESP for removal of particulate
matter followed by cooling for removal of mist (Fig. 5.6). Typical composition of iron
pyrite ore is given in Table 5.4.

Double Absorption Contact Process

Fig. 5.6: Sulfuric acid by DCDA process using sulfur

From Roster Gas (FeS2, CuS, ZnS) Pyrite

Pyrite contains sulfur which is roasted for the production of respective metal oxide.
During the process sulfur dioxide is also produced. The oxides of the iron, copper, zinc
are used for production of respective metals. The roasted gases are first sent to waste
heat recovery plant and for removal of particulate matter and after that the SO2 gas
is oxidized to SO3 using vanadium pentoxide. The process is similar to conventional
contact process. Absorption of SO3 is done now by double absorption process as in case
of DCDA process using sulfur. Composition of typical pyrite ore is given in Table 5.4.
Reaction involved in roasting of various pyrite ores are given in Figure 5.7.
Sulfur and Sulfuric Acid 91

Table 5.4: Chemical composition of high grade Amjhore pyrites and Saladipura pyrites
Amjhore wt% Saladipura wt %
Sulfur 22.6 23.6
Iron 19.03 26.5
Carbonaceous matter 2.56 —
Silica 46.5 25.7
Aluminum 9.0 10.9
As 0.007–0.15 —
MgO 0.1 1.73
CaO — 7.87
K2O — 0.96

Na2O — 0.41
Cu Traces 100 ppm
Zn — 100 ppm
Graphite — Traces
Mn — Traces
Moisture 3–5 —

FeS2 + 6O2 Fe7S8 + 6SO2

Fe7S8 + O2 7FeS + SO2
3FeS + O2 Fe3O4 + 3SO2
Fe3O4 + O2 2Fe2O3
Cu2S + 3O2 2Cu2O + 2SO4
2Cu2O + O2 4CuO
ZnS + 3O2 2ZnO + 2SO2

Fig. 5.7: Reaction in pyrite roasting

5.3 OLEUM
Oleum contains sulfuric acid with additional SO 3 absorbed. Twenty percent
oleum contains 20% SO3 by weight in the oleum. Common strengths of oleum are
20, 30, 40, 65%. To produce 20 and 30% oleum, only requires an additional absorption
tower. Oleum is used extensively in chemical industries for the production of detergent
and other products.
• Oleum is used in reactions where water is excluded
SO3 + H2SO4 H2S2O7 (disulfuric acid)

5.4 ALUM
Alum is one of the important products and find wide application in various industries
and water treatment plants. Alum has wide application in paper industry in sizing.
92 Chemical Process Technology

Other applications of alum are in fire retardant, cosmetics, medicine, leather tanning
and as flocculent. Aluminum-based alum is made by reacting bauxite with sulfuric acid
while potassium alum is natural occurring sulfate minerals. Process flow diagram for
the manufacture of alum from bauxite is given in Figure 5.8.

Fig. 5.8: Production of alum from bauxite and sulfuric acid

Material of construction for sulfuric acid: Choice of material of construction for handling
sulfuric acid is very important
• Ordinary carbon steel is widely used for sulfuric acid in concentration over 70%.
• Storage tanks, tank cars and shipping drums: steel for handling 78%, 93%, 98%.
• Corrosion of steel is strong function of temperature and concentration.
• Dilute acid attack steel very rapidly. Below 65% steel is not suitable.
• Lead is extensively used for lower concentration range.
• High silicon cast iron with 14.5% silicon posses best all round corrosion resistance
over the range 0–100% sulfuric acid.

BIBLIOGRAPHY
1. Austin George T. Shreve’s Chemical process Technology, McGraw Hill, International Edition,
(5th edn) 1984.
2. Comprehensive industry document on sulfury acid plant (COINDS?69?2007), CPCB MOEF New
Delhi, May 2007.
3. Gopala Rao M, Sitting Marshall. Dryden’s Outlines of Chemical technology for the 21st century,
(3rd edn.) Affliated East West Presss, New Delhi.
4. [Link]
5. Moulij JA, Makkee M Diepen. Anneelies van, Chemical Process Technology, John Wiley & Sons,
Ltd., 2001.
6. wikipedia[Link]
6
Fertilizer Industry

6.1 INTRODUCTION
Fertilizer industry has played important role in increased availability of food grains.
Fertilizer may be organic or inorganic and contains one or more of the nutrients
mainly nitrogen, phosphorus, potassium, and other essential elements required for
plant growth. The principal raw materials for fertilizer production are air, natural gas,
phosphate rock phosphate, potash and sulfur. The fertilizer industries are categorized
based on the type of nutrients, present in fertilizers. Based on the nutrients fertilizers are
categorized as straight run fertilizer (single nutrient) or complex fertilizer (containing
more than one nutrients). Various type of fertilizers are given in Table 6.1.

Table 6.1: Type of fertilizers

Nitrogenous fertilizers
Urea 46%N
Ammonium sulfate (AS) 21%N
Ammonium chloride (ACl) 26%N
Calcium ammonium nitrate (CAN) 25%N
Phosphatic and potassium fertilizers
Single superphosphate (SSP) 16% P2O5
Triple superphosphate 46% as P2O5
Nitrophosphate
Muriate of potash (MOP) 60% K2O
Sulfate of potash (SOP) 48% K2O
Ammonium phosphate (AP) 18–46
Di-ammonium phosphate (DAP) 18–46
Rock phosphate (RP) 16–20% P2O5

6.1.1 Elements Necessary for Plant Growth

Plants need nutrients at various stages depending on the crops and have specific and
essential functions in plant metabolisms. Nitrogen is the main driver of yield. Mineral
fertilizer is necessary to replace those nutrients which are removed from the field.
Nutrient improves the crop quality and size.
93
94 Chemical Process Technology

Primary or major nutrients (3): Nitrogen, phosphorus, potassium. Applied almost for all
crops on most soil.
Secondary nutrient (3): Calcium, magnesium, sulfur. Applied in fertilizers for certain crops.
Micronutrients (7): Boron, chlorine, copper, iron, manganese, molybdenum, zinc, etc.
Some beneficial nutrients useful for some plants: Na, Si, Co, Cl, Al, etc.
Organic fertilizer those derived from crop reside and animal nutrients while mineral
fertilizer from air and mineral from soil. Organic farming represents only a marginal
share of total cultivated land. Mineral fertilizer is essential to sustain future yield
increase. One ton of grain requires 25 kg of nitrogen. Increase production of mineral
fertilizers necessary to meet future nutrient demand. Driving force for increase in
fertilizer consumption is increase in population, economic growth, improved diets and
biofuels. Industrial use accounts for 19% of global nitrogen consumption.

6.1.2 Structure of Fertilizer Industry

Nitrogenous phosphatic fertilizers and potassic fertilizers are important segment of
fertilizer industry requiring wide variety of raw materials. Straight run and complex
fertilizers are produced. Structure of fertilizer industry using various raw materials
for the production of nitrogenous, phosphatic and mixed fertilizers based on NPK are
shown in Figure 6.1 and Table 6.2. Now many fertilizer complexes have diversified their
product especially synthesis gas chemicals. Chemicals derived from synthesis gas are
shown. GSFC, NVFC, and RCF are manufacturing some synthesis gas-based chemicals
and other chemicals apart from conventional fertilizers.

Fig. 6.1: Typical nitrogenous and phosphatic fertilizer complex

Fertilizer Industry 95

Table 6.2: Straight run fertilizer and complex fertilizer

Straight run nitrogenous fertilizer Urea, ammonium chloride, ammonium sulfate, ammonium
chloride, calcium ammonium nitrate
Straight phosphatic fertilizer Single superphosphate (SSP), triple superphosphate (TSP)
Potassium fertilizer
Mixed NP/NPK fertilizer Diammonium phosphate, nitrophosphate, ammonium
nitrophosphate, urea ammonium phosphate

Classification of Fertilizer
Fertilizer may be classified as natural fertilizer, biofertilizer and chemical fertilizer.
Fertilizers are generally classified according to chemical composition in four major
groups:
Nitrogenous fertilizers: Containing nitrogen as base element and is expressed by nitrogen
content.
Phosphatic fertilizers: Containing phosphorus as based element and is expressed by P2O5
content.
Potassium fertilizers: Containing potassium as base element expressed as K2O content.
Mixed fertilizer: Containing two or three major nutrient NP or NPK and generally
expressed in terms of NPK content.
Fertilizers are generally produced in solid granule form. However, liquid fertilizers
are also produced containing one or more nutrients along with trace element.

6.2 PROFILE OF FERTILIZER INDUSTRY

6.2.1 Global Fertilizer Industry

Fertilizer industry is playing important role in meeting the food grain demand.
Globally, innovation in agriculture with superproductive crops requiring more
nutrients have been the major driving force for growth of fertilizer industry.
Consumption of fertilizer has been consistently growing with increase of population
which is going to cross 7 billion in future. According to Agricultural Committee
Report, global fertilizer consumption is projected to reach 194.0 million tons with
an annual growth rate of 1.8% per year with average annual growth rates of 1.5%
N, 1.8% P and 3.0 K (Fertilizer Outlook 2013–2017, Patrick Hefferand Michel
Prudhomme, International Fertilizer Association (IFA) 81st IFA, annual conference
Chicago (USA) May 20–22, 2013). According to IFA total demand of urea (both
fertilizer and non-fertilizer) expected to be 195.2 million tons (Fertilizer demand
157.4 million tons) against 171.8 million tons (fertilizer demand 143.2 million tons)
in 2013. Global phosphate rock potential supply would be about 260 million tons in
2017. Global potassium demand is expected to be 37.4 million tons in 2017. World
fertilizer consumption is given in Table 6.3. World urea potential supply demand
(in million tons) is given in Table 6.4. Global fertilizer consumption per hectare is
given Table 6.5.
96 Chemical Process Technology

Table 6.3: World consumption of fertilizer

Nutrient 2012 million tons 2017 (forecast) MT
Nitrogen, N 107.8 115.8

Phosphorus, P2O5 41.3 45.0

Potassium, K2O 28.9 33.2

Total 178.0 194.0

Source: Hefler, IFA, June 2013.

Table 6.4: World urea potential supply demand (million tons)

2013 2017
Supply Capacity 198.4 236.3
Potential supply 182.1 207.4
Demand Fertilizer demand 143.2 157.4
Non-fertilizer demand 28.6 37.7
Total demand 171.8 195.2

Table 6.5: Global fertilizer consumption (kilogram per hectare of arable land)
Country 2012 Country 2012
United Kingdom 234.4 Canada 74.4
United States 131.1 India 163.7
United Arab Emirates 605.5 Japan 259.1
Australia 44.7 Malaysia 1570.7
Brazil 181.7 Pakistan 166.9
Bangladesh 278.6 South Africa 62.00
China 647.6 Sri Lanka 199.6
Source: FAO.

6.2.2 Indian Fertilizer Industry

Agriculture accounts for one fifth of GDP in India. It provides sustenance to thirds
of our population. There is substantial increase in agricultural production and
productivity. Food grain production has increased from 52 million tons in 1951–52
to about 259.32 million tons in 2011–12. Chemical fertilizer has played important role
in India’s green revolution and self-reliance in food grain production. As a result, the
annual consumption of chemical fertilizers has increased in nutrient terms (N, P, K). It
has increased from 0.7 lakh tons in 1951–52 to 277.39 lakh tons in 2011–12. Per hectare
consumption of fertilizer which was less than 1 kg in 1951–52 has risen to a level of
141.30 in 2011–12 (Ministry of Chemicals and Fertilizer Annual Report 2012–13). With
a very modest level of 52 million metric tons in 1951–52, food grain production has
Fertilizer Industry 97

increased to about 252.22 million tons in 2015–16 (Ministry of Chemicals and Fertilizer
Annual Report 2017–18).
India is the third largest producer and second largest consumer of chemical fertilizer in
the world. Indian chemical fertilizer industry started in 1906 with single superphosphate
production facility at Ranipet near Chennai. India started operation in a big scale since
1940s, when the Fertilizer and Chemicals Travancore of India Ltd. and the Fertilizer
Corporation of India were set up in Kerala and Bihar. Indian population continues
to increase and the provision of adequate supply of food remains a challenge. This
can be achieved only through further increase in yield, involving the enhanced use of
fertilizers. India has completed 100 years of manufacturing chemical fertilizer. In India,
there are 57 large sized fertilizer plants in the country manufacturing a wide range of
nitrogenous, phosphatic and complex fertilizers. Out of these, 29 units produce urea,
20 units produce DAP and complex fertilizers, 7 units produce low analysis straight
nitrogenous fertilizers and the remaining 9 units manufacture ammonium sulfate as a
by-product.
Commercial production of ammonia, a major raw material for production of urea,
was started in 1951 with first large scale ammonia plant using coke oven gas as raw
material. Only after a decade, another ammonia plant was started in Nangal in 1961
using electrolysis of water as source of hydrogen. However, it has changed the process
and raw material. Major nitrogenous fertilizer products were initially ammonium sulfate
and calcium ammonium nitrate. First urea plant based on once through process with 70
tpd capacity was commissioned in 1951 at Sindri. FCI Sindri plant was closed because
of lower capacity. In the beginning, capacity of both ammonia and urea plants was
less than 500 tpd. However, with various technological development in compressor,
synthesis gas feed stock, catalyst, modern energy efficient ammonia and urea plants
with higher capacity were commissioned in 1984–85 (Nand, 2008). In order to achieve
objectives of the food security bill, we have to increase food grain production from
263 million tons to 320 million tons by 2020.
India is the second largest producer of fertilizer in the world next to China.
Production of fertilizer was 34.6 million tons in 2012–13. Production and
consumption of fertilizer in India (lakh tons) is given in Table 6.6. Landmark in
Indian fertilizer industry is given in Table 6.7. Installed capacity and production
of fertilizer in ninth, tenth and eleventh plans is given in Table 6.8. Sector-wise
and nutrient-wise installed capacity of fertilizer manufacturing units in India as
on 31.03.2012 is given in Table 6.9. In terms of nutrient, the share of urea of total
nitrogen production was 85% in 2012–[Link] share of DAP, NP/NPKs and SSP to
total P2O5 production was 44%, 38% and 18%, respectively during 2012–13. Product-
wise share of urea and ammonium sulfate/calcium ammonium nitrate/ammonium
chloride of total fertilizer production was 60% and 2%, respectively. Product-wise
share of SSP, DAP/NP/NPKs were 12% and 26%, respectively (Chanda, TK and
Sati, K. “A relative review of all India capacity, production, dispatch, sale and stock
of fertilizers-2012–13”, Indian Journal of Fertilizer, August 2013, p.14). In order to
achieve the food grain production requirement of fertilizer by 2020 and 2030 is given
in Table 6.10. Various joint venture projects by India in various countries is given in
Table 6.11. Sector-wise capacity and production of all fertilizers during 2016–17 is
given in Table 6.12 (Ministry of Chemicals and Fertilizer, Annual Report 2017–18).
98 Chemical Process Technology

Table 6.6: Production and consumption of fertilizer in India (Lakh tons)

Year Production Consumption
2009–10 Urea 211.12 264.47
Diammonium phosphate (DAP) 42.47 103.91
NPK 80.38 82.2
Monoammonium phosphate (MOP) – 46.73
2010–11 Urea 218.81 282.10
DAP 35.37 112.68
NPK 87.7 102.98
MOP – 38.90
2011–12 Urea 219.84 290.37
DAP 39.63 111.85
NPK 77.70 113.63
MOP – 29.90
Source: Chemical Industry Annual Jan 2013, Ministry of Chemicals and Fertilizer.

Table 6.7: Landmarks in Indian fertilizer industry

Year Landmarks
1906 Fertilizer production
1943 Grow more food campaign launched in the wake of great famine in Bengal
1943 Fertilizers and Chemicals Travancore Ltd. (FACT)
1944 Central fertilizer pool created
1947 Independent India’s emphasis on improving domestic production of fertilizer
1957 Fertilizer control order enactment under Essential Commodities Act (ECA) 1955
1961 Fertilizer Corporation of India incorporated
1964 Government of India appointed Sivraman Committee to examine problems of fertilizer
1966 Inclusion of private trade in marketing of fertilizers
1967 GSFC one of the largest integrated fertilizer complexes started in Vadodara
1969 Shriram Chemicals and Fertilizer commissioned
1970 DIL, Kanpur
1971–72 Government of India brought control on distribution of fertilizer in view of shortage
after oil crisis
1971 Madras Fertilizer Limited (MFL), Chennai
1973 ZIL (Goa) was commissioned
1973 Fertilizer Movement Control Order enacted
1975 SPIC, Tuticoron
1976 MCFL, Mangaluru
1977 Retention Price and Subsidy Scheme was introduced
1978 IFFCO (Kalol) commissioned
Contd...
Fertilizer Industry 99

Table 6.7: Landmarks in Indian fertilizer industry (Contd...)

Year Landmarks
1978 NFL, Nangal
1979 NFL (Bhatinda) was commissioned
1982 GNFC (Bharuch) was commissioned
1982 RCF (Trombay) was commissioned
1985 RCF, Thal
1987 BVFCL Namrup III was commissioned
1989 IFFCO (Aonla) was commissioned
1988 Indogulf (Jagdishpur) was commissioned
1980–81 Block delivery scheme was introduced
1985 KRIBHCO (Hazira) commissioned
1992 Phosphatic and potassic fertilizers decontrolled
2003 Scrapping of retention price and introduction of group concession scheme for urea
2005 BVFCL Napmrup-II
2017 Revamping of Gorakhpur Fertilizer, Talchar Fertilizer by IIFCO

Table 6.8 Installed capacity and production of fertilizer in ninth, tenth and
eleventh plans (in lakh tons)
Particulars At the end of At the end of At the end of
ninth plan tenth plan eleventh plan
Nitrogen 120.58 120.61 120.61
Capacity
Phosphates 53.87 56.59 56.9
Nitrogen 107.68 115.78 122.59
Production
Phosphates 38.60 45.17 41.04

Source: Annual Report 2012–13, Department of Fertilizers, Ministry of Chemicals and Fertilizers,
Government of India.

Table 6.9: Sector-wise and nutrient-wise installed capacity of fertilizer manufacturing

units in India as on 31.03.2012
Capacity (lakh million tons) Percentage share
Sector
N P N P
Public sector 34.98 4.02 29.04 7.15
Cooperative sector 31.66 17.03 26.29 30.31
Private sector 53.78 35.14 44.67 62.54
Total 120.47 56.19 100.00 100.00

Source: Annual Report 2012–13, Department of Fertilizers, Ministry of Chemicals and Fertilizers,
Government of India.
100 Chemical Process Technology

Table 6.10: Fertilizer demand (million tons)

Nutrient demand meeting food grain demand by
Nutrient 2020: 277 million tons and 2030: 306 million tons
2020 Nutrient 2030 Nutrient
N 20.64 23.39
P2O5 10.32 11.69

K2 5.16 5.89

Total 36.12 40.97

Source: Suykumaran Nair, MP. Chemical Business March 2011, p.20.

Table 6.11: Joint venture projects in various countries

S. no. Joint venture project Product
1 Oman India Fertilizer Co (OMIFCO, Oman), 16.52 lakh tons urea and 2.48 lakh tons
Oman Oil Co, IFFCO, KRIBHCO ammonia
2 ICS Senegal (ICS Senegal and IFFCO) 5.5 lakh tons phosphoric acid
3 Indo-Jordan Chemicals, Jordan and SPIC India 2.2 lakh tons phosphoric acid
4 JPMC-IFFCO, Jordan 4.8 lakh tons phosphoric acid
5 IMACID, Morocco and Chambal and TCL 4.25 lakh tons phosphoric acid
6 Tunisia-India Fertilizer Company GCT (Tunisia), 3.60 lakh tons phosphoric acid
CIL and GSFC
Source: Ministry of Chemicals and Fertilizer Annual Report 2012–13

Table 6.12: Sector-wise capacity and production of all fertilizers during 2016–17 (lakh tons)
[Link]. Sector Urea DAP Complex fertilizer
1 Public sector 71.41 – 11.72
2 Cooperarative sector 66.81 17.87 23.5
3 Private sector 103.79 25.78 44.44
Total 242.01 43.65 79.66

Raw Material for Fertilizer Industry

Fertilizer industry uses wide variety of raw materials for production of nitrogenous,
phosphatic fertilizer and potassium-based fertilizer. Some of the important raw materials
for production of nitrogenous fertilizer are natural gas, naphtha, fuel oil, coal and lignite,
coke oven gas. At present, 80% of urea plants are based on natural gas, 9% on naphtha
while balance 11% capacity is based on fuel oil and LSHS as feedstock. Two coal-based
plants at Ramagundam and Talchar were closed due to technological obsolescence and
non-viability. However, the government of Odisha is again reconsidering to restart
the plant. Hydrogen content in natural gas is maximum about 25% while about 15%
in naphtha/fuel oil/LSHS, whereas very less in coal. As a policy now, conversion of
naphtha/FO/ISHS based urea units to natural gas and LNG was formulated in January
2004. The comparative cost of various feedstock is given in Table 6.13.
Fertilizer Industry 101

Table 6.13: Comparative cost of various feedstocks

Feedstock Price US$/MMBTU
Natural gas 5–9
LNG 10–16
Naphtha 30–35
Fuel oil 25–28
LSHS 25–28
Source: Chemical News, October 2012, p.42.

Rock phosphate and sulfuric acid are major raw material for phosphatic fertilizer.
Potassium sulfate, potassium chloride and potassium nitrate are source of potas-
sium. Some of the sources of sulfuric acid are elemental sulfur, pyrites and refinery gases.
Consumption of raw material for production of various fertilizers is given in Figure 6.2.

Fig. 6.2: Raw material consumption in fertilizer plant

Natural gas: Natural gas occurs as such and associated gas separated from crude oil.
Shale gas is also gaining importance as raw material due to availability of shale gas and
development of hydrofracturing and horizontal drilling. Methane which is the major
102 Chemical Process Technology

constituent in natural gas is used for the manufacture of fertilizer. Higher fractions
like ethane, propane, butane, etc. are separated before reforming process. Natural gas
availability and demand for fertilizer unit in 2011–12 is given in Table 6.14.

Table 6.14: Natural gas demand for fertilizer 2011–12

Natural gas allocation to fertilizer MMMSCMD 76.26
Natural gas availability MMMSCMD 57.06
Natural gas demand MMMSCMD 63.81
Source: Nair, 2011; Sukumaran MP. “Indian Fertilizer Industry: Challenges of growth” Chemical
Business, March 2011, p.17.

Fertilizer gas demand by 2015–16, 2021–22 and 2029–30 are 96.85, 107.85, 110.05
MMSWCMD, respectively (vision 2030 natural gas infrastructure in India report by
Industry group). Natural gas has been the preferred feedstock for the manufacture of
urea over other feedstocks like naphtha and fuel oil. Natural gas is clean and efficient
source of energy, energy efficient and more cost effective.
Natural gas is also traded globally in the form of liquefied natural gas (LNG) and
piped through cross country pipe lines. Compressed natural gas (CNG) is slowly
emerging as a low cost feedstocks for ammonia plant. The technology for CNG capture,
transport and delivery is proven. Transport and shipment of CNG is cheaper than LNG
up to distance of 3500 km. However, at longer distance, shipment of LNG is cheaper
(Sukumaran Nair, MP.” Ammonia industry—Today and tomorrow” Hydrocarbon
Processing, April 2006, p.47).
Shale gas: Shale gas is also a natural gas which is trapped within shale formations.
With development of horizontal drilling and hydrofracturing, shale gas availability
has increased tremendously and has revolutionized the petrochemical industry. Shale
gas has changed dramatically the gas scenario in US and Canada.
Coal-bed methane (CBM): Coal-bed methane offers tremendous potential due to high
coal reserves. With projected CBM reserves of about 92 TCF, government of India has
encouraged production of coal-bed methane. Already 33 blocks have been offered in
four bidding rounds (Chemical News, October 2012, p.42).
Naphtha: Naphtha is the light distillate fraction of crude oil having boiling point less
than about 215ºC. It is also produced during cracking processes which is called cracked
naphtha. A typical analysis of naphtha is made in Table 6.15.

Table 6.15: Typical analysis of naphtha

Specific gravity 0.7–0.72
Sulfur, wt % 11,500 ppm max.
Lead 5.0 ppb max.
Chloride 0.1 max.
ROE 5.0 ppm max.
Contd...
Fertilizer Industry 103

Table 6.15: Typical analysis of naphtha (Contd...)

Hydrocarbon
Paraffin 75% vol max.
Olefin 2%
Naphthene 36%
Aromatics 15%
C/H ratio 5.5–6.0
Boiling point 180ºC
Calorific value 10,500 (Kcal/kg)

Fuel oil: Fuel oil is the fraction obtained after separation of middle distillates like kerosene
and diesel. These are also obtained during various cracking processes. Earlier NFL units
started use of fuel oil as major source of ammonia. Some of the fuel oil based plants
are now using natural gas. Table 6.16 provides a typical analysis of fuel oil and heavy
stocks from Indian refineries.

Table 6.16: Typical analysis of fuel oil and heavy stocks from Indian refineries
Property LSHS EO
Specific gravity 0.92 0.896–0.928
Sulfur (wt%) 0.91 1.57–2.07
Ash (wt%) – 0.018–0.03
Carbon (wt%) – 84.67–86.64
C/H ratio 7.72 –
Calorific value (Kcal/kg) 10,360 9,421–9,932

Coke-oven gas: The gas obtained from carbonization of coal during production of coke
for blast furnace. The gas contains ammonia and other gases (Table 6.17). Ammonia
is neutralized by sulfuric acid to produce ammonium sulfate. SAIL is producing
ammonium sulfate and CAN in their units at Bhilai, Bokaro, Rourkela and Durgapur.

Table 6.17: Typical composition of coke-oven gas

Constituents H2 CH4 CnHm CO CO2 O2 N2
Volume percent 48.0 21.5 2.1 7.9 3.6 0.4 16.4
Net calorific value (Kcal/NM ) 3 3,750

Coal and lignite: Coal is one of the important raw materials for the production of ammonia.
However, cost of production and higher energy cost have been the major constraints. The
FCI’s two units based on coal started in Talchar (Odisha) and Ramagundam (AP) have
been closed because of economical reason. Now Talchar plant is going to be started by
IIFCO using natural gas as raw material. Typical analysis of coal and lignite is given in
Tables 6.18 and 6.19. Coal as feedstock for ammonia manufacture getting importance due
to uncertainty with long-term availability of hydrocarbons feedstock. Currently, about
70% of ammonia produced in China is based on coal. China has huge coal availability.
RCF is again planning to start coal based 2,700 TPD ammonia and 3500 TPD urea plant,
104 Chemical Process Technology

800 TPD nitric acid plant, and 100 TPD ammonia plants with estimated cost of ` 8000
crore in joint venture with Coal India Limited (Chemical News, October 2012, p.34).

Table 6.18: Typical composition of Table 6.19: Typical analysis of lignite

non-coking coal Constituents %
Analysis (wt.%) coal Moisture 50–56
Moisture 0.85–1.76 Ash 2–5
Ash 38.81–43.71 Volatile matter 24–26
Sulfur – Fixed carbon 20–24
Volatile matter 16.02–19 Sulfur 0.4–0.6
Fixed carbon 35.85–43.28 Bulk density 1.10–1.20
Hydrogen – Hard grove grindability 110–115
Calorific value (Kcal/kg) 3,994–4,395 Calorific value (Kcal/kg) (gross) 2,600–2,900

Indian Fertilizer Industry—Problems and Prospects

Raw material availability and price volatility, increasing cost of energy, stringent
environmental standards and imbalance use of fertilizer, efficiency and fertilize policy-
related issues are the challenges to fertilizer industry; volatility in the cost of raw materials
NG<LNG, naphtha, fuel oil, sulfur, sulfuric acid, phosphoric acid, rock phosphate, muriate
potash are major issues in fertilizer industry. Although there has been consistent reduction
in energy consumption in fertilizer industry, there are still chances of improvement. Better
feedstock and process technologies, together with improved operation and maintenance
practices and retrofitting, have resulted in significant reduction.

Raw Material Availability and Price Volatility

Supply of natural gas, dependence on high cost liquid fuels and volatility in the cost of
raw materials have been the major issues in price fluctuation of fertilizer industry: NG/
LNG, naphtha, fuel oil, sulfur, sulfuric acid, phosphoric acid rock phosphate. Muriate
potash forms 60–70% of turnover of fertilizer industry. Since 1980, raw material cost
has increased manifold, while the cost of fertilizer has increased marginally. Rock
phosphate quality in India is poor with low P2O5 content. Sulfur and potassium is
not available in abundant. So India depends on imported rock phosphate, sulfur and
potash. Entire requirement of potassic fertilizer (which is around five million tons) is
being met through imports.
Impact of energy: Although there has been consistent reduction in energy consumption
in fertilizer industry, there are still chances of improvement. Better feedstock and
process technologies, together with improved operation and maintenance practices
and retrofitting, have resulted in significant reduction. Energy consumption has been
reduced from 13.7 Gcal per ton in 1985–86 to 9.14 Gcal per ton 2003–04.
Environmental issues: Environmental standards are becoming more and more stringent
as fertilizer industry is one of the major polluting industries. Environmental pollution
control strategies are becoming more important. Some of the major issues related to
imbalance use of fertilizer are as follows:
• Eutrophication due to enrichment of nutrient
• Blue baby syndrome (methemoglobinemia) due to increase in nitrate level
Fertilizer Industry 105

• Soil acidification: Nitrogen-containing inorganic and organic fertilizers

• Heavy metal accumulation due to use of phosphatic fertilizer
• Radioactive element accumulation due to use of phosphatic fertilizer
• Atmospheric pollution due to methane emissions from crop fields (notably rice paddy
fields) are increased by the application of ammonium-based fertilizers
Imbalance Use and Low Fertilizer Use Efficiency
Fertilizers are still being used without giving adequate importance to soil nutrient
requirement resulting in higher consumption of fertilizers.
Fertilizer Policy-related Issues
Fertilizers are heavily subsidized in India. Urea is the major fertilizer consumed in India.
Except urea, all other fertilizer materials are placed under a nutrient-based subsidy
scheme. Urea is still kept under the administered pricing scheme which allows the
producers to sell urea at a price fixed by government.
Biofertilizer and Organic Fertilizer
Definition of biofertilizer as per Biofertilizers and Organic Fertilizers Covered in
Fertilizer (Control) Order, 1985 (Amendment, March 2006 and further amendment
November 2009).
Biofertilizers: Biofertilizers means the product containing carrier-based (solid or liquid)
living microorganisms which are agriculturally useful in terms of nitrogen fixation,
phosphorus solubilization or nutrient mobilization to increase the productivity of the
soil and/or crop.
Organic fertilizer: Organic fertilizer means substances made up of one or more
unprocessed material(s) of a biological nature (plant/animal) and may include unpro­
cessed mineral materials that have been altered through microbiological decomposition
process (Clause 2 NNA). “Non-edible de-oiled cake fertilizer” means substance obtained
as residue after oil extraction (by expeller and/or through solvent extraction) from
crushed seeds of non-edible oilseeds (such as castor, neem) for use in soil as fertilizer.
Biofertilizer holds lots of promise to meet nitrogen requirement of crops and also for
conversion of non–available or fixed phosphorus in soils to available form (Moley, SR.”
Biofertilizers, Biopesticides: Need/Scope and problems” Chemical Engineering World,
Vol 26, No. 11, 1991 p. 46). Biofertilizers contains living microbes which promotes growth
by increasing supply or availability of primary nutrients to host plant through natural
process of nitrogen fixation, solubizing phosphorus and stimulating plant through the
synthesis of growth promising substances ([Link]
(Vessey, JK. 2003 ”Plant growth promoting rhizobacteria as biofertilizers.” Plant soil
255, 2003 p. 571). Presence of microbes provides improvement in fertility, increases the
crop yield and reduces the health hazard of chemical nitrogen and phosphorus.
Different type of Biofertilizers are Nitrogen fixer bacteria: Rluzobium, Azotobacter, Mycobacterium,
Azospirillum, Bacillus. Blue green: Aabacena, Nostac, Tolypothrix, Anabaenopsis, phosphate
solubilizing microbes, Vesicular Arbscular Mycorrhiza fungi, Plant growth promoting:
Rhizobacteria, sulfur solubilizing microbes (http;//[Link]/
[Link]).
India has vast potential of organic waste resources which includes animal dung,
animal urine, bone metals, slaughter house waste, crop residue, other green biomass,
106 Chemical Process Technology

town garbage, sewage sludge are available which can be converted to biofertilizers by
quick degradation using microbial population.
General rules: Ministry of Agriculture, Department of Agriculture and Cooperation,
Government of India, New Delhi, vide their order Dated 24th March, 2006 included
biofertilizers and organic fertilizers under section 3 of the Essential Commodities Act,
1955 (10 of 1955), in Fertilizer (Control) Order, 1985. These rules were further amended
in respect of applicability, specifications and testing protocols vide Gazette notification
3 November, 2009.

Fertilizer (Control) Order 1985 as Amended up to June 2006

Fertilizer (Control) Act first came in 1957 essentially to regulate the sale, the price and
the quality of fertilizers in India. Since then nearly seventy and odd amendments were
carried out in the order. The revised FCO 1985, 2017 came into effect. The FCO contains
ScheduleI–IV, Form of Registration and Appendices. Content of various schedules
are given in Table 6.20. Some of the other important related order is The Fertilizer
(Movement Control) Order 1973 and The Essential Commodities Act 1973.

Table 6.20: The Fertilizer (Control) Order 1985

Schedule Content
Schedule I • Part A: Specifications of fertilizers
• Part B:Tolerance limit in plant nutrient and physical parameters for various
fertilizers
Schedule II • Part A: Procedure for drawl of samples of fertilizers.
Methods of analysis of fertilizers
• Part B: Methods of analysis of fertilizers
Schedule III • Part A: Specification of biofertilizer
• Part B: Tolerance limit of biofertilizers
• Part C: Procedure for drawl of sample of biofertilizers
• Part D: Methods of analysis of biofertilizers
Schedule IV • Part A: Specifications of organic fertilizers
• Part B: Tolerance limit of organic fertilizers
• Part C: Procedure for drawl of sample of organic fertilizers
• Part D: Methods of analysis of organic fertilizers
Forms of Registration
Appendices Important notifications/order regarding sale of small quantities of fertilizers
for gardening purpose-Exemption to dealers, Marking on containers,
Equipments required for Laboratories, Exemptions of the Food Corporation of
India, Summary trial for contravention of FCO; Fees for obtaining certificate;
Controller(s) of fertilizers and Central Fertilizer Committee; Specification of
Urea (granular) from Oman, specifications of Provisional Fertilizers

As per Ministry of Agriculture Farmers Welfare 2017 Schedule-1 Part A specifications

of straight run nitrogenous fertilizer, straight phosphorus fertilizers and straight
potassium fertilizers are given Tables 6.21 to 6.23.
Fertilizer Industry 107

Table 6.21: Specification straight nitrogenous fertilizers

Ammonium sulfate
Moisture percent by weight, maximum 1.0
Ammoniacal nitrogen percent by weight, minimum 20.5
Sulfate sulfur (as S) percent by weight, minimum 23.0
Free acidity (as H2SO4) percent by weight, maximum 0.025
Arsenic as (As2O3) percent by weight, maximum 0.01
Ammonium chloride
Moisture percent by weight, maximum 2.0
Ammoniacal nitrogen percent by weight, minimum 25.0
Chloride other than ammonium chloride (as NaCl) percent by weight, maximum 2.0
Calcium ammonium nitrate
Moisture percent by weight, maximum 1.0
Total amount of ammoniacal nitrogen and nitrate percent by weight, minimum 25.0
Ammoniacal nitrogen percentage by weight, minimum 12.5
Calcium nitrate percent by weight, maximum 0.5
Particle size: Minimum 90% of the material shall be retained between 1 mm and 4
mmm IS sieve
Urea (46%)
Moisture percent by weight, maximum 1.0
Total nitrogen percent by weight on dry basis, minimum 46.0
Biuret percent by weight, maximum 1.5
Particle size: Minimum 90% material shall be retained on 1.0 mm and 2.8 mm IS sieve
Urea supergranulated
Moisture percent by weight, maximum 1.0
Total nitrogen percent by weight on dry basis, minimum 46.0
Biuret percent by weight, maximum 1.5
Particle size: Minimum 80% material shall be retained on 13.2 mm and 9.5 mm IS sieve
Urea (granular)
Moisture percent by weight, maximum 1.0
Total nitrogen percent by weight on dry basis, minimum 46.0
Biuret percent by weight, maximum 1.5
Particle size: Minimum 90% material shall be retained on 4 mm and1 mm IS sieve
Urea ammonium nitrate (32% N) liquid
Total nitrogen (urea, ammoniacal and nitrate, % by weight on dry basis, minimum 32.0
Urea nitrogen, % by weight, maximum 16.5
Nitrate nitrogen percent by weight 7.5
Specific gravity (at 15ºC) 1.3–1.5

Neem-coated area
Moisture percent by weight, maximum 1.0
Total nitrogen percent by weight on dry basis, minimum 46.0
Biuret percent by weight, maximum 1.0
Neem solution in benzene, percent by weight, minimum 1.5
Particle size: Minimum 90% material shall be retained between 2.0 mm and 4.0 mm
IS sieve
Source: Ministry of Agriculture and Farmers Welfare, 2017.
108 Chemical Process Technology

Table 6.22: Specification of straight phosphatic fertilizers

Rock phosphate
Total phosphorus (as P2O5) 18.0
Particle size: Minimum 90% retained shall pass through 0.15 mm IS sieve and 10%
of material pass through 0.25 mm IS sieve
Single superphosphate (16% P2O5 powdered)
Moisture percent by weight, maximum 12.0
Available phosphorus as (as P2O5) percent by weight, minimum 16.0
Total phosphorus (as P2O5) percent by weight, minimum 14.5
Sulfate sulfur (as S) percent by weight, minimum 11.0
Free phosphoric acid phosphorous (as P2O5) percent by weight, maximum 4.0

Single superphosphate (16% P2O5 granulated)

Moisture percent by weight, maximum 5.0
Total phosphorus (as P2O5) percent by weight, minimum 16.0
Sulfate sulfur (as S) percent by weight, minimum 11.0
Free phosphoric acid phosphorus (as P2O5) percent by weight, maximum 4.0
Particle size: Minimum 90% material shall be retained between 1.0 mm and
4.0 mm IS sieve
Triple Superphosphate
Moisture percent by weight, maximum 12.0
Total phosphorous (as P2O5 ) percent by weight, minimum 46.0
Sulfate sulfur (as S) percent by weight, minimum 42.5
Free phosphoric acid phosphorus (as P2O5) percent by weight, maximum 3.0

Superphosphoric acid (70% P2O5 liquid)

Total phosphorus (as P2O5) percent by weight, minimum 70.0
Polyphosphate (as P2O5) percent by weight, minimum 19.0
Methanol insoluble matter percent by weight, maximum 1.0
Magnesium as MgO percent by weight, maximum 0.5
Specific gravity (at 24ºC) 1.95–2.0

Source: Ministry of Agriculture and Farmers Welfare, 2017.

Table 6.23: Specification of various NPK fertilizers

Particulars NPK NPK NPK NPK NPK NPK
15-15-15* 17-17-17 19-19-19 14-35-14 10-26-26 12-32-16
Moisture, max. 1.5 1.5 1.5 1.0 1.0 1.0
Total nitrogen, min. 15.0 17.0 19.0 14.0 10.0 12.0
Ammoniacal nitrogen, min. 7.5 5.0 5.6 12.0 7.0 9.0
Nitrogen in the form of urea, – 12.0 13.4 2.0 3.0 3.0
max.
Neutral ammonium citrate- 15.0 17.0 19.0 35.0 26.0 32.0
soluble phosphate as (P2O5),
min.
Contd....
Fertilizer Industry 109

Table 6.23: Specification of various NPK fertilizers (Contd...)

Particulars NPK NPK NPK NPK NPK NPK
15-15-15* 17-17-17 19-19-19 14-35-14 10-26-26 12-32-16
Water soluble phosphates as 4.0 14.5 16.2 29.0 22.1 27.2
(P2O5), min.
Water-soluble potash as 15.0 17.0 19.0 14.0 26.0 16.0
(K2O), min.
Particle size: Shall be such that 90% of the material shall be between 1 and 4 mm IS sieve and not
more than 5% shall pass through 1 mm IS sieve.
Source: Fetilizer Association of India, 2001.

BIBLIOGRAPHY
1. Annual Report 2012–13 Department of Fertilizer Ministry of Chemicals and Fertilizers, Govt of
India.
2. Annual Report Ministry of Chemicals and Fertilizer 2012–13.
3. Chanda, TK, Sati K. “A relative review of All India capacity, production, dispatch, sale and stock
of Fertilisers—2012–13” Indian Journal of Fertilizer August, 2013, p.14.
4. Chemical Industry Annual Jan, 2013.
5. Chemical News October, 2012, p.42.
6. Chemical News October, 2012, p.34
7. Fertilizer Outlook 2013–2017 Patrick Heffer and Michel Prud’-homme, International Fertilizer
Association (IFA) 81st IFA Annual Conference, Chicago (USA) May 20–22, 2013.
8. Handbook of Fertilizer Association of India 2001.
9. Helfer, IFA, June 2013.
10. [Link] Fertilizer, Vessey JK, 2003, plant.
11. [Link] [Link] Chemical News, October, 2012, p.34.
12. Ministry of Agriculture and Farmers Welfare, FCO, 2017 Amendment of FCO 1985.
13. Moley SR. “Biofertilizers, Biopesticides: Need/Scope and problems” Chemical Engineering
World, Vol 26, No. 11, 1991 p.46
14. Nand S, Goswami M. “Recent efforts in Energy conservation in Ammonia and Urea Plants.”
Indian Journal of Fertilizers, December, 2008, p.17
15. Sukumaran MP. “Indian Fertilizer Industry: Challenges of growth.” Chemical Business March
2011, p.17
16. Sukumarannair MP. “Ammonia industry—today and tomorrow.” Hydrocarbon Processing,
April 2006, p.47
17. Yara Fertilizer Industry Hand book, February 2014 [Link].com5.0
7
Nitrogenous Fertilizer and
Nitric Acid

7.1 INTRODUCTION
Nitrogenous fertilizer has played important role in the development of the agricultural
sector. Ammonia is the major raw material for production of nitrogenous fertilizer. Some
of the intermediates required for nitrogenous fertilizer are nitric acid, sulfuric acid, and
phosphoric acid. Some of the important nitrogenous fertilizers are urea, ammonium
nitrate, ammonium sulfate, ammonium sulfate nitrate, calcium ammonium nitrate,
and ammonium chloride. Apart from these, some of the fertilizers in the form of NPK
are also manufactured. Details of the nitrogenous phosphatic fertilizer are given in
Chapter 8. Synthesis gas (CO and H2) and N2–H2 are two major requirements for the
manufacture of ammonia. Urea is made from ammonia and carbon dioxide. Detail of
the raw material requirements for fertilizer industry is given in Chapter 6. Feedstocks
for synthesis gas production and process of synthesis gas are given in Table 7.1. Raw
material requirement for ammonia, urea and other nitrogenous fertilizer is given in
Table 7.2. Summary of process flow diagram for manufacture of different nitrogenous
fertilizer is given Figure 7.1.

Table 7.1: Feedstocks and process of synthesis in gas production

Feedstock Process
1. Water Electrolysis
2. Hydrogen rich refinery gas Steam reforming
3. Natural gas Steam reforming
4. Naphtha Steam reforming or partial oxidation
5. Crude or residual oil (fuel oil) Partial oxidation
6. Coal and carbonaceous material Water gas reaction and/or partial oxidation
7. Coke-oven gas Reforming or partial oxidation

110
Table 7.2: Raw material consumption in nitrogenous fertilizer industry

Raw material/ KCl Present energy Future energy

Sl. intermediates Rock H3PO4 Gyp-
NH3 CO2 H2SO4 HNO3 (as 60% consum-ption con­sumption
no. phosphate (as P2O5) sum
Fertilizer product K2O Gcal/MT Gcal/MT

1a Ammonium sulfate (AS) 0.27 – – 0.78 – – – – 1–2 0.8

1b AS from gypsum route 0.27 0.38 – – – – – 1.80 4–5 3

2 CAN (25%N) 0.16 – – – – 0.59 – – 4 3

3 Urea 0.58 0.75 – – – – – – 6–9 5–5.5

6 UAP ([Link]) 0.37 – – – 0.29 – – – 5–6 2

7 DAP ([Link]) 0.24 – – – 0.48 – – – 2–3 0.5

8 NPK ([Link]) 0.18 – – – 0.38 – 0.25 – – –

9 NPK ([Link]) 0.22 – – – 0.18 – 0.30 – – –

10 NPK ([Link]) 0.24 – – – 0.20 – 0.33 – 2–3 1

Nitrogenous Fertilizer and Nitric Acid

11 NPK ([Link]) 0.15 – – – 0.34 – 0.28 – – –

12 NPK ([Link]) 0.10 – – – 0.16 0.36 0.26 – – –

Requirement of raw materials/intermediates for (per ton)

(A) AMMONIA (NH3): NG 900 NM3 or, Naphtha 0.83 MT Fuel 0:1 0.9 MT
Coal 3.62 MT
(B) Sulfuric acid (H2SO4): Sulfur 0.34 MT or Pyrites 0.89 MT
(C) Phosphoric acid (H3PO4) (as P2O5): Rock phosphate: 3.3 MT and H2SO4: 2.82 MT
(D) Nitric acid (HNO3): NH3: 0.29 MT

111
112 Chemical Process Technology

Fig. 7.1: Process flow diagram for manufacture of nitrogenous fertilizer

7.1.1 Ammonia Production

According to IFA 2013 global capacity survey global ammonia capacity was 204.1 million
tons which is likely to increase by 10% to 247.2 million tons in 2017. The global production
of ammonia is dominated by China with 32% of total global production of ammonia
in 2012; the other major producers are India 9%, US 7% and Russia 7% (USGS, 2013).
Domestic production of ammonia is about 13.25 million tons in 2012. Other sources
are imported ammonia 1.67 million tons and ammonia in imported DAP, MAP and urea
is 4.05 million tons. Its uses and applications in various sectors are given in Figures 7.2
and 7.3.
Nitrogenous Fertilizer and Nitric Acid 113

Fig. 7.2: Uses of ammonia, urea and nitric acid

7.1.2 Characteristics of Ammonia

Ammonia (NH3) is a colorless alkaline gas. It is lighter than air and possesses a pungent,
suffocating odor. It is highly water-soluble and is soluble in chloroform and ether. It
is easily liquefied under pressure. Characteristics of ammonia are given in Table 7.3.

Table 7.3: Characteristics of ammonia

State: Colorless alkaline gas. Odor: Pungent and suffocating, Taste: Bitter. Corrosivity: Corrosive.
BP: 33.35ºC. MP: –77.7ºC. Sp. gravity: 0.680 at –33ºC. Vapor pressure at 15ºC: 630 KPa. Autoignition
temperature: 651ºC. Flammable limits: LEL 15%, UEL 28% (in air 15–18% by volume). Odor
threshold: 0.6–53 ppm (detection).
Solubility in water: Very highly
Short-term exposure limit (STEL): 35 ppm; 24 mg/m3. Fatal doss: 5000 ppm.
Time-weighted-average (TWA) exposure limit: 17 mg/m3 (25 ppm).
National Institute for Occupational Safety and Health (NOISH) REL: 25 ppm TWA; 35 ppm STEL.
American Conference of Governmental Industrial Hygienists (ACGIH): 25 ppm TLV, 35 ppm
STEL.
OSHA permissible exposure limit: 35 ppm STEL, 300 ppm DLH.
Reactivity: Ammonia is alkaline and caustic, and is a powerful irritant. It is incompatible or reactive
with strong oxidizers, acids, halogens, salts of silver and zinc. It is corrosive to copper and galvanized
surfaces. Liquid ammonia attacks some forms of plastics, rubber and coatings.
Warning properties: Odor and dense appearance of gas are distinctive warning properties.
Fire extinguishing materials: Water spray, CO2, foam, halon, dry chemical, any “ABC” class.
114 Chemical Process Technology

Fig. 7.3: Uses of ammonia

7.1.3 Raw Materials for Ammonia

Natural gas/assosiated gas, naphtha, fuel oil, coal, coke oven gas, water are some of the
major raw materils for ammonia manufacture. Presently major feedstocks for ammonia
manufacture is natural gas which accounts for 84.5% of total feedstock. First step in
the manufacture of ammonia is production of synthesis gas CO and H2 and nitrogen
and hydrogen. Nitrogen comes from air. Detail of the process for the manufacture
and raw material is given in Table 7.4. Consumption of natural gas, naphtha, fuel
oil and LSHS in fertilizer sector was about 15.0 billion cubic meter, 0.84 million tons
and 1.2 million tons, respectively. Share of natural gas, naphtha 5.3 and fuel oil for
production of ammonia was 84.55%, 5.35%, 10.2%, respectively in 2009–10. The relative
plant cost based on different feedstocks would be of the following order:
Gas : 1.0
Naphtha : 1.15
Fuel oil : 1.60
Coal : 2.00
Nitrogenous Fertilizer and Nitric Acid 115

Table 7.4: Process steps in production of synthesis gas and ammonia

Process steps Reaction Process condition
Desulfurization:
1st stage C2H5SH + H2 → H2S + C2H6 Al-Co-Mo
C6H5SH + H2 → H2S + C6H6 Al-Ni-Mo
C4H4SH + 3H2 → H2S + C4H9 Catalyst
CS2 + 4H2 → 2H2S + CH4 350–400ºC
COS + H2 → H2S + CO
CH3SC2H5 + H2 → H2S + CH4 + C2H4

2nd stage H2S + ZnO → ZnS + H2O Zinc oxide absorbent 200–500ºC

Steam reforming C H + 1/4(4n-m) H O → 1/8(4n + m)CH + Nickel catalyst 800ºC

n m 2 4
two stages 1/8(4n–m) CO2
CH4 + H2O → CO + 3H2
CO + H2O → CO2 + H2
CO-shift CO + H2O → CO2 + H2 Magnetite crystals stabilized
conversion using chromium oxide.
Low temperature shift catalyst:
copper oxide supported on zinc
oxide and alumina.
CO2 removal K2CO3 + CO2 + H2O → 2KHCO3 Vetrocoke: K2CO3 +AS2O3 +
by K2CO3 or glycine
2KHCO3 → K2CO3 + H2O + CO2
methanol amine
RNH2 + H2O + CO2 → (RNH3) HCO3 (RNH3) Carsol: K2CO3 + additives
HCO3 → RNH2 + H2O + CO2 Benfield: 25–30% K2CO3 +
Diethanolamine and additive
Methanation CO + 3H2 → CH4 + H2O Nickel-aluminum catalyst
250–350ºC
CO2 + 4H2 → CH4 + 2H2O
0.5 O2 + H2 → H2O
Ammonia N2 + 3H2 → 2NH3 Iron oxide with promoters
synthesis Low pressure 10–16 MPa
Medium pressure 20–50 MPa
High pressure 80–100 MPa
Temperature 400–500ºC
Radial or cross flow ammonia
converter
Source: Mall ID. Petrochemical process technology, 2007.

7.1.4 Process Technology for the Manufacture of Ammonia

Major raw material requirement for ammonia are hydrogen and nitrogen. Nitrogen
which is obtained from nitrogen. Some of the processes used for the manufacture of
hydrogen are electrolysis of water and from synthesis gas using steam reforming, partial
oxidation and gasification of coal or petro coke.
Electrolysis process: In this process hydrogen is produced by electrolysis of water.
Hydrogen thus produced is reacted with oxygen obtained from air separation to get
ammonia. This process is highly energy intensive. Typical power consumption is about
116 Chemical Process Technology

4.3 kWh/m3 of hydrogen which corresponds to 8600 kWh/MT of ammonia. At the

same time additional power is required for separation of air. However, there has been
recent interest in this process for production of hydrogen at low capacity. By-product
of electrolysis are oxygen and heavy water.
Partial oxidation: Partial oxidation is usually used for naphtha, fuel oil and other heavier
hydrocarbons. In this process hydrocarbon and oxygen are burnt in a reactor where
steam is added to moderate the temperature. Oxygen used in the process is obtained
from separation of air. Some of the advantage of partial oxidation process is flexibility of
feedstock, no prior desulfurization, no sensitivity to catalyst, all reforming accomplished
in single stage, lower hydrocarbon for process and fuel, pure synthesis gas because of
nitrogen wash.
Steam reforming: Steam reforming of natural gas is commonly used for producing
large quantity of ammonia. In refineries steam reforming of naphtha is also done for
production of hydrogen. Steam reforming process is proceeds in two stages using
primary and secondary reformer. Desulfurized naphtha or natural gas is subjected to
steam reforming which is followed by second stage reforming. Details of this process
is given in section 7.1.5.
Coal gasification: Coal gasification is another route for production of synthesis gas.
Because of availability of coal in large quantity, coal gasification process is gain getting
importance especially for production of gasoline and olefin. Following three processes
are used in coal gasification process:
• Lurgi process (Fixed bed)
• Winkler process (Fluidized bed)
• Koppers–Totzek process (Entrained bed)
The process consists of gasification of coal in two stages. In first stage, the coal is
first carbonized and finally gasified by the oxygen and steam entering at the bottom.
Two of the plants at Talcher in Odisha and Ramagundam in Andhra Pradesh, which
were based on coal gasification, have been closed because of economic consideration.
Talcher plant is now going to be started by IIFCO based on gas.

7.1.5 Ammonia Manufacture by Steam Reforming Process

The various steps involved in the production of synthesis gas and ammonia are:
• Desulfurization of natural gas in two stages
• Steam reforming of natural gas and naphtha
• CO-shift conversion
• CO2 removal by absorption in K2CO3 or MEA
• Purification for removal of traces of CO and CO2 by methanation or nitrogen wash
(in case of partial oxidation)
• Ammonia synthesis.
Reactions involved and process conditions are given in Table 7.4.
Desulfurization
The desulfurization process involves primary and secondary desulfurization. First the
NG with recycle gas is preheated to 390–400ºC in the waste heat section of primary
reformer, is passes over the hydrogenation catalyst. Sulfur containing compounds are
Nitrogenous Fertilizer and Nitric Acid 117

converted into H2S in the presence of H2 and at temperature of 390ºC using zinc oxide.
In the hydrogenation vessel the following typical reaction takes place.
In second stage, the process gas passes through the absorption vessel where H2S is
absorbed in ZnO in two stages. The normal operating temperature is 300–400ºC but
also at low temperature catalyst react H2S as ZnO + H2S = ZnS + H2O
At normal operating temperature catalyst l also react with carbonyl sulfide as:
ZnO + COS ZnS + CO2
The sulfur pickup rate is very dependent on temperature, porosity and surface area
of the zinc oxide pellets.
Process flow diagram for the manufacture of synthesis gas and ammonia is given in
Figure 7.4.

Fig. 7.4: Synthesis gas and ammonia by stem reforming and partial oxidation
Reforming section: Steam reforming consists of two-stage reforming: Adiabatic pre-
reforming and tubular reforming. In the primary reforming section a gas containing
the necessary compounds for preparation of ammonia synthesis gas is produced by
steam reforming of natural gas/naphtha and steam and addition of air.
Steam reforming of HC can be described by the following reactions:
CnH2n+2 + 2H2O Cn-1H2n + CO2 + 3H2–Q
CH4 + 2H2O CO2 + 4H2–Q
CO2 + H2 CO + H2O–Q
118 Chemical Process Technology

Adiabatic performing: Adiabatic performing uses nickel based on magnesium alumina

spinal oxide. The catalyst is characterized by high reforming activity, improved tolerance
for sulfur and resistance to carbon (Sukumar Nair” Ammonia industry—today and
tomorrow” Hydrocarbon Processing, April 2008, p.47). The performing process reduces
the burden on tubular reforming and improves the efficiency of total reforming. In the
performer endothermic reforming reaction takes place which is followed by exothermic
methanation.
Primary and secondary reforming: The steam reforming takes place in two reformers:
Primary reformer and secondary reformer in presence of nickel catalyst. Reforming
reaction is endothermic. In the primary reformer, heat is supplied indirectly by firing.
In the secondary reformer, the heat is supplied as reaction heat by mixing air into the
gas. In the primary reformer preheated HC after desulfurization and steam mixture,
preheated to 500ºC, passes downward through vertical tubes filled with nickel catalyst.
The tubes are placed inside a fired heater, where sensible heat and heat of reaction are
transferred by radiation from a number of wall burners to the tubes.
In order to ensure a complete combustion of the flue gas, the burners must be operated
with an excess of air. A reducing atmosphere is always avoided as it may be harmful
to the catalyst. The gas leaves the reformer tubes at a temperature of about 800ºC. Then
air is mixed into the partly reformed gas and reacts in the upper empty space of the
secondary reformer. The reaction here is exothermic and the necessary reaction heat
is provided by internal combustion air. Stoichiometric quantity of air is provided to
introduce the required nitrogen amount needed for ammonia synthesis (Khalid, 209).
From the empty space the gas passes the catalyst bed in the lower part of the reformer
where reforming reaction is completed with simultaneous cooling of the gas. The catalyst
in the second reforming is nickel oxide on alumina. It has high thermal resistance and
stable activity. The outlet temperature is about 990ºC and the methane concentration
approximately 0.3 mole% (dry basis). The outlet gas from the reforming section contains
approximately 13 mole% CO2 and 7.3 mole% in the dry gas. Consequently, there is a
theoretical risk of carbon formation according to reaction:
2CO CO2 + C
High pressure steam is generated by cooling the process gas from secondary reformer.
Shift convertor: The cooled reformed gases from steam reforming process contain 12–15%
CO with balance of hydrogen, nitrogen and carbon dioxide and small amount of argon
and methane. The CO is converted to CO2 in two shift converters: high temperature
shift converter (HTSC) and low temperature shift converter (LTSC), in the presence of
the catalyst. The temperature is about 370–400ºC in HTSC and 200–220ºC in LTSC. The
catalyst in the CO shift converter is iron oxide/chromium oxide in HTSC and copper
oxide/zinc oxide in LTSC. The residual CO content is around 0.2–0.4%.
CO2 removal: The gas from the CO shift converter is cooled and most of the steam is
condensed before entering the CO2 removal section. CO2 is removed by absorption in
hot aqueous solution containing approximately 25-weight% K2CO3 (Potash), activator-
glycine and V2O5–corrosion inhibitor. Hot solution increases the rate of absorption and
also maintain the temperature same as in regenerator. Some of the other absorbent
MEA, recti sol (methanol), Catacarb. Some of the typical absorbents for carbon dioxide
absorption processes. Solutions are given in Table 7.5.
Nitrogenous Fertilizer and Nitric Acid 119

Table 7.5: Carbon dioxide absorption processes and typical absorbent solution
Various absorbents Composition of absorbing media
Vetrocoke Potassium carbonate (20%) and arsenic trioxide (15%)
Benfield Potassium carbonate (30%)
Diethanolamine (3%) and arsenic trioxide (0.3–0.9%)
Monoethanolamide (MEA) MEA (15–20%)
Recti sol Methanol
Catacarb Potassium carbonate, diethanolamine, potassium carbonate and glycine

Several innovation has been done in the CO2 removal system for increasing the
absorption efficiency reduced CO2 slip, reduced energy consumption required to
regenerate CO2, effectively reduce corrosion of the plant equipment and environmentally
friendly solvent system and activators for absorption (Sukumar Nair, 2006).
Methanation: After the CO2 removal unit remaining traces of CO and CO2 are removed in
the methanation in presence of nickel catalyst by converting them to methane. CO and
CO2 must be removed, since these compounds are poisonous for ammonia synthesis
catalyst.
CO + 3H2 CH4 + H2O + Q
CO2 + 4H2 CH4 + 2H2O + Q
Low temperature, high pressure and low steam content tend favor the methane
formation. After methanation CO and CO2 become less than 10 ppm. Operating
temperature of methanation is 280–350ºC. Methane is an inert gas in the ammonia
synthesis reaction. Water formed during the process is removed by cooling and
condensing.
Ammonia Synthesis
Ammonia synthesis takes place in ammonia convertor in the presence of according to
the reaction:
N2 + 3H2 2NH3 + H = – 91.8 kJ/mol Kcal/kg
The heat liberated during reaction is utilized for producing HP steam. The ammonia
reaction is favored by high pressure and low temperature tends to favor ammonia
formation. The optimum pressure and temperature are 220 kg/cm2 and 370–520ºC,
respectively. Catalyzed reaction rates are increased by higher temperature and pressure.
Most ammonia synthesis loops use converters with multiple beds with inter bed cooling.
According to the fact that the reaction is an equilibrium reaction, only a partial
conversion can be obtained and it is necessary to recycle the unconverted synthesis gas
to the convertor. Approximately 30% of the hydrogen and nitrogen contained in the
synthesis gas at convertor inlet is converted into ammonia per pass. In addition to the
convertor the synthesis loop includes a recirculating compressor as well as equipment
for steam generation, boiler feed water preheat, for cooling of the synthesis gas and
condensation as well separation of ammonia. The convertor effluent gas is cooled in a
number of steps:
• In the waste heat boiler (455–350ºC)
• Boiler feed water preheater (350–274ºC)
• Hot heat exchanger, two chillers-12ºC
120 Chemical Process Technology

The ammonia converter is one of the most important units in ammonia plant
because its performance affects the ammonia production and operating cost (catalyst
and energy consumption) (Lin, et al. 1999). A breakthrough in ammonia synthesis
technology is development of ruthenium metal-based catalyst on a proprietary graphite
structure, which has an intrinsic activity up to 20 times higher than conventional iron
based catalyst. Another development in ammonia catalyst technology is the granular
promoters as Ca, aluminum, potassium and rare earth elements with higher activity at
low temperature and pressure, faster reduction rates and increased mechanical strength
and resistance to poisons.
Advances in ammonia technology: Ammonia processes have undergone significant
changes during the past. The major focus on the development has been the improving
production economics through improvement in process efficiency and catalyst. Before
1942, synthesis gas for ammonia was manufactured from water gas and electrolysis of
water. Hydrogen obtained from electrolysis of water is mixed with nitrogen obtained
from liquefaction of air. However, with the development of partial oxidation and
steam reforming above processes have disappeared (Nandini Chemical Journal March
2002, p.25). From techno-economic reason and availability of natural gas, major area of
technology development in ammonia production have been concentrated around natural
gas based ammonia plant. Due to high cost of production and energy consumption
gasification of heavier hydrocarbon feedstocks fuel oil, coal has not made much
commercial headway in the last decade (Kapur, 1996). Some of the major advances in
ammonia production are as follows:
• Higher capacity plants with less energy consumption
• Raw material changes from naphtha fuel oil to natural gas, use of CNG and LNG,
shale gas, coal bed methane
• High efficiency compression equipment with advent of centrifugal compressors
• Introduction of adiabatic performer
• Developments in the reformer tube metallurgy
• Improved CO2 absorption efficiency with new absorbents
• Improvement in ammonia catalyst and ammonia converter configuration.
Modern ammonia converters are designed on the radial flow concept which has
inherently low pressure drop, high conversion per pass, heat removal between catalyst
beds and enable smaller sized catalyst (Sukumar Nair, 2006). Some of the catalyst in
ammonia manufacture is given in Table 7.6.

Table 7.6: Catalyst in ammonia manufacture

Operating temperature
Sl. no. Service Catalytic system
range (ºC)
1. Hydrodesulfurization CoO-MoO-Al2O3 350–400
2. Desulfurization ZnO 350–400
3. Performing NiO–Al2O3 400–500
4. a. Primary gas reforming NiO–Al2O3 700–850
b. Secondary naphtha reforming NiO–support 700–800
Contd...
Nitrogenous Fertilizer and Nitric Acid 121

Table 7.6: Catalyst in ammonia manufacture (Contd...)

Operating temperature
Sl. no. Service Catalytic system
range (ºC)
5. Secondary reforming NiO–Al2O3 900–1200

6. High temperature shift Fe2O3–Cr2O3 350–550

Fe2O3–Cr2O3–CuO 300–480

7. Medium temperature shift CuO–ZnO–Cr2O3 260–350

8. Low temperature shift CuO–ZnO–Al2O3 180–250

9. Methanation NiO–Al2O3 280–350

10. Ammonia synthesis Fe3O4–K2O–Al2O3–CaO 350–550

7.2 UREA (NH2CONH2)

Urea is one of the most important nitrogenous fertilizer and accounts for total nitrogenous
fertilizer consumption. Some of the important uses of urea as petrochemical feedstock
is in the manufacture of urea formaldehyde, hydrazine, melamine, fire retardant, paint,
pharmaceuticals, dyes, etc.
Urea is made by reaction of ammonia with carbon dioxide at 180–190ºC and 160–170
kg/cm2 pressure in a highly corrosion resistant reactor. The reaction takes place in two
stages:
2NH3 CO2 = NH2COONH4 H = –155 MJ/kg mole

NH2COONH4 NH2CONH2 + H2O H = 42 MJ/kg mole

The first reaction is highly exothermic and rapidly goes to completion whereas
the second reaction is endothermic and is relatively slow. Some of the urea synthesis
processes are once through processes, partial recycle process and total recycle process
(Fig. 7.5). Some urea production technologies are given in Figure 7.5. Due to economical
reason urea is made by total recycle process.
The process steps involved in the manufacture of urea are:
• Urea synthesis and high pressure recovery
• Urea purification and low pressure recovery
• Urea concentration
• Urea prilling
• Urea bagging and storage.
Different processes employ different operating parameters and molar ratio of feed in
order to achieve the desired degree of conversion. They differ principally in the manner
the converted reactants are recovered and recycled. The separation of the converted
reactants from the urea solution is either by reactor effluent under successive stages
of pressure reduction and recycling back to the reactor (conventional processes) or by
reducing the partial pressure of synthesis mixture by injecting NH3 or CO2 followed
by heating of the separated mixture recycled to the reactor stripping processes. Major
urea production technologies based on the stripping processes are Snampragettiammonia
process, Stamicarbon’s CO2 stripping process, MTC total recycle ‘C’ improved process,
122 Chemical Process Technology

Toyo Engineering’s advance cost and energy saving (ACES) process, and heat recycle
used process for Urea Technologies Inc. Typical industrial specification of urea is given
in Table 7.7.

Fig. 7.5: Urea production technologies

Nitrogenous Fertilizer and Nitric Acid 123

Table 7.7: Specification of typical technical grade urea

Specifications Nitrogen 46% by weight, min.
Moisture 0.5% by weight, max.
Biuret 0.8% max.
Free ammonia 0.015–0.22% by wt.
Iron (as Fe) 0.0002% by weight, max.
Ash 0.002% by weight, max.
pH of 10% solution 7.5–10
Size Prill which shall pass IS sieve 200 and not less than 80%
by weight. It will be retained on IS sieve 100
Courtesy: Rashtriya Chemicals and Fertilizers Ltd.

Liquid ammonia at about 240 kg/cm2 pressure and CO2 mixed with a small quantity
of air (passivator) is fed to the urea synthesis reactor. A high mole ratio of ammonia
and CO2 (3.6:1) is maintained. Carbamate is formed during reaction which dehydrates
in the reactor to form urea and water. The oxygen in the air forms a passive oxide layer
inside of vessel surfaces to prevent corrosion ammonia plant.
Raw material for urea: Ammonia-liquid, carbon dioxide-gas
Ammonia: Pressure min/normal: 23/26 ata
Temperature: 120ºC (–33ºC in the storage tank)
CO2: Pressure min/normal: 1.69 kg/cm2
Temperature: 40ºC
Ammonia Ammonia: 99.5% by weight
Oil: 10 ppm max
Water: 0.5% by weight

CO2 CO2: 99% by volume, inserts: 0.31% by volume, H2: 0.69% by volume
All utilities are available at battery limits.
Ammonia 0.588, steam 1.21, power 85 kWh

Process description: Urea production takes place in five main steps.

Urea synthesis and high pressure recovery: Urea is produced by synthesis from liquid
ammonia and gaseous CO2. In the reactor 1 the ammonia and CO2 react to form
ammonium carbamate, a portion of dehydrates to form urea and water. The reactions
are as follows:
2NH3 + CO2 = NH2COONH4
NH2COONH4 = NH2CONH2 + H2O

In synthesis condition reactor 188ºC, temperature and 156–158 kg/cm2 pressure are
maintained. The first reaction occurs rapidly and is completed. The second reaction
occurs slowly and determines the reactor volume. The fraction of ammonium carbamate
that dehydrates is determined by the ratio of the various reactants, the operating
temperature, and the residence time in the reactor. The molar ratio of water and carbon
dioxide is around 3.6:1. The molar ratio of water and carbon dioxide is around 0.67–1.
124 Chemical Process Technology

Carbon dioxide along with passivation air is compressed up to the reactor pressure and
fed to the reactor along with ammonia feed.
The reaction product leaving the reactor flow to the steam heated falling stripper,
which operate at the same pressure as the reactor. The mixture is heated up as it
flows down the falling film exchanger. The CO2 content of the solution is reduced
by the stripping action of the ammonia as it boils out the solution. The carbamate
decomposition heat is supplied by 24 atm saturated steam. The overhead gases from
the stripper and the recovered solution from the medium pressure absorber, all flow to
the high pressure carbamate condensers where the total mixture, except for few inserts,
is condensed and recycled to the reactor by means of ejector. The liquid ammonia is
drawn and compressed at about 22.4 kg/cm2g pressure. Part of this ammonia is sent to
the medium pressure absorber, the remaining part enters the high pressure synthesis
loop. The liquid ammonia and carbamate enter the reactor where ammonia reacts with
compressed CO2. The carbon dioxide drawn at urea plant limit at about 1.6 ata pressure
of about 160 ata. A small quantity of air is aided to the CO2 at the compressor suction
in order to passivate the stainless steel surfaces, thus preventing them from corrosion
due to both reagent and reaction product. The condensation of gases at high pressure
and temperature permits the production of 4.5 ata steam in high pressure carbamate
condenser. In the carbamate separator, the incondensable gases, consisting of inert gases
containing a little quantity of NH3 and CO2 unreacted in the condenser, are separated
from the carbamate solution and sent to the medium pressure decomposer.
Urea purification and low pressure recovery: Urea purification takes place in two stages at
decreasing pressures as follows:
• Medium pressure stage: 17–18 kg/cm3
• Low pressure stage: 3.5 kg/cm2
Medium pressure stage purification and recovery stages at 18 atm: The solution, with a low
residual CO2 content, leaving the bottom of stripper (46% urea, 23% ammonia and 5%
CO2 enters the medium pressure separator where gases are flashed and the solution
flows to the MP decomposer at about 18 atm where the carbamate is decomposed to
large extent. 24 ata steam condensate flowing out of the stripper.
The NH3 and CO2 rich gases leaving the top MP separator are send to MP condenser
where they are partially absorbed. The mixture from the MP condenser flows to the
MP absorber where CO2 absorption and ammonia rectification take place. Ammonia
leaving top of the MP absorber is partially condensed in ammonia condenser from
where the liquid and gaseous ammonia are send to ammonia receiver and ammonia
recovery tower for recovery of ammonia. The ammonia water solution is send back to
MP absorber.
Low pressure purification and recovery stage at 4.5 atm: The solution leaving the bottom of
the medium pressure decomposer is about 64% urea, 7% ammonia and 1.4% CO2 are
sent to LP separator and LP decomposer. In the LP separator, the gases are removed
and are sent to condenser where they are absorbed in carbonate solution. In the LP
decomposer, residual carbamate is decomposed. The solution from LP decomposer
contains about 71% urea, 2% ammonia and 0.8% carbon dioxide which is further
concentrated for prilling.
Urea concentration: The solution containing about 71% urea, 2% ammonia and 0.8%
CO2 leaving the LP decomposer are concentated in two-stage vacuum concentrator
from which 99.7% urea solution is obtained which is sent to prilling section.
Nitrogenous Fertilizer and Nitric Acid 125

Urea prilling: The user leaving the concentrator is sent to the top of the prilling tower
where they are sparyed. Urea coming in the form of droplets are cooled by ambient
air while flowing downward. The solid urea prills are fed to the belt conveyor by the
rotary scraper through aslit and finally conveyed to bagging section.
Process of urea production is described in Figure 7.6.

Fig. 7.6: Process of urea production

7.3 NITRIC ACID

Nitric acid was originally manufactured from Chile saltpeter (sodium nitrate) which has
been replaced by ammonia oxidation process. Nitric acid demand is heavily dependent
on the demand for fertilizers and explosives which consume about 85% of nitric acid
production. Other major consumers for nitric acid are aniline and toluene di-isocyanate
and polymeric MDI. Some of the other uses are in the manufacture of nitrates of sodium,
potassium and calcium. Glycol, H-acid, nitrobenzene dyes and dyes intermediates,
drugs and pharmaceuticals, pickling of steel and metallurgy, etc. (Bhagat, 2007). NO
emissions from nitric acid have become cause of major concern, and about 7.0 kg of NO
per ton of nitric acid is produced. Some of the major producer of nitric acid are Deepak
Fertilizer and Petrochemicals (DFPC), TALOJA, GNFC (Bharuch), NFL (Nangal), RCF
(Trombay). Other manufacturers are Indian Explosive Limited, HOCL (Bhagat, 2007).
7.3.1 Uses of Nitric Acid
Nitric acid is one of the important mineral acid which find application not only in
fertilizer manufacture but also in manufacture of large number of chemicals. Some of
the uses of nitric acid are:
• In manufacture of nitrogenous fertilizer, phosphoric fertilizer (Nitrophosphate)
• Explosive (TNT, nitroglycerine, ammonium nitrate), cellulose nitrate, picric acid,
pentaerythrilol tetranitrate (PETN), cyclonitec (RDX)
• Nitration of organic chemicals
• Metal nitrate
• Polyurethane
• Synthetic dyes
• Synthetic drugs
• Adipic acid, synthetic fiber (Nylon 6, Nylon 6,6 )
126 Chemical Process Technology

• Steel pickling
• Potassium and silver nitrate, copper nitrate
• Nitroparaffins
• Rocket propollent for nuclear fuel processing.
About 85% of nitric acid by-product is consumed captively on site, primarily in the
production of ammonium nitrate, fertilizers and explosive. 10% of nitric acid is used
as organic interemediates and 5% account for small industries using nitric acid for
pickling, electrolating(Bhagat, 2007). Dilute nitric acid 60%, concentrated nitric acid
68% and 72% is used in various industrial application.
7.3.2 Nitric Acid Process Technology
Some of the Processes used in production of nitic acid are:
• From reaction of sodium nitrate and sulfuric acid. Old process in 1920.
• 2NaNO3 + H2SO4 → 2HNO3 + H2SO4
• N2 fixation from air: Atmospheric nitrogen and oxygen are combined in presence
of electric arc resulting nitrogen peroxide dissolved in water to get nitric acid.
Temperature 2260ºC
• N2 fixation by nuclear fission: Air exposed to radiation in a nuclear reactor
• Ammonia oxidation and abosrption of NO2 in water.
Weak Acid Processes
Weak acid processes are either monopressure process or dual pressure process.
Monopressure process is either medium pressure [0.3–0.6 MPa (3–6 atm) or high pressure
process (0.7–1.2 MPa (7–12 atm)].
Higher pressure process lower capital cost, more by product steam, higher strength
of acid, increase in rate of reaction (50-fold increase). Lower catalyst cost slightly higher
yield. Reduced equipment size.
Dual pressure processes have medium pressure at front end and high pressure at
tail end for abosrption. Improved ammonia yield with better catalyst performance.
Direct Strong Acid Process
The proces is similar to weak acid process but differs from weak acid plants as additional
processing steps are involved to achieve super azeotropic sterngth of nitric acid.
Nitric acid from oxidation of ammonia: The foundation of modern nitric acid process was
laid by Kuhlmann in 1838 when he filed patent for the catalytic oxidation of ammonia
using platinum catalyst (Platinum Metals Rev, 1967, 11(1) p.2). Nitric acid is produced
by step-wise oxidation of ammonia using platinum catalyst.
Original process: At atmospheric pressure. However, large equipment required low
concentration of HNO3.
Raw material: Ammonia, air, water, platinum 104, rhodium gauze catalyst.
Basic 1 metric ton of nitric acid (100%)
NH3—290 kg
Platinum—170–340 mg
Air—3600 m3
Water—125 m3
Electricity—10–30 kWh
Steam credit—1 metric ton.
Nitrogenous Fertilizer and Nitric Acid 127

Various steps involved in nitric acid manufacturing are given below:

Catalytic oxidation of ammonia: First step in the production of nitric acid is catalytic
oxidation of ammonia. Reaction involved is:
4NH3 + 5O2 4NO + 6H2O DH = –330 kJ/mol
The above reaction is exothermic and following side reactions may take place
depending on the conditions:
4NH3 = 5O2 4NO + 6H2O
4NH3 =4O2 N2O + 6H2O
4NH# + 3O2 2N2 + 6H2O

Ammonia oxidation is highly exothermic and very rapid. Oxidation only proceeds
at high temperature; however, too high temperature above 900ºC elemental nitrogen
is formed. Platinum catalyst is used in the form of platinum gauge made of platinum-
rhodium alloys. Oxidation reaction on platinum gauge proceeds at very high rate.
The overall rate of oxidation process, depending on converter design and operating
conditions, is controlled by the rate of diffusion of ammonia from the core of gas stream
to the surface of the platinum catalyst and only when agitation is intense by the rate of
reaction between ammonia and oxygen absorbed on the paltinum (Mukulyonov, et al.
1974).
Oxidation of nitric oxide (NO) to nitrogen oxide (NO2)
NO + O2 → NO2
The oxidation of nitric oxide (NO) to nitric oxide is a non-catalyzed reaction and is
favored by low temperature and high pressure. Oxidation of nitric oxide to nitrogen
peroxide results in decrease in volume and liberation of considerable ammount of heat.
Lower temperature favors the formation of nitrogen dioxide.
Absorption of nitric per oxide with water:
NO2 + 6H2O HNO3 + NO
This process is now being used. Location near an ammonia plant is desirable.
As nitric acid makes azeoptrop, maximum concentartion of nitric acid firmed is
around 50–65% weak processes. However, concetration up to 99% is possible by direct
srong process strong acid can be also made from weak nitric acid by extractive or
azeotropic distillation.
Low pressure process: Higher ammonium concentration, less loss of platinum.
The principal design variables for the ammonia oxidation and subsequent stages of the
plant are temperature, pressure and gas flow rate. Effects of major process variables
on nitic acid manufacture are given in Table 7.8. Figure 7.7 depicts manufacturing of
nitric acid by medium pressure oxidation process.
Concentration of Weak Nitric Acid
Nitric acid above 67% concentration makes azeotrop, so for higher concentration,
azeotropic or extrative distillation is used.
Concentration by azeotropic distillation using sulfuric acid: The process involves concentration
of weak nitric acid by distilaation and further concentration by azeotropic distillation
using conc. H2SO4.
128 Chemical Process Technology

Table 7.8: Effect of major processes variables on nitric acid manufacture

Process variable Oxidation of ammonia Oxidation of NO Absorption of NO2
Increased Greater yield Lower yield Reduced absorption,
temperature lower HNO3 strength
Increased Oxidation rate sightly Increased yield Improved absorption,
pressure reduced. Increase in NH3 higher nitric acid
oxidation per unit time strength
Increased Optimum operating tempe­ Reduced secondary Minor improvements
flow rate rature increased. Increase in reactions. More turbu­ only
NH3 oxida­tion. Improved lance and increased
NO yield yield

Montecatini Intermediate Pressure Process

Fig. 7.7: Nitric acid by medium pressure oxidation process

Concentration by extractive distillation: This process involves concentration of nitric acid

by extractive distillation using magnesium nitrate. It has less operating cost; capital cost
is also less; acid quality and yield is improved. Deepak Fertilizers and Chemicals is the
largest producers of concentrated nitric acid (98%) with an annual instaled capacity of
1,38,600 metric tons based on Adolf Pinke Gmbh, Germany, Technology.

Properties and Specification of Nitric Acid

Nitric acid is colorless liquid. The BIS (IS:264-1976) has prescribed for technical grade
nitric acid: specific gravity at 15.5ºC 1.42, nitric acid content % wt. min 52.00, residue on
ignition, percent wt. max.0.10, heavy metals (as Pb) percent wt. to pass test, chlorides
(as HCl), percent wt. max. 0.03, sulfates (as H2SO4) percet wt. max. 0.20, ammonium
salts, % wt. max. 0.0005.
Nitrogenous Fertilizer and Nitric Acid 129

7.4 AMMONIUM NITRATE

Although ammonium nitrate contains 35% nitrogen; however, it is not used as fertilizer
due to its explosive properties. It is also hygroscopic. Ammonium nitrate is mainly used
in explosive. As fertilizer it is being made in the form of calcium ammonium nitrate.
Properties
Nitrogen content: 35%
Specific gravity: 1.66
Bulk density 998.7 kg/m3
Hygroscopic in nature.

7.4.1 Process Technology

Ammonium nitrate made by neutralization of ammonia vapor with 50–60% nitric acid.
Ammonia is vaporized and reacted with nitric acid in SS neutralizer at 4–5 at pressure
and 170–180ºC. It is further contrasted in vacuum evaporator, crystallized in vacuum
crystallizer, dried in rotary drier, and screened (Fig. 7.8).

Fig. 7.8: Process flow diagram for the manufacture of ammonium nitrate

7.5 CALCIUM AMMONIUM NITRATE

To reduce the explosive hazards of ammonium nitrate, it is used in the form of calcium
ammonium nitrate containing about 25–28% nitrogen containing about 75% ammonium
nitrate to reduce the explosive hazards of ammonium nitrate.
Properties
Specifications as given in FCO (Table 7.9).

Table 7.9: Properties of calcium ammonium nitrate

Particulars CAN 25% N CAN 26% N
Moisture, percent by 1.0 1.0
weight, max.
Total ammoniacal 25.0 26.0
and nitrate nitrogen,
percent by weight, min.
Contd...
130 Chemical Process Technology

Table 7.9: Properties of calcium ammonium nitrate (Contd...)

Particulars CAN 25% N CAN 26% N
Ammoniacal nitrogen, 12.5 13.0
percent by weight, min.
Calcium nitrate, percent 0.5 0.5
by weight, max.
Particle size The particle size of the The particle size of the
material shall be such that material shall be such that
80% material shall pass 90% material shall pass
through 4 mm IS sieve and through 4 mm IS sieve and
be retained on 1 mm sieve. be retained on 1 mm IS sieve.
Not more than 10% shall be Not more than 5% shall be
below 1 mm IS sieve below 1 mm IS sieve
Source: Sundram, KP.” Handbbok of Fertilizer Technology. The Fertilizer Corporation of India,
New Delhi; Sixth edition 2001.

7.5.1 Process Technology

In manufacture of calcium ammonium nitrate, first ammonium nitrate is made by
reacting ammonia vapor obtained by vaporization with preheated nitric acid in
neutralizer where 82–83% ammonium nitrate is produced which is further concentrated
to 92–94% in vacuum concentrator. Concentrated ammonium nitrate solution is spayed
over powder lime stone in a rotary granulator. The granulated CAN is further dried
in rotary drier. Dried granules further coated with soap stone dust in coating drum.
Figure 7.9 presents a process flow diagram describing calcium ammonium nitrate
manufacture.

Fig. 7.9: Process flow diagram for calcium ammonium nitrate manufacture

7.6 AMMONIUM SULFATE

Ammonium sulfate is one of the important fertile containing 21% nitrogen and 24%
sulfur.
Various routes for making ammonium sulfate are:
• Neutralization of ammonia from coke-oven gas with sulfuric acid
• Neutralization of ammonia by sulfuric acid
Nitrogenous Fertilizer and Nitric Acid 131

• Gypsum route
• By product from caprolactam plant

7.6.1 Process Technology

It is manufactured from coke-oven gas and direct neutralization of ammonia with
sulfuric acid. Coke- oven gas is one of the important sources of ammonium sulfate, and
steel plant coke-ovens manufacture ammonium sulfate by recovering ammonia from
coke-oven gas, which contains about 1% ammonia by volume. Ammonium sulfate is
also made directly by neutralization of gaseous ammonia by sulfuric acid (Fig. 7.10).
2NH3 + H2SO4 (NH4)2 SO4

Fig. 7.10: Ammonium sulfate from ammonia/ammonia from coke-oven gas

7.7 AMMONIUM SULFATE FROM GYPSUM

Ammonium sulfate is also manufactured from gypsum route. The process involves
carbonation of ammonia to produce ammonium carbonate which is further reacted with
gypsum to produce ammonium sulfate. Calcium carbonate is obtained as by-product.
This process was used in Sindri FCI plant. The calcium carbonate was used for cement
manufacture. GSFC was also manufacturing earlier ammonium sulfate by this route.
Both the plants are closed now.
2NH3 + H2O + CO2 (NH4)2CO3

CaSO4.2H2O + (NH4)2CO3 (NH4)2SO4 + CaCO3 + 2H2O

7.7.1 Ammonium Sulfate as By-product from Caprolactam Plant

During the manufacture of caprolactam which is monomer for Nylon 6, ammonium
sulfate is obtained as by-product. Two units manufacturing caprolactam in India are
GSFC and FACT, Travancore. Ammonium sulfate is by-product from these plants.

7.8 AMMONIUM CHLORIDE

Ammonium chloride contains 25% nitrogen having specific gravity 1.53 and bulk
density 4.5–5.0 kg/cm3 and used for rice and other crops. Ammonium chloride is made
by neutralization of ammonia with hydrochloric acid. It is also obtained as by-product
from modified Solvay dual salt process during manufacture of sodium carbonate.
Modified Solvay process is discussed in Chapter 4. In the process, direct neutralization
of hydrochloric acid by ammonia takes place in reactor which is further centrifuged
and dried.
132 Chemical Process Technology

7.8.1 Ammonium Chloride Direct Neutralization

NH3 + HCl NH4Cl

7.8.2 Ammonium Chloride by Modified Solvay Process

2NH3 + H2O + CO2 (NH4)2CO3

(NH4)2CO3 + H2O + CO2 NH4HCO3

NH4HCO3 + NaC Na HCO3 + NH4Cl

2Na HCO3 Na2CO3 + CO2 + H2O

FCO Specification of Ammonium Chloride (Handbook on Fertilizer Technology,

2001)
Moisture, percent by weight 2.0
Ammoniacal nitrogen, percent by weight 25.0
Chloride other than ammonium chloride 2.0
as NaCl, percent by weight

BIBLIOGRAPHY
1. Austin George T.” Shreve’s Chemical process Technology” McGraw Hill International edition
Fifth edition 1984.
2. Bhagat, DV.” Nitric acid industry in India”. Chemical Industry Digest Annual 2007, p. 141.
3. Gopala Rao, M. Sitting Marshall “Dryden’s Outlines of Chemical technology for the 21st century
“Edited and Revised by Gopala Rao M. Sitting Marshall Third edition Affiliated East West Press,
New Delhi.
4. Gupta DP. “ Nitric acid manufacturer”. Chemical Business, Oct 20–Nov 4, 1991.
5. Hefler P, Pruud’ homme IFA, June Short term Fertilizer Outlook 2015-16, International Fertilizer
Association (IFA) IFA Strategic forum, Paris. Nov 18–19, 2015.
6. Kapur ON. “An overview of low energy ammonia process technology and future options”.
National seminar on Indian Fertilizer scenario options for the future”. March 22–23, 1996.
Department of Chemical Eng. BHU, Varanasi.
7. Khalid W. “Update catalyst technology for syn. gas production” Hydrocarbon processing. April
2009, p.81.
8. Lin R, deBoer R, Poe B. “Optimize ammonia plant operation” Hydrocarbon processing. June
1991, p.91.
9. Mall ID. “Petrochemical process technology’, 2007, Reprint 2015, Second Edition, 2017.
10. Mukhalyonov I, Kuznetsov D, Averbukh A, Tumarkina E, Furmer I. “ Chemical technology”
MIR Publishing, Moscow, 1974.
11. Sundram KP. “Handbook of Fertilizer Technology”. The Fertilizer Corporation of India, New
Delhi; Sixth edition, 2001.
8
Phosphorus, Phosphatic,
Potassium and Mixed Fertilizers

8.1 INTRODUCTION
Phosphorus is essential for the existence of plant and animal lives. Phosphorus is
critically-life essential, alarmingly poisonous. Phosphorus fine example of an element
occurring in more than one form with varying in appearance and starkly different
properties (Patwardhan, 2019). The various phosphatic fertilizers, depending on
their composition, have different solubility in the soil solutions and therefore are
assimilated by plants differently. The raw material for manufacture of elemental
phosphorus, phosphorus containing compounds, and phosphatic fertilizers are
naturally occurring phosphates—phosphate rock and appetite (Mukhalyonov, et
al. 1974) where phosphorus is in insoluble form, mainly in the form of fluorapatite
[Ca5F(PO4)3] or tricalcium phosphate [Ca3(PO4)]. Composition of rock phosphate
and its various sources are given in Table 8.1. As per the Fertilizer Control and
Order and as amended by Ministry of Agriculture and Rural Development for the
specification of rock phosphate: P2O5 content should be minimum 18% and particle
size should be: 90% of the material shall pass through 0.15 mm IS sieve and balance
10% should pass through 0.25 mm IS sieve.
Phosphorus industries consist of pure phosphorus and phosphorus compound
manufacture, phosphoric acid manufacture, phosphatic fertilizer containing only
phosphorus and sulfur and other containing phosphorus, nitrogen and potash. Some
of the major phosphatic fertilizer and their nutrient content is given in Table 8.1.

Table 8.1: Composition of rock phosphate from various country

Composition Jordan Morocco Togo Udaipur

Total P2O5 32.53 32.24 36.13 35.50

CaO 51.69 51.76 48.70 48.28

SiO2 1.97 1.36 1.75 9.36

F 3.48 4.10 3.28 3.65

Fe2O3 0.13 0.46 0.30 2.20

Al2O3 0.18 0.19 2.63 0.32

Contd...

133
134 Chemical Process Technology

Table 8.1: Composition of rock phosphate from various country (Contd...)

Composition Jordan Morocco Togo Udaipur
MgO 0.20 0.84 0.21 0.32

SO3 1.58 1.55 0.39 0.01

CO2 4.40 5.90 1.14 0.56

Chlorine 0.003 0.008 0.008 0.008

Color of acid Greenish-brown Green Pink Greenish-brown
Source: Sharma, 1992.

Availability of phosphorus is an emerging issue, and it is estimated that by 2035 the

demand for phosphorus may outpace the [Link] thirds of world’s resources of
phosphorus are in China, Morocco and Western Sahara.

8.2 PHOSPHORUS
The word phosphorus comes from an ancient Greek word phosphoros which means light
bringer (Chemical Industry Digest, April 2010). Phosphorus having atomic number 15
resembles sulfur. Although method of producing phosphorus by evaporating urine
until 1775 when CW Scheele prepared it from bones which contain calcium phosphate
Ca3(PO4)2. Being very reactive, phosphorus does not occur on earth in free state but
always occurring as phosphate salt (Patwardhan, 2019). Phosphorus occurs in the
combined form of appetite minerals. Now phosphorus is manufactured from rock
phosphate.
Phosphorus forms building block for a large number of important chemicals
which find application in defense and building blocks for larger number of
chemicals which find application in the manufacture of agrochemicals, lube oil
additives, dyestuffs, water treatment chemicals, and pharmaceuticals. Some of
the important phosphorus derivatives are phosphorus pentasulfide, phosphorus
trichloride, phosphorus pentachloride, phosphorus pentoxide, red phosphorus,
and phosphoric acid. Phosphorus compounds find application in water treatment,
soap and detergent builder, tanning and many other industries. Phosphorus in the
form of P4S3 is used in pyrotechnic mixtures. Although some of the phosphorus
compounds are toxic, orthophosphate and other compounds are nontoxic and can
be added to food. Calcium phosphate is used in baking powder, while basic salt
trisodium phosphate is also used as baking powder. Dicalcium phosphate is vital
primary abrasive constituent in a number of toothpastes. Diammonium phosphate
is used in brewing as nutrient. It is also used in fire extinguisher powder and fire
retardant.
Phosphorus is available in two forms: Yellow phosphorus and red phosphorus.
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 135

Yellow phosphorus: Yellow phosphorus is manufactured by electrochemical reduction

of rock phosphate. Reduction of rock phosphate takes place in presence of carbon
at about 1600ºC using silica as a flux for the calcium the fluorine is recovered by
scrubbing.
Red phosphorus: Red phosphorus is relatively inactive allotrope of yellow phosphorus.
It can be ignited by friction in presence of an oxidizing agent. It is used in safety
matches. It is also used in the manufacture of metallic phosphides, fire crackers,
smoke and flame signaling devices in defense semiconductors and GLS lamps
(Iyer 1991).

8.3 PHOSPHORUS COMPOUNDS

Apart from phosphatic fertilizer large tonnage of phosphorus compounds are used
in water treatment, soap and detergent industry, leather tanning, fire retardants, etc.
Various sodium-based phosphorus compounds are commonly used and finds wide
use in various chemical industry. Some of the important sodium-based compounds are
monosodium phosphate (MSP), disodium phosphate (DSP) and trisodium phosphate
(TSP). MSP and DSP are made by reacting soda ash with phosphoric acid reacted in
proper molecular proportion; the solution obtained is evaporated, dried and milled to
get solid product. TSP is also made by reacting soda ash, with phosphoric acid; however,
caustic soda is also added.
Trisodium phosphate is another important phosphorus compound which finds
application in water treatment, soap and detergent industry as builder TSP is made by
reacting soda ash and phosphoric acid to yield DSP which is further calcined to yield
TSP.
Baking powder: It is used as leaving agent. It consists of sodium bicarbonate and
monocalcium phosphate while baking soda consists of sodium bicarbonate.

8.4 PHOSPHATIC FERTILIZER

Phosphorus is essential for plant growth. Several phosphatic fertilizers are used
to meet the phosphorus demand of crops. Some of the major phosphatic fertilizers
are single superphosphate (SSP) and triple superphosphate (TSP). Apart from SSP
and DSP, some of the important fertilizers are monoammonium phosphate (MAP),
diammonium phosphate (DAP), nitrophosphate of different compositions. In
addition to rock phosphate, sulfuric acid, phosphoric acid, ammonia, nitric acid are
also required. Mixed fertilizer containing potash in combination with phosphorus
is also available. Raw material requirement of phosphatic fertilizer is given in Table
8.2. Process flow diagram for the manufacture of various phosphatic fertilizer is
given in Figure 8.1. Glossary of terms used in phosphoric fertilizer industry are
given in Table 8.3.
136
Table 8.2: Raw material consumption in phosphatic fertilizer industry
Raw material/
KCl Present energy Future energy

Chemical Process Technology

Sl. intermediates Rock H3PO4
NH3 CO2 H2SO4 HNO3 (as 60% Gypsum consumption consumption
no. Fertilizer phosphate (as P2O5) K2O) Gcal/MT Gcal/MT
product
1 SSP – – 0.60 0.36 0.4 0.3
2 TSP – – 0.46 – 0.36 1 0.8
3 UAP 0.37 – – – 0.29 5–6 2
([Link])
4 DAP 0.24 – – – 0.48 2–3 0.5
([Link])
5 NPK 0.18 – – – 0.38 – 0.25
([Link])
6 NPK 0.22 – – – 0.18 – 0.30
([Link])
7 NPK 0.24 – – – 0.20 – 0.33 2–3 1
([Link])
8 NPK 0.15 – – – 0.34 – 0.28
([Link])
9
NPK 0.10 – – – 0.16 0.36 0.26
([Link])

Requirement of Raw Materials/Intermediates (Per ton)
A. Ammonia (NH3) : N.G 900 NM3 or Naphtha 0.83 MT; Fuel 0:1 0.9 MT; Coal 3.62 MT
B. Sulfuric acid (H2SO4) : Sulfur 0.34 MT, or pyrites 0.89 MT
C. Phosphoric acid (H3PO4) (as P2O5) : Rock phosphate :3.3 MT and H2SO4 : 2.82 MT
D. Nitric acid (HNO3) : NH3: 0.29 MT
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 137

Fig. 8.1: Process flow diagram for the manufacture of phosphoric acid and phosphatic fertilizer

Table 8.3: Glossary of terms in phosphoric acid technology

Terms Description
TPA Total P2O5
Water-soluble phosphatic Phosphorus present as natural form can be easily absorbed by plants
fertilizer
Citric acid soluble Citric acid soluble fertilizer is suitable for acidic soil
Water and citrate insoluble Phosphorus present is insoluble in water and citric acid. Suitable in
strongly acid soils fertilizer. Citrate insoluble P2O5 determined by
solubility in a solution
APA Available P2O5
Black acid Ordinary wet phosphoric acid
Contd...
138 Chemical Process Technology

Table 8.3: Glossary of terms in phosphoric acid technology (Contd...)

Terms Description
BPL Bone phosphate of lime, P2O5 content of the rock phosphate is
expressed as Ca3PO4
Furnace acid Acid produced by electric furnace process by reduction of rock
phosphate
I and A Iron and aluminum content expressed as sum of these two oxides
Insoluble Material which is not dissolved in sulfuric acid
SSP Single superphosphate
TSP Triple superphosphate

8.5 PHOSPHORIC ACID

Phosphoric acid is one of the important mineral acids which finds application in
manufacture of fertilizer and important phosphorus compounds which find application
in soaps and detergents, food industry, water treatment, tooth paste and in other
applications. Different grade of phosphoric acid is made depending on its end uses.
Different types of phosphoric acids are given Table 8.4.
About 90% of the phosphoric acid is used in making fertilizers. Wet phosphoric acid
is used in the manufacture of fertilizer while electric furnace grade phosphoric acid is
used for the manufacture of various chemicals.
FACT Udogmandal phosphoric acid plant was the first plant set up with an installed
capacity of 8000 TPA of P2O5.

Table 8.4 Different types of phosphoric acid

Type of phosphoric acid Process
Wet process phosphoric acid Production made by digestion of phosphate rock with sulfuric acid.
It is used in impure state for manufacture of triple superphosphate
and ammonium phosphoric acid
Ca3(PO4)2 + 3H2SO4 + 6H2O → 2H2PO4 + 3CaSO4.2H2O
(phosphor gypsum)
Electric furnace phosphoric It is obtained in very pure form by first reduction of phosphate rock
acid to phosphorus in presence of silica and coke and then oxidation
and then hydration:
Ca3(PO4)2 + 6SiO2 + 10C → 6CaSiO3 + P4 + 10CO
3SiF4 + 2H2O → 2H2SiF6 + SiO2
4P + 5O2 → 2P2O5
P2O5 + 3H2O → 2H3PO4

Used mostly for nonfertilizer and detergent.

Energy input 12000 KWH per ton of recovered phosphorus.
Hydrochloric acid (HCl) as Digestion of phosphate rock with HCl to phosphoric acid and
acidulant soluble calcium chloride and separation of phosphoric acid by
solvent extraction (Butanol or amyl alcohol)
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 139

8.5.1 Wet Phosphoric Acid

Wet phosphoric acid is made by reaction of sulfuric acid and rock phosphate. Various
steps involved are:
• Grinding of rock phosphate 65% 200 mesh
• Acidulation of finely ground rock phosphate with sulfuric acid to form phosphoric
acid and gypsum.
Ca10(PO4)6 F2 + 10H2SO4 + 20H2O 6H3PO4 + 10 (CaSO42H2O) + 2HF

• Separation of phosphor gypsum from the acid by filtration

• Washing of gypsum to remove adhering phosphoric acid
• Concentration of the acid by evaporation to the desired concentration if required.
Phosphoric acid may be classified according to the hydrate formed in which calcium
sulfate crystallizes: anhydrate (CasO4), hemihydrates (CaSO4.½H2O and hydrate
(CaSO4.2H2O). Phosphor gypsum quality varies from the type of phosphoric acid
produced. The conventional dihydrate processis still being used in spite of some of its
shortcomings like poor acid strength, poor gypsum quality. Process flow diagram for
wet Phosphoric acid is shown in Figure 8.2. A typical analysis of wet phosphoric acid
is given in Table 8.5.

Raw material
1 ton 100% H3PO4 in 90% yield: 2.7 tons gypsum
Phosphate rock 32% P2O5: 2.5 tons
Sulfuric acid 93–98%: 2.0 tons

Fig. 8.2: Process flow diagram for wet phosphoric acid

140 Chemical Process Technology

Table 8.5 Typical analysis of wet phosphoric acid

Constituents Percent
P2O5 54.0

H3PO4 74.6

CaO 6.1
Fe2O3 plus Al2O3 6.7

SO3 3.0
F 0.5
Suspended solids 5.5

Recommended specifications of rock phosphate

The general specifications of rock phosphate are recommended for use in the
manufacture of phosphoric acids given in Table 8.6.

Table 8.6: Specifications of rock phosphate are recommended for use in the
manufacture of phosphoric acid
P2O5 32–34%

CaO/P2O5 1.5% by weight (max.)

Fe2O3 + Al2O3 2.0% (max.)

CO2 3.0% (max.)

SO3 Should not be in sulfide form

SiO2 2.5–5.0 (max.)

F 4.0% (max.)
MgO 0.5% (max.)
Cl 0.015 (max.)
Organic matter 1.5% (max.)
Source: Hydrochloric acid acidulation process produces technical grade phosphoric acid.

8.5.2 Electric Furnace Acid

Phosphoric acid is obtained in very pure form. Various steps involved are:
• Reduction of phosphate rock to phosphorus in presence of silica and coke
• Condensation of vapor phosphorus
• Oxidation of elemental phosphorus to P2O5
• Hydration of P2O5 to phosphoric acid.
The reaction involved in manufacture of electric furnace process is as follows:
Ca3(PO4)2 + 6SiO2 + 10C 6CaSiO3 + P4 +10CO
3SiF4 + 2H2O 2H2SiF6 + SiO2
4P + 5O2 2P2O5
P2O5 + 3H2O 2H3PO4
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 141

Process flow diagram of electric furnace acid is given in Figure 8.3. Electric furnace
acid is mostly used as non-fertilizer agents and detergents. Energy input is 12000 kWh
per ton of recovered phosphorus.

Fig. 8.3: Process flow diagram of electric furnace acid

8.5.3 Technological Development in Phosphoric Acid Plant

Various technological development in phosphoric acid technology are reduction
in energy consumption, improvement, quality of rock phosphate, improvement in
grinding, better filterability of phosphor gypsum and better environmental protection
to meet the stringent environmental protection.

8.6 SINGLE SUPERPHOSPHATE

Process steps involved in manufacture of single superphosphate (SSP) are:
• Phosphate rock blending and grinding
• Superphosphate manufacture
• Granulation.
Process flow diagram for sigle superphosphate (SSP) is given in Figure 8.4. Grinding
of rock phosphate (90% passing through 100 mesh) of 30% P2O5. Ground rock phosphate
and sulfuric acid are mixed in horizontal mixer. The fluid material from the mixer goes
to broad field den where it solidified. Solidification results from continued reaction
and crystallization. Partially matured superphosphate is removed from den and
conveyed to storage for final curing which takes about 2–6 weeks. The cured product
is reclaimed, milled, screened and either bagged or sent for granulation. Granulation
is done in the presence of steam in drum granulator. Fluorine compounds generated in
the mixer/dryer are recovered by scrubbing with water. FCO specifications for single
superphosphate are given in Table 8.7.
142 Chemical Process Technology

Reactions
• Ca3(PO4)2Ca F2 + 7H2SO4 + H2O 3Ca(H2PO4)2.7Ca SO4 + HF
• 4HF + SiO2 Si F4 + H2O
• 3Si F4 + 2H2O 2H2SiF6 + SiO2
• H2SiF6 + NaCl NaSiF6 + 2HCl

Fig. 8.4: Process flow diagram for single superphosphate

Table 8.7: FCO specifications for single superphosphate

Single superphosphate 14% P2O5 16% P2O5 16% P2O5

powder powder granulated
1. Moisture percent by weight, max. 12.0 12.0 5.0
2. Free phosphoric acid (as P2O5) percent by weight, max. 4.0 4.0 4.0

3. Water-soluble phosphates (as P2O5) percent by weight, 14.0 16.0 16.0

min.
4. Particle size* – *
*Particle size for granulated SSP: Not less than 90% of the material shall pass through 4 mm IS sieve
and shall be retained at 1 mm IS sieve. Not more than 5%shall pass through 1 mm IS sieve.

8.7 TRIPLE SUPERPHOSPHATE

Triple superphosphate is excellent source of plant nutrient containing about 46–48%
P2O5. Wet phosphoric acid and rock phosphate are required for the manufacture of wet
phophoric [Link] should contain 42.5% (minimum) water soluble P2O5. Bulk density
(about 800–880 kg/m3).

8.7.1 Process
The rock phosphtae is ground to fine mesh and reacted with concentrated phosphoric
acid (52–54% P2O5) in cone mixer and fed to den where it solidifies in 10–30 minutes.
The product is disintegrated after discharge from den and piled for curing. After
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 143

curing for 3–6 weeks the run of pile material is bagged. Process flow diagram for
triple superphosphate is given in Figure 8.5. Table 8.8 presents specifications of triple
superphosphate as given by FCO.
Reaction
Ca10(PO4)6 F2 + 14H3PO4 10Ca(H2PO4)2 + 2HF

Fig. 8.5: Process flow diagram for triple superphosphate

Table 8.8: Specifications of triple superphosphate as given by FCO

Moisture, percent by weight, max. 1.5
Free phosphoric acid (as P2O5), percent by weight, max. 3.0

Total phosphates (as P2O5), percent by weight, min. 46.0

Water-soluble phosphates (as P2O5), percent by weight, min. 42.5

Note: Particle size of granulated TSP shall be such that 90% of the material shall pass 4 mm IS sieve
and shall be retained on 1 mm sieve and not more than 5% shall pass through 1 mm IS sieve.

8.7.2 Potassic Fertilizer and Mixed Fertilizers

Potassium is essential as one of the three primary nutrients (NPK fertilizer). Muriate
of potash in the form of potassium chloride is commonly used as fertilizer. Principal
potash mineral is sylvite which is mixture of sylvite (potassium chloride) and
halite (sodium chloride). Potassium chloride is recovered either by hot leaching or by
flotation. Potassium chloride and potassium sulfate are commonly used as potassic
fertilizer.
To meet the requirement of NPK, various grades of NPK are being made as mixed
fertilizer. Specification of various grades of NPK 20-20-0, 18-18-9, 15-15-15. Some of the
important mixed fertilizers are ammonium phosphate, diammonium phosphate, urea
ammonium phosphate, ammonium phosphate sulfate, nitro-phosphate which may or
may not have potash depending on requirement. Specifications of various NPK fertilizer
is given in Table 8.9.
144 Chemical Process Technology

Table 8.9: Specifications various NPK fertilizer

Particulars 15-15-15* 17-17-17 19-19-19 14-35-14 10-26-26 12-32-16
Moisture, max. 1.5 1.5 1.5 1.0 1.0 1.0
Total nitrogen, min. 15.0 17.0 19.0 14.0 10.0 12.0
Ammonical nitrogen, min. 7.5 5.0 5.6 12.0 7.0 9.0
Nitrogen in the form of urea, max. – 13.4 2.0 3.0 3.0 12.0
Neutral ammonium citrate soluble 15.0 17.0 19.0 35.0 26.0 32.0
phosphate as (P2O5), min.
Water-soluble phosphates as 4.0 14.5 16.2 29.0 22.1 27.2
(P2O5), min.

Water-soluble potash as (K2O), 15.0 17.0 19.0 14.0 26.0 16.0

min.
Note: Particle size hall be such that 90% of the material shall not pass between 1 and 4 mm sieve
and not more than 5% pass through 1 mm IS sieve. *Nitro phosphate: Nitrogen in the nitrate form,
max. 7.5%, calcium nitrate max. 1.0
Source: Fertilizer Control Order, 1985.

8.8 AMMONIUM PHOSPHATE

Ammonium phosphate contains 20% P2O5. It is made by reacting phosphoric acid with
anhydrous ammonia.
NH3 + H3PO4 NH4H2PO4

8.8.1 Urea Ammonium Phosphate

To lower amount of potassium, urea ammonium phosphate is manufactured.
Specifications of urea ammonium phosphates given in Table 8.10.

Table 8.10: Specifications of urea ammonium phosphate

28-28-0 24-24-0
1. Moisture percent by weight, max. 1.5 1.5
2. Total nitrogen percent by weight, min. 28.0 2.0
3. Ammoniacal nitrogen percent by weight, min. 9.0 6.4
4. Neutral ammonium citrate soluble phosphate (as P2O5) percent by weight, min. 28.0 2.0

5. Water soluble phosphates (asP2O5) percent by weight, min. 25.2 17.0

Note: Particle size: 90% of the material shall pass through 4 mm IS sieve and be retained on 1 mm
IS sieve. Not more than 5% shall be below 1 mm IS sieve.
Source: Fertilizer Control and Order and as amended by Ministry of Agriculture and Rural
Development.

8.8.2 Diammonium Phosphate

Diammonium phosphate is one of the important phosphatic fertilser. It is made by
reaction of ammonia with phosphoric acid. Typical specification of diammonium
phosphate is given in Table 8.11.
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 145

Table 8.11: Typical specification of diammonium phosphate

Moisture, percent, max. 1.5
Total nitrogen, percent by weight, min. 18.0
Ammoniacal nitrogen, percent by weight, min. 15.5
Total nitrogen in the form of urea, percent, max. 2.5
Total neutral ammonium citrate soluble phosphates (as P2O5), percent by weight, min. 46.0

Total water-soluble phosphates (as P2O5), percent by weight, min. 41.0

Note: Particles size for 24-224-0: 90% of the material shall pass through 4 mm IS sieve and be retained
on 1 mm IS sieve. Not more than 5% shall be below 1 mm sieve.

Reactions
NH3+ H3PO4 NH4H2PO4

NH3 + NH4H2PO4 (NH4)2HPO4

Diammonium phosphate plant consists of three sections:
Wet section: This section consists of scrubbing of fumes from preneutralizer, granulator
and dust from cyclones, by phosphoric acid.
Preneutralization of ammonia and phosphoric acid from scrubber. Ammonia is fed
at 55ºC and 3.5 kg/cm2g through sparger. Slurry temperature is controlled at 120ºC.
The mole ratio in the preneutralizer is maintained at 1.4–1.5.
Dedusting section: Separation of dust from air stream containing dust from various section
is scrubbed by scrubber effluent liquor.
Dry section: This consist of rotary granulator, dryer cooler, conveying system, and
screening. The slurry from prenetralizer is sparyed in rotary granulator. Ammonia is
introduced to the granulator to neutralize free acid. Ammoniation and granulation are
achieved simultaneously in the granulator. The granules are dried with hot air in the
rotary dryer screened.

8.8.3 Ammonium Phosphate Sulfate

Ammonium phosphate sulfate is made by reacting ammonium sulfate and phosphoric
acid followed by ammoniation, addition of urea, granulation, drying and screening
(Fig. 8.6).

Fig. 8.6: Ammonium phosphate sulfate

146 Chemical Process Technology

8.9 NITROPHOSPHATE
Manufacture of nitrophosphate is given in Figure 8.7 which includes either acidulation
of rock phosphate with nitric acid and phosphoric acid, followed by granulation,
drying, screening and cooling or acidulation with nitric acid alone or nitric acid and
phosphoric acid followed by ammoniation and carbonation and addition of potash if
needed followed by granulation, drying, screening and cooling.
Various grades of nitrophosphate are made containing N and P alone or sometimes
NPK. Typical Specification of nitrophosphate is given in Table 8.12.

Fig. 8.7: Process flow diagram for nitrophosphate

Table 8.12: Typical specification of nitrophosphate

20-20-0 23-23-0
1. Moisture percent by weight max. 1.5 1.5
2. Total nitrogen percent by weight, min. 20.0 23.0
3. Nitrogen in ammoniacal form percent by weight, 10.0 13.0
4. Nitrogen in nitrate form percent by weight, max. 10.0 10.0
5. Neutral ammonium citrate soluble phosphates (as P2O5) percent by weight, min. 20.0 23.0

6. Water soluble phosphates (as P2O5) percent by weight, min. 12.0 20.5
7. Calcium nitrate, percent by weight, max. 1.0 –
Note: Particle size: 90% of the material shall pass through 4 mm IS sieve and be retained on 1 mm
IS sieve. Not more than 5% shall be below 1 mm IS sieve.
Phosphorus, Phosphatic, Potassium and Mixed Fertilizers 147

BIBLIOGRAPHY
1. Austin George T. “Shreve’s Chemical Process Technology”, McGraw Hill International edition
Fifth edition 1984.
2. Chemical technology, MIR Publishing, Moscow, 1974.
3. Chemical Industry Digest April 2010.
4. Gopala Rao M, Sitting Marshall. Dryden’s Outlines of Chemical technology for the 21st century
“Edited and Revised by Gopala Rao M, Sitting Marshall, Third edition Affiliated East West Press
New Delhi.
5. Handbook of Fertilizer Technogy, Fertilizer Association of India, Sixth edition, 2001.
6. Hefler P, Pruud’ homme IFA, June Short term Fertilizer Outlook 2015–16, International Fertilizer
Association (IFA) IFA Strategic forum, Paris Nov 18–19, 2015.
7. Iyer SP. “Phosphorous and its major derivatives”, Chemical Engineering World, No. 8, Aug.,
1991.
8. Mukhalyonov I, Kuznetsov D, Averbukh A, Tumarkina E, Furmer I. “Chemical Technology”,
MIR publishers Moscow Second edition 1974.
9. Patwardhan V. “Phosphorous is critically-life essential, alarmingly poisonous”, Chemical Industry
digest, March 2019 p. 44.
10. Sharma RP. “Phosphoric Acid For Phosphatic Fertilizers”, Chemical Engineering World, Vol.
27, No. 11, November 1992, p.41
11. Sundram KP. Handbook of Fertilizer Technology: The Fertilizer Association of India, New Delhi,
Sixth edition 2001.
12. Annual Report 2017–18 Govt of India Ministry of Chemicals and Fertilizer, Department of
Fertilizer.
9
Cement and Lime Industries

9.1 INTRODUCTION
Cement is one of the important sectors of industrial activity and is playing a significant
role in providing shelter to mankind, thus, satisfying one of the three basic needs of
human viz. food, shelter and clothing. It is playing an important role in the infrastructural
development of the nation. Cement production is yardstick for measurement of
civilization and industrialization. Cement industry is playing an important role in the
infrastructural development of a nation.
Modern hydraulic cement began to be developed from start of the Industrial
Revolution (around 1800) driven by three needs—hydraulic render for finishing
buildings in wet climates, hydraulic mortars for masonry construction of harbor works,
and development of strong concretes ([Link]
Indian cement industry has made tremendous growth during the last five decades
and has come a long way since the first bag of cement was packed in 1914 at Porbondar.
On the basis of number of plants and installed capacity, India ranks second next only
to China in the field of cement production. Now most of the cement plants are based
on dry process.
Advances in grinding and pyroprocessing have brought energy consumption in
modern cement plants considerably. Only pyroprocessing has brought down the energy
consumption to 700 kcal/kg clinker in dry processes with conventional wet process
consuming about 1400 kcal/kg clinker produced. Like other industries automation in
plants has taken substantially. Optimization of process, fuel mix, product mix, power
mix, in condition monitoring and predictive maintenance even from remote, ensuring
better EHS management in cement production (Jayant Saah and Titas Saha, 2018).
Some of the industrial wastes which find interest in cement plants are flyash, blast
furnace slag, phosphogypsum lime sludge, paper mill sludge, carbide sludge calcium
chloride from sodash plants. However, water content in some wastes is detrimental in
their use in dry process.

9.2 PROFILE OF CEMENT INDUSTRY

According to report of working group on cement Industry for XII five-year plan
(2012–17), global cement industry is expanding with 2568 million tons in 2006. Around
56% of global cement production is from China, and India has been the drivers of
148
Cement and Lime Industries 149

global cement output. India has attracted huge investment both from Indian and global
investors because of lot of development in the infrastructure and availability of raw
materials—limestone and coal, in different part of country which are the main raw
material for cement. Several global players like Lafarge-Holcim, Heilberg cement and
Vicat have invested in India.
According to IBEF ([Link] [Link], India) India is
the second largest producer of cement in world after China. Cement production capacity
stood 502 million tons per year during 2018. Cement consumption is expected to grow
by 4.5% in financial year 2019. Indian cement industry is dominated by large cement
plants and a total of 210 large plants account for a capacity of 350 million tons while
reaming 350 small plants accounting for rest. Although the per capita consumption
of cement in India is low against Asian average World average. However, with the
growing industrialization and overall improvement in infrastructure and development
activities and the living standards, the consumption and demand of cement is likely
to go up. Due to increasing demand in various sectors, cement production is expected
to reach 550–600 million tons per annum by the year 2025 ([Link]
industry/cement- [Link]) (Table 9.1). According to cement statistics the total world
production of cement ([Link] [Link]) is expected
to be around 4.8 billion metric tons by 2030 from 1100 billion tons in1990 ([Link]
[Link]/373845/ global–cement—production forecast).
Top cement manufacturing companies in India are ACC Ltd., JK Cement Ltd.,
Ultra Tech Cement Ltd., Shri Cement Ltd., Ambuja Cement, Ramco Cement Ltd., India
Cement Ltd., Cement Corporation of India, and Orient Cement Ltd.

Table 9.1. Cément consumptions 1985–2020 (million tons)

% PA growth
Continent 1985 2003 2020
2003–2020
Developed countries 323 410.5 475 0.80%
Developing countries 363.7 1202.5 2586.5 4.30%
Total 686.7 1612.9 3061.5 3.60%

9.3 PROCESS TECHNOLOGY

Different variety of cement like ordinary Portland cement, Portland blast furnace slag
cement, low heat Portland cement, rapid hardening cement, oil well cement, white
cement, etc. are manufactured in India by employing four alternative technologies:
• Acquisition and transportation of raw materials
• Preparation of raw materials
• Pyroprocessing of raw materials to form cement clinker
• Grinding clinker with gypsum into cement
• Storage and packaging
Wet process has become largely outdated because of tremendous energy requirement
i.e. about 5.5 GJ/ton of cement clinker produced. As compared to wet process, dry
process only requires 60% of the above value thus making savings in terms of coal
150 Chemical Process Technology

utilization (5) Figure 9.1 shows the process flow diagram of cement manufacture by
dry process. Different cement processes are given in Table 9.2.

Fig 9.1: Flow diagram of cement manufacture by dry process

Table 9.2: Different cement processes

Process Process details
Wet process Grinding of the raw feed is done in slurry form. Moisture in the slurry: 30–35%.
Semi-wet process Wet grinding of the kiln feed is done and then moisture is reduced to about 18%
Semi-dry process Dry grinding of the kiln feed is done and then the water is added in order to
make nodules in the nodulizer. Moisture content in the nodules about 12%
Dry process Dry grinding of the raw material is done. The kiln feed in the form of powder
is fed to kiln through suspension preheater
Note: All the above-mentioned processes usually consist of following major steps.

9.4 PROCESS TECHNOLOGY OF DRY PROCESS OF PORTLAND CEMENT MANUFACTURE

Dry process has now replaced the older wet process of cement manufacture where raw
material was grinded in wet condition. Major units in a typical dry process cement
plant consist of:
Raw material storage: Limestone, coal and raw material gantry

Raw mills: For crushing and grinding of raw material. Ball mill and vertical roller mill
are being used.
Coal mills: For crushing and grinding of coal
Cement and Lime Industries 151

Rotary kiln: Rotary kiln with precalciner and suspension preheater

Clinker cooling: Grate cooler
Cement mill: For grinding of clinker and gypsum. Ball mill and press roll are commonly
used
Silos: For storage of ground cement.

Most of the cement plant have their own limestone captive mines selective, controlled
and computerized mining of limestone is done in modern cement mill to get consistently
the desired quality of lime stone. The variation in the quality of limestone is monitored
on continuous basis by an on-line gamma ray bulk analyzer for monitoring of quality
of crushed lime for having suitable blend.
The manufacturer preblends crushed material to get a consistent quality of mill feed.
After controlled addition of argillaceous correctives material is ground to the fines (10%
residue using 90% micron sieve) to achieve better reactivity and burnability of the raw
material and to have good quality of clinker. Raw material grinding in modern mills is
done in vertical roller mill instead of conventional ball mill. Desired fines of raw meal
is achieved by the computerized control of the vertical roller mill and with the help of a
high efficiency classifier. The raw meal is fed to a constant flow storage homogenization
silo through different charging points of silo top. The homogenizing material from the
silo is subjected to a sequential extraction gates, which work on auto mode to give all
possible permutations and combination, two at a time to achieve the best homogeneity
of material.
Coal is pulverized in vertical roller mill and fed into the rotary kiln and the flash
calcifer. The homogenized material from blending silo is to the 5 stage preheater top
by an air lift and fed to the top most twin cyclone. Direct exchange heat takes place
between the down flowing material and hot waste gases coming up from rotary kiln.
The material goes preheating followed by calcinations to the extent of p0% by virtue
of recirculation flash calciner where calcinations is maximum and heat consumption
is minimum. The calcine meal is then enters the rotary kiln where clinker of desired
quality is produced. Clinker produced is air quenched in a grate cooler the computer
controlled temperature profile in the kiln and together with well balanced cooling rate
of high efficiency grate cooler ensure an optimum mineralogical structure and size of
alite and belite crystal which helps the product to gain better compressive strength
at early as well as later ages. The system also ensures the glassy form of trialcalcium
alluminate and helps the product attained an excellent volume stability. The clinker is
stored in weather proof silo to protect from weather deterioration. Typical reactions
taking place in the kiln are:

Removal of moisture
• CaCO3 CaO + CO2
• 2CaO + SiO2 2CaO • SiO2
• 2CaO • SiO2 + CaO 3CaO • SiO2
• 3CaO • Al2O3 + CaO + Fe2O3 CaO • Al2O3 • Fe2O3
• Cooling and crystallization of various mineral phases.
152 Chemical Process Technology

Final grinding of clinker with gypsum is done in cement mill using ball mill or
press roll. Modern mills have roller press grinding unit. Roller press have advantage
of low energy consumption and maintain best particle size distribution which is as
decisive factor better workability, impermeability, durability and high strength of
cement concrete. The dynamic hybrid classifier helps to get high blain which is also an
indispensable factor for high strength cement.
The fine ground cement is stored in silo and then packed by a microprocessor-based
sophisticated packing bags.

9.5 RAW MATERIAL REQUIREMENT

Calcareous—limestone, marl, chalk
Argillaceous—clay shale, laterite, alumina
Gypsum—4–5%

9.6 PROCESS TECHNOLOGY FOR PORTLAND SLAG CEMENT (PSC)

Portland slag cement has received wide acceptance throughout world because of
availability of cement grade slag having high hydraulic properties. The grinding of
clinker with gypsum (3–4%) is done in high pressure roller presses which are very
energy efficient to a blain fineness of about 4200 cm2/g. Slag is ground in finish mode.
Grounded cement in semi-finish mode and slag in finish are mixed uniformly in required
site proportion by paddle mixer. Typical raw material consumption in Portland slag
cement (PSC) is given below.
Per ton of PSC
Clinker = 0.4876 tons Slag = 0.4818 Gypsum = 0.0306 tons
Power 53.31 kWh, Fuel HSD = 2.07 L, Packing bag = 20

9.7 TECHNOLOGICAL DEVELOPMENTS IN CEMENT PLANT

Continuous development has been made in cement plant during last three decades
to improve the efficiency of grinding, reduce raw material and energy conservation,
improvement in the product quality, and improve overall efficiency of plant. Now the
mills are based on dry process phasing out the old wet process.
In electrical side use of VFD drive has become a regular feature in cement plants
reducing the electrical power saving. Use of microprocessor, computer control system,
robotics and optics (camera) for seeing the burning and size of quality have been
introduced in most of cement plants (Sahha and Sahha, 2018).
Ball mills have been used in cement industry over decades for grinding of raw
materials and clinker which have been replaced by vertical roller mill for raw meal and
clinker grinding and high press roll for cement mill and grinding of clinker and slag.
Vertical roller has advantage of lower space requirement, simplicity of operation, higher
reliability of operation, easy replacement of grinding components, reduced energy
consumption, increased output and more favorable size distribution. High pressure
rolls due to high pressure result in more fine particles of uniform size. Some of the
advantages of high pressure rolls are lower energy consumption, increased output,
less space requirements and less wear and tear.
Cement and Lime Industries 153

The suspension preheaters are used in dry process. The kiln consist of 4 or more
cyclones type preheater vessels arranged vertically and supported by structures known
as the preheater tower. In the suspension preheater, the dry feed is preheated by the
kiln’s hot gases prior to entering the actual kiln.
Use of alternative fuel has reduced energy consumption in addition to grinding and
pyroprocessing. In recent years online emission monitoring and reducing emission, use
of low NOX technology have become regular feature in cement plants and considerable
reduction emission especially particulate matter, fugitives, SOx, NOX, ammonia has been
achieved by cement plants. In addition to energy consumption reduction, environment
safety and health are being given importance in cement plants and has become a
important feature in all cement plants.
Steps have been taken by cement plants to reduce CO2 emission, and it has been
brought down. Cements plants are also giving importance to training program to their
employees for their overall growth. Water management of reducing water consumption
cooling to meet zero discharge has been also given due importance.
Vertical roller mill: Vertical roller mill is the new addition in cement plant for grinding the
raw materials and in many plants conventional ball mill has been replaced with vertical
roller mill in many plants because of the higher capacity and low power consumption.
Vertical roller mill is equipped with a grading system to which the fine particles will
have no coarse materials
Preheater/precalciner: Preheater/precalciner dry process kiln is the further development
of the preheater kiln described above. These kilns are similar except that a secondary
firing device called precalciner is added to the lower stage of the preheater section
where further recalcining occurs. Approximately 30–60% of the kiln fuel may be burnt
in the precalciner to release up to 95% of the carbon dioxide in the raw materials prior to
introduction to the kiln. Thus, majority of the material that enters the kiln is completely
calcined resulting in lower energy consumption in kiln. Other advantages of precalciner
technology are the increase in the capacity of the kilns, ability to burn lower grade coal,
improved kiln operation and greater stability of kiln, alkali and sulfate buildup and
operational stability.
Use of high efficiency separators reduces specific energy consumption of the system
and the performance of raw grinding mills and cement mill grinding mills with reduction
in maintenance cost, increased output and better cement quality because of improved
particle size distribution.
Many of the grinding aids have been found effective in reducing grinding time
and improved grinding efficiency raw mix and clinker. Some of the commonly used
grinding aids are glycols, glycerol, celex, ethanol amines salts, sodium lauryl sulfate,
acetyl trimethyl ammonium bromide, organic silicones urea and morphiline.
Waste gases from kiln and clinker cooling system can be utilized for power
generation. Huge amount of industrial waste like blast furnace slag from iron and steel
industry, fly ash, lime sudge from paper industry, red mud from aluminum industry,
phosphogypsum from phosphoric acid plant, chromium sludge from electroplating
industry, etc. can be used as partial substitute of raw material. Figure 9.2 presents the
function of suspension preheater technology.
154 Chemical Process Technology

Fig. 9.2: Suspension preheater technology

In cement manufacturing process, 60% of the total electrical power consumption is

consumed in size reduction. With a typical plant having power consumption of 100
kWh/ton of cement, the breakup of power consumption in the different section is given
in Table 9.3.

Table 9.3: Power consumption in different section of a typical cement plant kWh/t cement
Limestone quarrying, crushing, stacking, reclaiming 3.0
Raw material transport, grinding, storage 27.0
Raw meal homogenization, kiln feed, clinkerization, clinker transport and storage 35.0
Clinker grinding, cement storage 30.0
Packing and dispatch 2.0
Plant light ing, transformer/distribution loss 3.0
100.0
Cement and Lime Industries 155

Now, out of the total electrical power supplied to the mill for size reduction in actual
only 20% of the energy is actually utilized for size reduction, whereas balance 80% of
the energy is loosed as friction between particles, friction between particles and mill
elements, generation of sound, heat and vibration, material turbulence inside the mill,
loss of mechanical efficiency from motor to mill.
In a tube mill or ball mill with three chambers takes place in following stages:
• Impact crushing in the first chamber
• Impact crushing and attrition in the second chamber
• Attrition only in the third chamber.
Roller press: Roller press is also grinding equipment for size reduction and here the
comminution process takes place by:
• Pressing of material between two rollers
• Comminution by inter-particle pressing
• Breaking of material microstructure under high pressure
• If feed size to the roller press is less than 50 mm, then only inter-particle comminution
takes place.
• By roller pressing and by this comminution process cake of 31–33 mm thickness is
produced.

Fig. 9.3 Typical roller miIl

Operating principle: The material feed is subjected for a short time to extreme pressure
between the opposing rollers. This operation reduces the feed particle size within the
treated material layer (Fig. 9.3). The thickness of material layer is governed primarily
by the characteristics of the feed material and by the pressure exerted. The feed particle
size range is not of much importance, be it 0–1 mm or 0–50 mm.
The products discharged from the roller press are compacted cakes or irregular size
which are very suitable for additional reduction. They have little mechanical strength
and the cakes may be broken up using very little force. The deagglomerated cake product
156 Chemical Process Technology

from the roller press typically shows that approx. 30% of the particles have a size less
than 90 microns.
The high-pressure treatment also produces flaw like cracks in the particles, even in
the smallest fines. These flaws are an important factor in the low energy requirement
for additional reduction, whether carried out in a tube mill or by a recirculation system
to the roller press with no separate grinding in a mill.
This material treatment is carried out in the roller press very efficiently and at low
energy consumption.
Other benefits of roller press are less space requirement, maximum utilization owing
to controlled material feeding and adjustable pressure.

Vertical Shaft Kiln (VSK) Technology

The evolution of VSK technology for manufacture of Portland cement in India dates back
to the sixties when large number of mini-cement plant came into existence with lower
capacity. The process involve sinter grinding of well proportionate lime stone, clay,
low volatile coal and other corrective materials to maintain alumina and Fe2O3 content.
The pulverized raw meal is homogenized and conveyed to silo. The homogenized raw
meals are noduli zed by adding water spray which is fed at the top of the vertical shaft
kiln with uniform rate.
The shaft kiln consists of a conical sintering zone at the top and along cylindrical
shell at the bottom lined uniformly with refractory brick. Below the cylindrical shell,
the rotary grate and air lock discharge gates take care of uniform rate of discharge of
clinker from kiln (Dutta, et al. 1985).

9.8 DIFFERENT TYPES OF PORTLAND CEMENT

9.8.1 Ordinary Portland Cement (OPC)

Ordinary Portland cement is commonly used cement made by grinding clinker
(about 95%) with gypsum (about 5%).
There five types of OPC (as per ASTM 150):
Type I: C3A shall not exceed 15%
Type II: Moderate sulfate resistant C3A not to exceed 8%
Type III: Relatively high early strength, C3A 10% similar to type I, with have higher
fineness
Type IV: Low heat hydration. Percentages of C2S and C4AF are high and C3S and C3A
are relatively lower
Type V: Sulfate resistance, very low C3A. Maximum amount of C3A is 5%. C4AF +
2C3A not to exceed 20%.
Major constituents of Portland cement are described in Table 9.4. Its
chemical requirements and physical properties are discussed in Tables 9.5 and 9.6,
respec­tively.
Cement and Lime Industries 157

Table 9.4: Major constituents of Portland cement

Compound Chemical formula Typical content (%)

Dícalcium silicate (C2S) 2CaO•SIO2 10–20

Tricalcium silicate (C3S) 3CaO•SiO3 60–70

Tricalcium aluminate (C3A) 3CaO•Al2O3 5–10

Tetracalcium alumina ferrate (C4AF) 4CaO•Al2O3•Fe2O3 3–8

C3S and C3A: Responsible for the strength

High C3S and low C2S result in high early strength with high heat generation
Low C3S and high C2S develop strength slowly and generate less heat
C3A causes undesirable heat and rapid reaction
C4A results in more resistant to sea water with slower reaction and less heat evolution
Source: Heather Wans Brough IX-Materials-B-cement-8

Table 9.5: Chemical requirements for ordinary Portland cement (IS: 12269)
Sl. no. Characteristics Requirement
1. (CaO–0.7SO3)/(2.8SiO3 + 1.2 Al2O3 + Not greater than 1.02 and not less than 0.8
0.65 Fe2O3)
2. Ratio of alumina to iron oxide Not less than 0.66
3. Insoluble residue, percent by mass
4. Magnesia, percent by mass
5. Total sulfur content calculated as sulfuric Not more than 2.5 and 3.0 when tricalcium
anhydride (SO3), percent by mass aluminate percent by mass is 5 or less and greater
than 5, respectively
6. Total loss on ignition Not more than 4%
Tricalcium aluminate (C3A) is calculated by the formula
C3A = 2.65 (Al2O3) – 1.69 (Fe2O3)

Table 9.6: Physical properties and requirement of ordinary Portland cement

Sl. no. Physical properties Requirement
1. Freeness by Blain’s air permeability method 225 m2/kg
2. Soundness, by Lechatelier method Expansion not more than 10 mm
and 0.8%, respectively
3. Setting time
Initial setting time in minutes Not less than 30 min
Final setting time in minutes Not more than 600
4. Compressive strength the average compressive strength
of at least three mortar cubes (area of face 50 cm2)
72 + 1h, not less than 27 MPa
168+ 2 h, not less than 37 Mpa
672 + 4h, not less than 53 MPa
158 Chemical Process Technology

9.8.2 Oil Well Portland Cement

This type of cement is used for grating the annular space between the steel casing of
gas and oil well drilling at depth often 3000 m when temperature may be high (100°C).
Apart from lengthening the settling time the most important requirement is to reduce
if not eliminate C3A in the cement. This is generally achieved by having high iron content
in the raw slurry so as to produce C4AF practically to exclude C3A.
Sugar or cellulose derivatives are added in controlled quantity. The cement has to
remain fluid under conditions of high temperature and pressure before setting begins
so as to provide a good strength against soft and porous earth formation.

9.8.3 Waterproof Portland Cement

This is OPC to which is added during grinding a very small quantity of water repellent
agents like calcium stearate or rosin, oleic, stearic acids or pentachlorophenol, which
are hydrophobic agents. This is also called as hydrophobic cement.

9.8.4 Sulfate-resisting Portland Cement

In this type of cement, composition is so adjusted that final product becomes resistant
to sulfate or chloride bearing waters. This cement is higher in C4AF and lower in C3A.

9.8.5 High Alumina Cement

Made by fusing lime stone and bauxite. High alumina cement has following properties:
• Rapid rate of strength development to high ralves
• Superior resistance to sea water and sulfate
• Rapid hardening and high strength
• Total alumina >32%

9.8.6 Pozzuolana Cement

Pozzolana cement is made by grinding 2–4 parts of pozzuolana with 1 part of hydrated
lime. Natural pozzolana cement is volcanic ash; artificial pozzuolana are fly ash mixed
with RC as cheap extender. Pozzuolana cement has better resistance to sea water and
better corrosion resistance.

9.8.7 Special or Corrosion Resistance

Corrosion resistance cement is also used in various applications.

9.8.8 White Cement

For the production of white cement raw material free from iron is used. In India
Raymond cement is the largest manufacturer of white cement.

9.8.9 Blended Cements

Portland slag cement: PSC is made by mixing portal and cement and grounded blast
furnace cement. Portland slag cement typically contains 50% blast furnace slag. Blast
furnace slag (granulated) is made when molten clay at <100°C is brought into contact
with a high pressure of a jet of water, the sudden quenching break the molten stage
into millions of light fine mass granules.
Cement and Lime Industries 159

Pozallana cement: Pozzolana is defined as a material which while it has no hydraulic

property in itself is activated into a hydraulic water. It has lower heat of hydration,
lower porosity and better sulfate resistance than OPC. This type of cement is suited for
construction of dams, lining of canals.
A pozzolana is a substance which is not cement in itself but which becomes so upon
mixing with lime. The natural pozzolana is volcanic ash and the artificial one is fly ash.
This type of cement is obtained by grinding together Portland clinker with burnt clay
or powdered coal ash or burnt shale or any other pozzolana in proportion with 3–6%
of gypsum. fly ash content is around 30%.
Portland Fly ash cement: Portland flays cement is manufactured by mixing Portland
raw material and fly ash in different proportion.

Masonry Cement
Masonry cement are used only for masonry work like brick laying or stucos. It is not
used in concrete. It is produced by intergrading PC with ground limestone, hydrated
lime, an inert filler, an air entraining agent, retarders, coloring matter. Normally the
surface area of these cements is high. It has high plasticity and water retaining power.

High Alumina Cement

This calcium aluminate cement is manufactured by fusing a mixture of limestone and
bauxite. It is characterized by a very rapid rate of development of strength and resistance
to sea water containing sulfur bearing water.
Magnesium oxychloride: Lightly calcined MgO mixed with MgCl2 forms excellent high
strength, spark proof, wear resistance flooring, high bonding strength. So, useful in
indoor construction material with only fair resistance to water.

9.9 STEPWISE ENVIRONMENTAL IMPACT DUE TO DRY PROCESS FOR CEMENT

MANUFACTURE

Cement manufacture is dusty operation. Environmental impact due to dry process

for cement manufacture is given in Figure 9.4 during off-plant and in-plant pollution.
Application generated pollution is also there while handling of cement during
transportation and use is also there and proper precaution is to be taken during
handling.

9.10 LIMESTONE AND LIME

Limestone and lime are important feedstocks for a large number of industries. Large
amount of limestone is used in cement plants. Limestone reserves are available in MP,
Chhatishgarh, Rajasthan, Andhara Pradesh, Telangana, Karnataka, Gujarat, Odisha,
Himachal Pradesh, Uttrakhand, UP, Bihar, Meghalaya, and Assam. Some of the
perspective industries associated with limestone are agrochemical, construction, alkali,
iron and steel. Lime as such or in the form of slaked lime is used in large number of
industries like metallurgical industries both ferrous and non-ferrous, pulp and paper,
soap, caustic-chlor industries for production of bleaching powder, bleach liquor, and
soda ash (sodium carbonate), calcium carbide, sugar industry calcium carbide and water
160 Chemical Process Technology

Fig. 9.4: Stepwise environmental impact due to dry process for cement manufacture

and sewage treatment agricultural sector and many other industries. Cement industries
are one of the major limestone-consuming industries and location of cement plant is
totally dependent on the availability of limestone. Cement industry consumes about
1.46 tons of limestone per ton of cement. Precipitated calcium carbonate is produced in
the area where limestone quality is very good. Many of the lime-consuming industries
have their own generation of limestone using vertical kiln. Lime being manufactured
both in organized and unorganized sector mostly in Rajasthan and MP and other part
of countries. Demand of quicklime is set to grow with development of infrastructure
sector requiring more and more steel.
Lime is obtained by calcining of limestone in lime kiln which may be vertical kiln or
rotary kiln along with coal. Limestone mixed with coal is fed at the top of the vertical
kiln and moved down words during which calcining of limestone takes place. The
vertical kin may vary in diameter and height depending on the capacity.
CaCO3 CaO + CO2
Cement and Lime Industries 161

Poor quality of limestone in many places are major constrain in production of good
quality lime. Lime contains some of the impurities like silica, MgO, Fe2O3 and Al2O3
which are inherently present in limestone.
Slaked lime is obtained by reacting CaO with water.
CaO + H2O Ca (OH)2

Precipitated calcium carbonate is made by passing CO2 in slaked lime

Ca (OH)2 + CO2 CaCO3 + H2O

Lime sludge which is obtained as waste from Kraft pulp industries is now being
calcined to get lime which is being used in causticizing section.

9.10.1 Uses of Lime

Lime has wide application starting from household to industry.

9.10.2 Development in Lime Processing Equipments

There has been continuous development in calcinations of limestone and hydration of
lime. Both batch and continuous system are being used for calcinations of limestone.

BIBLIOGRAPHY
1. Cement Expo 2018 (http//[Link]/[Link]? nld=1Topylal5zu
MHoK0PduQ==).
2. Dutta DK, Borkakoti PK, Bora UC. “Vertical shaft kiln (VSK) Technology for mini/tiny cement
plant, Proceedings of Seminar on energy conservation in process industries” July 1-–2, 1985. The
Institution of Enginerers (India) Roorkee Local Centre pIE-7.
3. Global Cement Report 2010.
4. Report of working group on cement industry for XII five year plan (2012–17), Department of
Industrial Policy and promotion, Ministry of Commerce and Industry December 2011).
10
Glass and Refractories

Glass

10.1 INTRODUCTION
Glass making as old as the ancient civilization. The Egyptian and Mesopotamian regions
had glass makers even in the third millennium BC. Early glass making was slow and
costly. Glass blowing and glass pressing were unknown, furnaces were small; clay pots
were of poor quality. Glass manufacture had developed in Venice by the time of the
Crusades (AD 1096–1270). By the late 1400s and early 1500s, glass making had become
important in Germany and other northern European countries. First factory in United
States was a glass plant built at Jamestown, Virginia, in 1608. In the early 1800s window
glass was in large demand.
Glass has existed in India since ancient times. Archaeological surveys have unearthed
glass pieces and crucibles that can be dated back 2000 years. Glass has been mentioned
in Mahabharat and Yuktic Kalpataru. India has a long and distinguished history of
making glass beads. Black and brownish colored glass beads found at Hastinapur
(100 BC). Indian glass makers had well developed technological skills in manufacture
of beads, bangles and other articles.
Organized glass manufacturing was started in Firozabad in India. Although
ancient name of Firozabad was Chandwar Nagar. There are larger number of glass
manu­facturing units in Firozabad which produces variety of glasses including
bangles and glass domestic, artwares, scientific and lab wares glass automotive
wares, glass street and domestic wares, glass marriage wares (file:\\C:\Documents
and Settings\a\Destock Glass\[Link]). Although float glass, plate glass for
railways and building, glass and reinforced glass, glass containers are manufactured
in other part of countries also.
With the availability of coal during end of eighteenth century and development of
newer technology of cutting, welding, sealing and tempering, use of glass increased
rapidly. Modern glass industry has is producing wide variety of glasses starting from
conventional soda lime glass to silica glass, safety glass, lead glass, optical grade glass,
high impact resistance glass, tempered glass, window glass, glass fibers and so on.
Glass application is not now confined to original decorative and ornamental use, but it
is finding wide application in automotive industry, cookware, laboratory glass wares,
162
Glass and Refractories 163

packaging, optical glass with photochromic glass, insulation, lining of vessels, missiles
radomes, industrial equipments, buildings, kitchen cookware, infrared transmitting
glass, etc. With the ban on single use plastics the blowing process for manufacture
of glass containers is going to gain importance in future, in spite of its mature status.
Automotive industry is major user of glass. With recent trends and developments in
construction industry, the use of glass sheets using float process is increasing. With
increasing corrosion problem, fiber glass is also getting importance. It is expected that
with market size of glass is going to increase in future. Coated glass is getting importance
all over world due to their anti-scratch, anti-reflective low surface emissivity, or corrosion
resistance, improved impact resistance, unwanted UV and IR radiation reflection,
superior energy efficient properties. Low emissivity and heat reflective properties have
resulted in increased use of coated glass in construction.

10.2 STATUS OF GLASS INDUSTRY

Major glass company in India are Asahi Glass, Borosil Glass Works, La Opala
RG Limted, Glass wall System India, Hindustan National glass and Industries,
Saint-Gobain Sekurit India, Hadyan Glass limited, and Modi Glass. The glass
companies are located at various place all over countries looking to the availability
of raw materials, market and government incentives. Globally, the construction
and automobile industry is driver of glass consumption. However, in India
container glasses consumption is still more and domestic demand of container
glass is growing by 6–7% per year. With increase in automobile and development
in construction industry, glass production is likely to increase. In Europe also
container glasses continue to be the strongest growth area. In 2018 as per EU-28
glass production reached a volume of 36.5 million tons in Europe. Consumption
of glass in automotive and construction in China is also likely to increase (http//
[Link]/Article/3779340/Glass production-a-global-look-at-demand-for-2018.
html). Coated glass is getting importance all over world due to their anti-scratch anti
reflective low surface emissivity, corrosion resistance, improved impact resistance,
unwanted UV and IR radiation reflection, and superior energy efficient properties.
Low emissivity and heat reflective properties hav resulted in increased use of coated
glass in construction. The global coated glass is expected to grow from US$16.17
billion in 2017 to US$25.4 billion in 2025.

10.3 DEVELOPMENTS IN GLASS INDUSTRIES

Some of the development in glass industries are:
• Photochromic glass which changes color due to exposure to light (lithium silicate
modified by potassium oxide and Al oxide and traces of cerium and silver as
photosensitive ingredients).
• Bendable glass sheets
• Radiation controlling glass
• Metallic coated glass sheets—find use in building exteriors to reflect 90% solar
heat
• Optical wave guides—used to transmit voice, video and data signal.
164 Chemical Process Technology

10.4 GLASS RAW MATERIAL AND PROCESS TECHNOLOGY

Some of major types of glass are flat glass and pressed and blown glass. Flat glass
includes plate and architectural glass, automotive wind screens and mirrors. Pressed
or blown glass includes containers of various shapes, machine blown, and hand blown
glassware, lamps television tubing, etc. (Pollution Prevention and Abatement Handbook,
Word bank group July 1998).

10.4.1 Raw Materials

Basic raw material: quartz, nepheline syenite, limestone and dolomite, soda ash, sodium
sulfate, dolomite, borax, feldspar, limestone, slag, etc.
Typical specification of glass raw material
• Silica (sand or quartz)
• Specification of sands : SiO2 97–99%
Iron oxide 0.02–0.12%
TiO2 0.1%
• Lime as CaCO3 : 94.5%, insoluble 2%
• Total lime and magnesia as CaCO3 and MgCO3 97.5
• Total iron Fe2O3 % max 0.2.
• Feldspar (K2OAl2O3 6SiO2), soda ash, salt cake, borax, boric acid, fluorspar, litharge,
potash, barium carbonate.
• For special and technical grade glass: lead oxide, potash, zinc oxide, reefing agents
like arsenic oxide, antimony oxide, nitrates and sulfates.
• Refractory—low porosity alumino-silicate refractory, mullite, corrundum and
zirconia.
• Side walls—silica, sillimanite, fire bricks
• Opacifier: SinO2, Ca3(PO4)2, Na3AlF6, As2O3
• Fuel oil, producer gas, natural gas.
• Coloring agents: Various coloring agents used in glass manufacture are iron oxides
(green brown color), manganese oxides (deep amber, amethyst), cobalt oxide (deep
blue color), gold chloride (ruby red). Mix of manganese, cobalt and iron (black),
antimony oxides (white).
• Uranium oxides (yellow green), copper compounds (light blue, red), tin compounds
(white), lead with antimony (yellow), cobalt oxide (blue), nickel oxide and cobalt
oxide (dark gray), and chromite powder (cool green).
Some of the factors which affect the color glass production are temperature of melt,
temperature of reheat during working of glass, temperature of Lehr, type of colorant
being used, atmosphere of furnace, concentration colorants and composition of colorant
within glass.
Various common properties of glass are melting point, working point (pressing,
blowing and gob forming), softening point, flow point, dilatometric softening
point, deformation point, glass transition temperature, annealing point, strain point
([Link] Wikipedia. Org glass/wiki/Glass_production).
Glass and Refractories 165

10.4.2 Recycling of Glass

Recycling of glass has received considerable interest from raw material and energy
conservation point and for improving overall plant economy. Crushed recycled glass
is called and fed to glass manufacturing unit along with raw material. Main constraint
is the quality of recycled glass which necessitates additional process of sorting and
cleaning.

10.4.3 Fining and Fluxing Agents

Fining agents are added in the glass to enhance the removal of dissolved gases and gas
bubbles from the melt for getting seed-free glass. Sodium sulfate is commonly used as
in soda-lime glass, oxides of arsenic, antimony, cerium oxide.
Fluxing agents are used as additive for accelerating the batch melting reactions and
lowering the temperature at which the first aggressive melt phase occurs. The most
commonly used fluxing agents are sodium sulfate, fluorspar, lithium compounds,
spodumene blast furnace slag and cullet.

Glass Defects
Some of the major defects in glass are stones, knots, cords metallic inclusions, bubbles,
devitrification, etc.

Effect of Various constituents in the glass

SiO2: It gives the strength. It is characterized by high melting point, viscosity, low
thermal expansion, and good chemical durability.
Na2O and K2O: It acts as network modifier and reduces melting point, increases the
strength and diversification.
CaO and MgO: they reduce melting temperature, viscosity of glass and increases
chemical durability.
Al2O3: It helps in hardness by counteracted the softening of Na2O.
Fe2O3: It imparts color and present as impurities.

Various steps involved in processing of silica in glass manufacture are washing,

crushing, screening and storage of crushed and screened silica.

10.4.4 Process Technology of Glass Manufacture

The production of glass involved two main processes: float process for the manufacture
of sheet and blowing process which is used for the production of glass bottles and other
containers. The process of glass which is used in both the process involves melting
of sand along with alkaline oxide and other metallic oxide along with culet in a glass
melting tank using gas or electric heaters. The liquid glass coming out of the tank is
passed to blowing, pressing machine or on to tin bed of liquid to make float glass.
Some of the reactions taking place in glass making are solid state reactions, formation
of primary melt phases and alkali rich carbonates, dissociation reaction, and dissolving
reactions of SiO2.
Process flow diagram for glass manufacture is shown in Figure 10.1.
166 Chemical Process Technology

Fig. 10.1: Process flow diagram for glass manufacture

10.5 TYPES OF GLASSES

10.5.1 Soda Lime Glass

Soda ash glass is most commonly used glass and find application in bottles, jars, flat
glass for windows, drinking glasses. The typical composition of soda lime glass is silica
70–74%, sodium oxide 12–16%, calcium oxide 5–11%, magnesium oxide 1–3%, and
aluminum oxide 1–3%. The raw mix is also mixed with culet. The raw material consists
of sand, sodium carbonate, limestone. Soda ash in the form of sodium oxide reduces
the temperature of fusion whereas the presence of calcium oxide and magnesium oxide
gives stability to the soda lime glass.

10.5.2 Borosilicate Glass

Borosilicate glass is made by 70–80% silica and 7–13% boric oxide and smaller amount
of sodium, potassium and aluminum oxide. Borosilicate glass has good chemical and
heat resistance and good thermal shock resistance making them suitable for oven
wares, laboratory wares, high intensity light applications for glass fiber, textile or plastic
reinforcement.
Glass and Refractories 167

10.5.3 Lead Glass

Lead glass has high refractive index making sparkle brightly and relatively soft.
Higher lead content facilitate grinding, cutting and increase the brilliancy. Lead
glass contains about 24–30% lead oxide. Lead crystal glass is characterized by high
refractive index and is used in high quality drinking glass, decanters, bowels and
decorative items.

10.5.4 Silica Glass

Silica glass contains high silica and high resistance to temperature and find application
in high temperature applications.

10.5.5 Laminated Glass

Laminated glass is made of two or more sheets of glass bonded together by a flexible
transparent material which hold the glass fragments even when the glass is cracked
or broken.

10.5.6 Wired Glass

In the wired glass, wire mesh is incorporated in the middle of glass which tends to hold
the glass during crack or breakage.

10.5.7 Coated Glass

One layer of glass is coated with thin coating of minerals especially China clay gives
coated glass.

10.5.8 Fiber Glass

Fiber glass is made by passing the melted glass through high-speed rotating spinnerets.
Fiber is commonly used for lining and insulation purpose in various industries.

10.5.9 Rolled Glass Process

In this process, glass made by passing molten glass through rollers. In this process,
the semi-molten glass is squeezed between metal roll to produce flat glass ribbon with
predefined thickness and patterned surfaces.

10.5.10 Float Glass Process

Float glass term derived from the process developed by Sir Alastair Pilkington
in 1959 in UK. 905 of total flat glass is manufactured by this process. The process
consists of processing of raw materials in requisite proportioning, weighing and
mixing. The raw material is fed to the furnace where the raw material is melted at
about 15000ºC. The molten glass then flows from the furnace onto a molten bath of
tin in a continuous ribbon. As the glass material is very viscous while tin is very
fluid, the glass does not mix so that the contact between these two is perfectly fat.
The flat glass then enters the annealing chamber called lehr where cooling under
controlled condition takes place to room temperature. The flat glass can be cut in
different size (Fig. 10.2).
168 Chemical Process Technology

Fig. 10.2 : (A) Typical process flow diagram of a float glass plant; (B) Flowchart of a continuous process
for manufacture of a floot glass
Source: Shreve’ Chemical Process Industries George Austin Fifth Edition 1984.

10.5.11 Glass Lined Steel

Glass lined vessels are commonly is used in plant handling corrosive [Link]
glass lining, low carbon steel (10–25 mm thickness) is used. Vessel is annealed and then
surface to be coated is cleaned. Paste containing glass in finely ground form is applied
and fired at softening temperature of glass.

10.5.12 Fiber Reinforced Plastic (FRP)

FRP is composite material having high strength to mass ratio, electrical, chemical and
fire resistance with good heat and sound insulating properties and dimensional stability.
Epoxy resins, polyester is commonly used as binding material. FRP is commonly used
in aerospace, lining of equipments, building, etc. FRP lining is used whenever light
weight and corrosion resistant material is required.

10.6 REFRACTORY IN GLASS INDUSTRIES

Refractory play an important role in performance of glass furnaces as they are exposed
to widely varying environmental like thermal shock physical wear and corrosive nature
of processing components.
Glass and Refractories 169

REFRACTORIES
10.7 INTRODUCTION
Various refractories bricks in different sizes and shape are now available for diverse
applications. Refractories are natural or synthetic inorganic material which withstand
high temperature without showing any sign of melting or deformation and can withstand
the action of abrasive or corrosive environment at high temperature. Refractories are
used for lining of furnaces in metallurgical, cement, glass and other process industries
using furnaces with varying combinations with different shape and size. Life of any
refractory lined equipment rely on right choice of refractory quality, appropriate design,
proper application and heat up, maintenance.

10.7.1 Indian Refractory Industry

Indian refractory industry comprises over 100 established units with 11 large, 24
medium and the rest small scale plants with 4000 crore size which is growing at
10–12%. Currently, the aggregate production capacity of the industry is about two
million tons with average of 60% capacity utilization. About 75% of the refractories
produced find application in the steel industry another 12% in cement industry.
Energy, raw materials, environment, absence of skilled manpower poses challenges
to Indian refractory industry. Import of cheaper finished refractory from China is
also posing serious challenge to refractory industry. Although government of India
has put banned on Chinese material in recent time, its impact on Indian refractory
industries yet to be seen.
Some of the characteristics of refractories are:
• Resistance to chemical reaction
• Resistance to high temperature
• Resistance to abrasion
• Resistance to thermal shocks due to sudden change of temperature
• Ability to withstand the charge load at working temperature
• Low thermal change—permanent or reversible
• Low permeability and porosity
• Thermal conductivity low/heat dependency upon requirement
• Low electrical conductivity.
• Inert to working atmosphere
• Refractoriness (this is measure of fusibility).
• Low price
• Spalling (fracturing or flaking of refractory brick)
Refractories are classified as:
a. Low heat duty, intermediate heat duty or high heat duty in terms of pyrometric cone
equivalent.
b. Nature of refractory as acid, basic or neutral refractories or special refractories
c. Based on application
170 Chemical Process Technology

Classification based on heat duty:

• Low heat duty 19–28 pyrocone equivalent (PCE)
• Intermediate heat duty 28–30 PCE
• High heat duty 30–33 PCE
PCE 12 18 20 26 30 38 40
Fusion temp. 1337 1522 1564 1605 1654 1850 2015

10.7.2 Classification
Classification based on nature of refractories is given in Table 10.1.

Table 10.1: Classification based on nature of refractories

Type of refractories Description
Acid refractories Consist of acidic material, not attracted by acidic material (siliceous material):
alumina silicate, mullite, similarity, kyanite, zirconia. Readily combines with
bases
Basic refractories Consist of basic materials which are not attacked by other basic chemical,
attacked by acidic material: Magnesite, chrome magnesite, bauxite, dolomite.
Neutral refractories Consist of feebly acidic, feebly basic and does not combine with acids or bases.
Thus, resist acidic as well as basic. Fireclay bricks, chrome and pure alumina
Special refractories Carbon, silicon carbide, zirconia

Classification of refractories based on application: Blast furnace refractories, glass

refractories, steel plant refractories.
Classification based on method of manufacture: Dry press process, Fused cast, hand molded,
Formed normal fired or chemically bonded or unformed.

10.7.3 Important Refractory Materials

Properties of some of the refractory raw materials are given in Table 10.2. Important
properties of refractories are melting point, fusion point, load-bearing capacity, spalling,
resistance to slags and glasses, expansion shrinkage, heat transmission, porosity, low
or high thermal conductivity (Table 10.3).

Table 10.2: Important properties of refractory raw materials

Fire clay 1600–1750ºC Alumina (Al2O3) 2050ºC

Silica (SiO2) 1710–1720ºC Spinel (Al2O3 MgO) 2135ºC

Kaolinite (Al2O3SiO2.2H2O) 1785ºC Chromite (Cr2O3FeO) 2180ºC

Mullite (3Al2O3 2SiO2) 1810ºC Chromic oxide (Cr2O3) 2270ºC

Sillimanite (Al2O3 SiO2) 1816ºC Silicon carbide 2700ºC

Forsterite (2MgOSiO2) 1890ºC Zirconia (ZrO2) 2710ºC

Fire clay brick 1600–1750ºC Beryllia (BeO) 2570ºC
Magnesite brick 2200ºC Zirconia boride 2940ºC
Boron carbide (B4C) 2450ºC Thoria (ThO2) 3200ºC
Source: Shreve’ Chemical Process Industries George Austin Fifth Edition 1984.
Glass and Refractories 171

Table 10.3: Important properties of refractories

Melting point Melting point of refractory is the point at which the test
pyramid (cone) fails to support its own weight.
Size Size and shape of the refractory is important, since it
affects the stability of furnace as accurate size and shape
is extremely important to properly fit the refractory shape
inside the furnace.
Bulk density Bulk density is important property of refractory and is
the amount of refractory material in the refractory within
a volume and is expressed as kg/m3. High bulk density
results in high volume stability, heat capacity and resistance
to slag penetration.
Porosity Porosity of a refractory is volume of the open pores as
percentage of total refractory volume and is important
characteristics when refractory comes in contact with molten
charge, and low porosity results in less penetration of molten
material.
Cold crushing strength Cold crushing strength of a refractory is its resistance to
crushing.
Creep at high temperature Creep at high temperature is the deformation of refractory
material under stress at given time and temperature.
Pyrometric cones and pyro­metric cone Pyrometric cones are used to test the refractoriness or fusion
equivalent (PCE) point of refractory. Each pyrometric cones are mixture of
oxides which melt at a specific narrow temperature range.
Pyrometric cone equivalent is the temperature at which the
cone bends together with refractory brick.
Thermal conductivity Thermal conductivity of refractory depends on the
composition and silica content and changes with rising
temperature. High thermal conductivity is desirable when
heat transfer through brick is required while low thermal
conductivity is desirable for conservation of heat.
Spalling Spalling of refractory is fracture of refractory which may be
due to sudden heating or cooling, compression in a structure
of refractory due to expansion, variation in coefficient of
thermal expansion between the surface layer and body of
the brick (Lee S).
Permanent linear change (PLC) PLC determines the volume stability, expansion and
shrinkages of refractory (Lee S).

During use certain permanent changes occur in refractory due to change in allotropic
form, chemical reaction, liquid phase formative and sintering reactions (Lee S).

Various Type of Refractories

Fire Clay Refractory: Fire clay refractory is most commonly used refractory because of its
cheapness, and easily availability finds wide application in lining of blast furnace, open
hearth, lime kilns, pottery kilns, glass furnace, boilers, brass and copper furnace, cement
industry. Fire clay refractory has resistance to acid, slag–medium, a basic slag–low, to
oxidizing atmosphere–high, to spalling–high.
172 Chemical Process Technology

Fire clay refractories are hydrated aluminum silicate consist aluminum silicates with
varying silica content; up to 80% alumina content up to 45% silica. Fire clay refractories
are of four different classes: super duty, high duty, medium, duty, low duty with varying
amount of alumina (18–44%) and silica (50–80%) (Table 10.4).

Table 10.4: Properties of typical fire clay bricks

Brick type % SiO2 % Al2O3 % of other constituents PCEºC
Super duty 49–53 40–44 5–7 1745–1760
High duty 50–80 35–40 5–9 1690–1745
Intermediate 60–70 26–36 5–9 1640–1680
High duty (siliceous) 65–80 18–30 3–8 1620–1680
Low duty 60–80 23–33 6–10 1520–1595
Source: Bureau of Energy Efficiency, Ministry of Power, India Energy Efficiency in Thermal Utilities,
2005.

Silica Refractory: Silica refraory high silica refracory containig silica as high as 93% a with
Al2O3 1.5 max. Silica refractories are characterized by high fusion point, high mechanical
strength, high resistance to thermal shock (spalling) and high refractoriness. Silica
refractory has rsistance to: acid slag–high; basic slag–low; oxidizing atmosphere–low;
thermal and abrasion–high.
Typical composition: 94% silica (min), Al2O3 1.5% max, Quartzite ferric oxide 1.5% max,
CuO 2.5% max
Super duty silica bricks have low Al2O3 (0.4–0.5% and alkalies (0.15–0.2%) which
considerably improves refractoriness.
Application: Coke-oven battery, glass tank crown and other locations, high temperature
furnaces, e.g. soaking pit, copper refining furnace, slag pockets, regenerator and other
application furnace.
High Alumina Refractories (Neutral): High alumina refractories contains high alumina.
Alumina 50–85%. Refractoriness of high alumina increases with increase in alumina
content. High alumina refractories find application in hearth and shaft of blast furnaces,
ceramic kilns, glass tanks crucibles for melting.
Raw Material: Aluminous fire clay, bauxite, diaspore, kyanite, sillimanite, calcining temp.
1400–1500ºC.
Refractoriness: High, increases with alumina content.
Resistance to: Acid slag–high; basic slag–medium; oxidizing atmosphere–high; reducing
atmosphere–high; abrasion spalling–high.
Alumina refractory find application in hearth and shaft of blast furnaces, lime and
ceramic kilns, cement lime kilns, glass tanks and crucibles for melting a wide range
metal.
Magnesite Refractory (Basic): Magnesite refractories are chemically basic and contains at
least 85% magnesium oxide and are made from magnesite and silica which is used in its
calcined or dead burned forms. Magnesite refractory has high resistance to basic slags.
Glass and Refractories 173

These refractory finds wide application in basic steel. They also used in metallurgical
furnaces and in lime and cement lime kilns (Lee S).
Typical Composition: MgO 85% min., SiO2 5.5% max., CaO 2.5% max.
Resistance to: acid slag–low; basic slag–high; oxidizing atmosphere–high; reducing
atmosphere–high
Fire Bonded Magnesite: Resistance poor to spalling.

Chemically bonded (Oxychloride, Oxy sulfate): Resistance to spalling better.

Chromite refractories: Two types of chrome refractories are commonly in use—Chrome

magnesite or magnesite chrome.
Chrome magnesite: Chrome magnesite refractory generally contain about 15–35% Cr2O3
and 42–50% MgO and chracterized by higher resistance toward corrosive slag and high
refractoriness.
Resistance to: acid slag–low; basic slag–high; oxidizing atmosphere–high; load bearing
capacity–high.
Magnesite chrome: In magnesite chrome predominates magnesite and usually contains at
least 60% MgO and 8–18% Cr2O3 and are having better spalling resistance than chrome
magnesite.
Zircon refractory: Zircon refractory is characterized by high strength at varying temperature
condition, low thermal conductivity, very low thermal losses, and resistance to liquid
melts and finds application as high temperature insulating refractory in furnaces and
kilns. This type of refractory is used as a high temperature insulating refractory. Glass
furnace uses zirconia refractory.
Resistance to: acid slag–high; basic slag–low; thermal shock and fracture is high.

Monolithic refractories: Monolithic refractories are single piece casts in the shape of
equipment, and they are replacing the conventional type of fired refractories. Many
types of furnace hearth are constructed of monolithic slab. Monolithics are put into
place using ramming, casting, guniting, spraying, sand slinging. The material may be
magnesite grain, chrome plastic or beach sand. Some of the advantages for monolithics
are: elimination of joints which is an inherent weakness, faster application method,
special skill for installation, ease of transportation and handling, better scope to reduce
downtime for repairs, considerable scope to reduce inventory, heat saving, better
spalling resistance and greater volume stability (Energy efficiency guide for industry
in [Link] UNEP 2006).

10.7.4 Application of Refractory in Various Industries

Iron steel industry: Some of major area of application of refractory in iron and steel industry
are: blast furnace, coke ovens, basic oxygen furnace, electric arc furnace, twin hearth
furnace, energy optimizing furnace, secondary refining ladles, stainless steel vessels,
slide gate refractories, purging refractories, tidish refractories, and induction furnace.
Cement plant refractories: Dolomite, magnesia-chrome spinell, fireclay and high alumina.
Dolomite refractory for cement plant is characterized by excellent coating stability, very
good resistance to thermal shock and alkali attack in varying kiln operating conditions,
174 Chemical Process Technology

zirconia enrichment for crack arresting. Magnesia alumina sponel variety with high
thermoelastic and thermomechanical property, high alumina (45–80%). Refractories
are characterized by high strength.
Glass industry: Glass melter/refiner and regenerators operating conditions is characterized
by high operating temperature, high pull rates and low melting rates, corrosive vapors
and batch dust, and the refractory suitable for these application should have resistance
to high alkali vapor resistance, high thermal shock, high hot strength and high corrosion,
creep resistance with good volume stability at service temperature, close dimensional
tolerance, low flux factor, high heat transfer in case of regenerator.
Aluminum industry: Refractories application in aluminum industry are anode baking
furnaces, melting holding furnace, induction furnaces ladles and laundaries. Refractory
should have resistance to aluminum penetration, high strength, high corrosion
resistance. Some of the major refractories used are super duty fire clay and high alumina
bricks, phosphate bonded high alumina bricks.
Copper industry: The diversity in the operating conditions in different equipments
demands different type of refractories. Direct-bonded magnesia refractories are
commonly used. Some of the different quality of refractories for copper industry are
direct-bonded bricks based on in situ spinel formation, rebounded bricks based on
fused magnesia-chrome graining, rebounded bricks on cp-sinter of Mag-chrome grains.
Petroleum petrochemical and fertilizer industry: Refractories find wide application in the
petroleum, petrochemical and fertilizer industry for lining of various equipments which
are be exposed to aggressive service conditions such as high temperature, slagging,
erosion, abrasion, chemical attack, reducing atmosphere. Some of the major areas of
application are fired heaters, catalytic reformer, FCC unit, visbreaker, coker, gasifiers,
reformers for hydrogen production, CO ducts, cyclones, stacks, etc.
Percentage refractories consumption in various industries is given in Table 10.5.

Table 10.5: Percentage refractories consumption in various industries

Industry Percent of refractories consumption
Steel 69
Cumin and lime 7
Ceramics 6
Glass 4.8
Chemicals 4.0
Nonferrous metal 3.0
Others 6
Source: Glass worldwide May June 2018 www. Glass [Link].

Process Technology of Refractory (Fig. 10.3)

• Calcining: Certain raw materials like fire clay, bauxite, kyanite magnesite, dolomite
are calcined.
• Crushing and grinding, screening separation and recycling
• Mixing and blending
Glass and Refractories 175

Fig. 10.3: Process of refractory manufacture. (Source: Tata Refractories Product Range)

• Molding or forming—soft mud process and stiff mud process

• Dry processing
• Drying—to remove water (too quick or too slow drying causes cracks)
• Firing of burning—development of permanent bond by partial vitrification, develop­
ment of stable mineral forms
• Mineral dressing—to purify refractory material during: tubling, settling, magnetic
separator, floatation, etc.

BIBLIOGRAPHY
1. Bureau of Energy efficiency, Ministry of Power, India Energy Efficency in Thermal Utilities, 2005.
2. Glass worldwide May June 2018 www. Glass [Link]
3. Lee S. [Link] types-refractory-materials-applications-le-sylvia
4. Shreve’ Chemical Process Industries George Austin Fifth edition 1984.
5. Tata Refractories Product Range.
11
Oil and Fats

11.1 INTRODUCTION
Oil and fat are being used for edible and industrial purpose sin ancient time.
Although technology of oil extraction from seed was done since long. However,
with development of solvent extraction process and availability of food grade
hexane solvent yield of the oil has increased considerably. Oil and fats are important
sector of food industry. Oil and fats are not only important source of edible oil and
vegetable oil but also feedstock of soap, lubricants and greases. Oils may be edible
or nonedible. Edible oils are important constituent of food. Use of oils and fats for
edible purpose has been used since prehistoric age because of ease of separation of
from seeds and also animal tissues. Oil and fats provide unique texture of flavor,
lubricity, and satiety to food and are important part of human nutrient (O’Brien, RD,
”Fats and oils” CRC press Second edition, 2004). In the food preparation, fats and
oils modify product texture, carry flavors, improve mouth feel, provide a sensation
of product richness and induce satiety (Lusa and Rhees,1997). India is one of the
largest consumers of edible oil. Edible oils are used in the three different forms:
raw oil, refined oil, and vanaspati. Industrial application of oils and fats include
soap, paint, printing ink, carriers for pesticides, lubricating grease and feedstock
for chemical industry.
Many of the fatty acids which are present in edible oil have high energy content.
Large variety of oil are available from oilseeds and tree fruits and kernels. Some
of the important oils from oilseeds are mustard, rapeseed, sunflower, groundnut,
linseed oil, soybean oil, peanut, cottonseed, corn, and canolas. Some oils from tree
and kernels are coconut, palm oil, olive, palm kernel, palm oil, etc. Some of the
nonconventional oils are rice bran oil and cotton seed oil. These oilseeds and tree
fruits and kernel are presently available in different parts of word depending upon
climate and soil. The yield of the oilseeds depends upon the soil and agricultural
practices. Fats are an important ingredient of human diet and are present in the
edible oil in different proportion.

11.2 PROFILE OF EDIBLE OIL INDUSTRY

India is one of largest consumer of edible oil and also importer of edible oil to meet the
requirement of rising population which has increased to 1.3 billion at present. Edible oil
industry in India is highly fragmented with large number of extraction and vanaspati
176
Oil and Fats 177

plants. Some of the major brands of vanaspati are Dalda, Rath, Gemini, Gagan, Panghat,
and Jindal.
Oilseed production in India: The diverse agro ecological conditions in India is favorable for
production of nine oilseeds which include edible oilseeds and nonedible seeds—castor
and lineseed, ground nuts, rapeseed, mustard, soybean, sunflower, sesamum, Niger.
The production of oilseeds in India has increased from 24.5 million tons to 30.49 million
tons in 2012–13. The oilseeds yield which was 885 kg per hectare in 2004–05 increased
to 1169 kg per hectare (Ministry of Agriculture, Government of India, March 2014).
Profile of world and India production of oils and fats is given in Table 11.1. Production
by oilseed sector during 2012–13 (Nov–Oct) is given Table 11.2. Present status of
Indian vegetable industry is described in Table 11.3. Changing scenario of edible oil
consumption in India is shown in Table 11.4.

Table 11.1: Profile of world and India production of oils and fats
Oil and fats World India
Plam oil 56.95 0.08
Soybean oil 42.29 1.78
Rapeseed oil 24.26 2.34
Sunflower oil 13.74 0.21
Cottonseed oil 4.95 1.11
Groundnut oil 3.78 0.28
Ricebran oil 1.20 0.93
Other oils and fats 41.59 1.49
Total 187.4 8.20

Table 11.2: Oilseed sector 2012–13 (Nov–Oct)

Particulars
Area under oilseed cultivation 26–27 million hectare
Average yield 1100 kg
Output of cultivated oilseeds 30.7 million tons
Output of cottonseed and copra 10.8 million tons
Production of vegetable oil (edible) 8.20 million tons
Demand of vegetable oil 17.5 million tons
Import of vegetable oil 2012–13 (Nov–Oct) (edible) 10.4 million tons
Per capita consumption (2011) 14.3 kg
Per capita consumption is rising by 3–4% per annum
Source: Mehta “India’s Demand supply of edible oils with special reference to scope for sustainable
Palm oil in India Workshop organized by Global Canopy Programme and UN-ORCID, Jakarta,
Indonesia, Feb. 17, 2014.
178 Chemical Process Technology

Table 11.3: Status of Indian vegetable industry

Annual capacity %Capacity
Particulars No. of units
million tons utilization
Oil mills (crushing unit) 15000 36.0 20–30
Solvent extraction plants 600 31.0 35–40
Vegetable oil refineries 650 20.0 35–40
Vanaspti (hydrogenated units) 250 3.0 25–30

Table 11.4 Changing scenario of edible oil consumption in India

2001–2002, ‘000 tons 2012–2013 ‘000 tons
Particulars
Quantity Percentage Quantity Percentage
Palm oil 2944 29.08 8572 49.49
Soybean oil 2258 22.30 2729 15.76
Mustard oil 1721 17.00 2043 11.80
Sunflower oil 309 3.05 1171 6.76
Cottonseed oil 443 4.38 1130 6.52
Groundnut oil 1216 1201 148 0.85

11.3 CLASSIFCATION OF OIL AND FATS

Oil and fats are tri-ester of glycerol and aliphatic fatty acids generally containing up to
24 carbon atoms (Lusas, EW, Rhee, KH.” Animal and vegetable fats, oils and waxes” in
Riegel’s Handbook of Industrial Chemistry, 1997, p.2734 Ninth Edition edited by Kent,
JA. CBS Publishers and Distributors: New Delhi). Oils and fats have been classified in
different way depending on origin, drying, nondrying, edible or inedible.

11.3.1 Based on Origin

Animal origin or vegetable origin.
Animal origin: Fish oil, fish liver pool, lard tallow
Vegetable origin: Oil obtain from various seeds from vegetable: sunflower, mustard oil,
linseed oil, corn oil, soybean oil, etc.

11.3.2 Based on Iodine Value

Drying, semidrying, or drying.
Drying oil: Oil having iodine value above 130
Semidrying oil: Oil having iodine value of 90–130
Nondrying oil: Iodine value below 90 (coconut, castor oil)

11.3.3 Based on Edible Nature

Edible oil or inedible oil
Edible oil: Sunflower, mustard oil, linseed oil corn oil, soybean oil
Inedible oil: Mahua oil, ricebran oil, palm oil, coconut oil.
Oil and Fats 179

11.4 CHARACTERIZATION OF OIL AND FATS

Oil and fat are esters of glycerol and fatty acids and vary widely in their physical and
chemical properties. Properties vary widely depending upon source which may be from
different type of seeds and animal species. Glycerides of various fatty acids are solid at
room temperature are called fat and those liquid at room temperature are called oils.
The chemical and physical properties of fats and oils are largely determined by fatty
acid contents and their position in triglycerol molecules (O’Brien, RD.”Fats and oils”
CrC Press, Second edition, 2004). Fatty acid may be present as saturated fatty acid,
unsaturated fatty acids or polyunsaturated fatty acids.
Saturated fatty: Lauric, mystric, palmitic, stearic, arachide, behlinic and ligceric.
Unsaturated fatty acids: Oleic and erucic.
Polyunsaturated fatty acids: Linoleic and linolenic.
Fatty acid contents of the of the oil vary. Some of the factors which affects the
vegetable oil fatty acid composition are climatic condition, soil type, growing season,
plant maturity, plant health, microbiological condition, seed location within the flower,
etc. (O’Brien, RD.”Fats and oils” CRC Press, Second edition, 2004).
Unsaturated fatty acids have deficient carbon atoms. Average degree of unsaturation
of fatty acids can be expressed as iodine value.

11.5 PROCESSING OF OILS AND FATS

Major process involves in processing of oil and fats are:
• Processing of vegetable oil
• Processing of animal fat
• Hydrogenation of oil
Processing of vegetable oil: Various steps involved in the processing of vegetable oil from
the seed are given below:
Preparation: Without dehulling or with dehulling.
Dehulling: There are two different front-end dehulling processes: the “conventional front-
end dehulling system” and the “hot dehulling system”. Front-end dehulling involves
cleaning, weighing, drying, tempering and cracking, dehulling, conditioning and flaking.
The separation of the coarse hulls and the coarse bean particles on the upper sieve
takes place via the rotary motion of the sieve
Cracking: After the seed cracker (two pairs of rolls) a mixture of broken beans and hulls
are obtained.
Extraction of oil: Mechanical press: Expeller or screw or hydraulic press
Extraction: Using food grade extraction
The conventional expeller process involves pressing the seeds mechanically and
squeezing of oil. Because of the low recovery with conventional process, extraction
process is commonly used using food grade hexan to increase the oil recovery from the
seeds. The flakes from the extraction process contain the solvent which is desolventized
before use. Both conventional desolventizing using toaster and flash desolventizing of
flakes is used depending on end use—human or animal feed.
180 Chemical Process Technology

Refining of crude oils derived from oilseeds (Singh, 2017)

Crude oil derived from oilseeds and other oil bearing by expelling, rendering or solvent
extraction contains impurities and contaminants which includes gums, phosphatides
and other phosphorus-bearing materials, proteinous materials, sugar and glycolipids,
trace metal, contaminants, stearines and high melting waxes, tocopherols, flavors and
odoriferous compounds, chlorinated pesticide residues, free fatty acids, pigment and
coloring bodies (Singh, 2017). In the purification of edible oil, a number of purification
steps to retain the desirable components to the maximum extent with minimum possible
loss of oil.
Good refined oil must be:
i. Low in phosphorus (<0.15–<5 ppm)
ii. Low in FFA (<0.1)
iii. Low in soaps (Nil).
Chemical refining process includes (Fig. 11.1):
Step 1: Degumming
Step 2: Neutralization
Step 3: Bleaching
Step 4: Deodorization/deacidification
Step 5: Dewaxing/crystallization/winterization.
Step 6: Filtration (PP filter press/Andritz filter)

Fig. 11.1: Various steps in refining of oil from oilseeds

Types of degumming: Water degumming, acid degumming, dry degumming, enzymatic

degumming, membrane filter degumming, super degumming, top degumming, alfa
laval special degumming.
In dry degumming, gums are not separated through centrifugation but are removed
through adsorption during bleaching. Gums are of two types: Hydrable gums and
nonhydrable gums. Hydrable gums are phospholipids better known as phosphatides
and together with carbohydrates and resins are known as gums. Nonhydrable gums
are phospholipids where one of three fatty acid chains are substituted by phosphatide,
e.g. phosphatidylcholine or phosphatidylethanolamine (phosphatide—a class of
compounds with a nitrogenous base linked to phosphate group). Percent of gums in
most oils may be up to 5% (Table 11.5). They act as emulsifiers and hinder the separation
of oil and water phases in chemical refining [Link] of crude oil with water
and dilute acids (phosphoric/citric acids) is required to remove the phosphatides and
mucilaginous substances. For hydrable gums, wet degumming is done at 60–80ºC for
20 min followed by centrifugation. For NHP, acid degumming with phosphoric acids
(0.1–0.3% of 85% solution) with either a brief retention high temperature, or a longer
retention lower temperature.
Oil and Fats 181

Table 11.5: Gum present in edible oil

Edible oil 5 of gums
Soybean oil Up to 3%
Deg. soya Up to 0.5%
Solvent mustard Up to 2–2.5%
Sunflower Up to 0.5–1%
Ground nut Up to 0.1%
CPO Up to 0.05%

Deguming temperature is usually kept at 65–75ºC. In enzymatic degumming

temperature is 50–55ºC.
Types of Bleaching: Bleaching is done by bleaching earth (a type of clay-attapulgite,
bentonite and montmorillonite containing aluminum silicates with [Link] silicates).
Bleaching earth is activated by acid (to improve adsorption). Bleaching earth not only
removes color but other contaminants, residual soap, trace metals, oxidation products,
phosphatides if any. Different grades of bleaching earth are used to produce different
grades of refines oil. Bleaching is done in vacuum (700–720 mm Hg) and at 110ºC
(90–125ºC).
Deodorization/Deacidification
Deodorization/deacidification is done to remove volatile components, mainly aldehydes
and ketones (odoriferous). Essentially a steam distillation process carried out at low
pressures (2–6 mbar) vacuum followed by filtration or centrifugation. It is carried out
at temperature between 240 and 260ºC.
Stripping process (by superheated steam) under vacuum (to prevent oxidation and
hydrolysis).
Apart from FFA, tocopherols, sterols, pesticide residues, PAH, dioxins, etc. also
removed (also the pigments).
Deodorized oil has extremely low FFA, high oxidative stability, light color, bland odor
and Taste, should also contain low trans fatty acid levels, high amount of tocopherols
(antioxidants) .
Some oils contain waxes, e.g. sunflower 1%; RBO 2–3%; corn oil, etc. Therefore,
Dewaxing is done to obtain a clear table product.
Bleaching improves the quality of oil (for deep frying oil phosphorus content should
be as low as possible.) Bleaching time (15–45 min) but most common 20–30 min. After
bleaching-oil is flown to PP filters or PLF to separate oil and spent earth (may contain
up to 20% oil). Activated carbon combined with bleaching earth (1:10–20) can be more
effective than bleaching earth alone.
Winterization/Dewaxing/Crystallization
Some oils contain waxes, e.g. sunflower 1%; RBO 2–3%; corn oil, etc. Therefore, dewaxing
is done to obtain a clear table product. Refined, bleached, deodorized oil is heated to
55ºC (sunflower)—70ºC (to ensure liquid state) and sent to crystallizer. In crystallizer,
it is slowly cooled to about 10ºC (For RBO dewaxing at 28ºC winterization at 10ºC).
Crystallizer is specially insulated tank with a special slow speed mechanical agitator.
After the appearance of grains of solid fraction, oil is passed through PP press to separate
182 Chemical Process Technology

solid (stearin) and liquid fraction, e.g. RBD oil (final oil). In Palm oil fractionation,
RBD palm oil is subjected to following steps: Feed oil heating, crystal formation under
controlled cooling, crystal growth, crystal maturation and filtration’s). Solid fraction
stearin (for frying fats, margarine and shortenings) and liquid fraction olein (cooking,
salad oil).

11.6 PROCESSING OF SOYBEAN OIL

The processing of soybean oil which contains about 18–22% oils, 7–8% hull and 10–11%
moisture is processed for extaction of oil. Both conventional process using mechanical
press or extraction are used. The process of soybean seeds using extraction process
involves cleaning, cracking, dehulling, screeening for removal of hulls, conditioning,
flaking and extraction of crude oil and finally refining. The soybean is dried in order to
obtain optimal conditions for the subsequent dehulling process. Before flaking crushed
seeds are conditioned to reduce power consumption in flakers.

11.7 REFINING OF OIL

Degumming, treatment with phosphoric acid, neutralization of free fatty acids, bleaching
using clay, deodorizing.
Preparation of oil before extraction may require dulling in some seeds for removal of
shells or [Link] seed oil after preparation stage are then processed for extraction of
oil. The extraction of oil from the seed is done by mechanical pressing using screw or
hydraulic press. The cake left after extraction of oil are further processed for extraction
of remaining oil from the cake using solvent extraction process where food grade hexane
is used to enhance the recovery of oil. In the process of solvent extraction, the various
steps involved in processing of oilseed is given in Figure 11.2.

Fig. 11.2: Processing of oilseed for extraction

Oil and Fats 183

Solvent extraction: Solvent extraction of the cake or pressed seeds enhance the recovery of
oil from the seeds. Food grade hexane is commonly used for extraction. Various steps
involve in extraction is given in Figure 11.3.

Fig. 11.3 Process flow diagram for solvent extraction

Processing of oil-bearing fruits: Olive and palm are very important source of oil. Oil from
olive and palm. Processing of these foil-bearing fruits is different than the oilseeds.
Extraction of oil from olive: Olive after maturity is processed for extraction of oil. After
separating the foreign material and washing olive cannot be stored for longer time.
Olive is crushed and oil is extracted from the crushed material.
Extraction of oil from palm: Palm oil extraction involves cooking and pressing. Oil is
extracted from cooked fruits. Cooking loses the pericarp from the nuts and break the
oil cells. The oil is extracted from the liquid and semisolid by screw press.
Processing of animal fat: Various steps involve in the processing of animal fat is given in
Figure 11.4. First stage in the processing of animal fat is rendering. Rendering involves
chopping of oil-bearing tissues and boiling with water. The oil is separated from the
surface of water by skimming process. Degumming is also done to remove the easily
hydrable phospholipids.

Fig. 11.4: Processing of animal fatty tissues

11.8 HYDROGENATION OF OILS

Hydrogenation of oil is one of important steps used in oil industry for modification of
degree of unsaturation in the fatty acids. By hydrogenation unsaturated fatty acid is
converted to saturated fatty acid resulting in decrease in iodine value. Hydrogenation
process increases the melting point of the vegetable oils. Hydrogenated oil remains
in solid state and after coming in contact with human body get liquefied. A typical
hydrogenation unit consists of following unit.
Pretreatment: Refining and bleaching of oil.
184 Chemical Process Technology

Hydrogen production: Smaller unit uses hydrogen cylinders while large units generate
hydrogen using the conventional process of hydrogen generation.
Hydrogenation of oil: The hydrogenation process may be carried out either in batch or
continuous process. Hydrogenation process is commonly used for manufacture of
vanaspati which essentially cooking oil fully or partially hydrogenated. The process
involves preheating of oil and then catalytic hydrogenation of oil in presence of solid
supported nickel catalyst at about 180ºC and in a batch reactor. For large scale production
continuous reactors are used. The hydrogenation process is exothermic reaction and
the heat of reaction is utilized for heating the preheated oil to reaction temperature.
After hydrogenation the catalyst is separated using water washing or filtration through
acidic filter. Recovered catalyst is reused. Figure 11.5 presents a typical hydrogenation
process flow diagram.

Fig. 11.5: Typical hydrogenation process flow diagram

Oil yields of oilseeds and tree fruits and kernels vary widely. Oil contents of peanut,
cottonseed, soybean, sunflower are about 40–45%, 16–20%, 18–20%, 35–3%, respectively.
Oil contents in coconut, palm, and olive are 65–68%, 45–50%, respectively (O’Brien, 2004).
Oil yields of peanut, cottonseed, soybean, sunflower are 83–95, 181–204, 208–267 kg per
acre, respectively. Oil yields in case of tree fruits and kernels are 294–394, 1210–2016,
and 40–118 kg, respectively.

Typical oil extraction from 100 kg of oilseeds

Castor seed 50 kg Palm fruit 20 kg
Copra 62 kg Rapeseed 37 kg
Cottonseed 13 kg Sesame 50 kg
Groundnut kernel 42 kg Soybean 14 kg
Mustard 35 kg Sunflower 32 kg
Palm kernal 36 kg
Source: [Link]

Blended Edible oil:Blended edible oil is mixture of two edible vegetable oils. BIS
has provided guidelines for blending (IS 14309, 1995) of vegetable oil to avoid
adultration.
Oil and Fats 185

Type 1: An admixture of any two refined edible oils (expressed or solvent extracted)
where one oil may be refined, solvent extracted rice bran oil.
Type 2: An admixture of any one of the edible grades of raw (expressed) edible oil and
one refined edible oil (expressed or solvent extracted rice bran oil.
Type 3: An admixture of any two two edible grade expressed raw edible oils, except
rice bran oil.
As per IS specification blended vegitable oil shall be clear and free from ranacity,
adultration, suspended or foreign mateer, separated water, added or flavoring
substances
The blended oil shall not less than 20% by mass of any edible oil. The blended edible
oil shall be free from argemone oil, hydrocyanic acid, mineral oil and other edible oil
and adultrants.
Palm oil: Palm oil is an edible vegetable. The oil palm tree produces high-quality, versatile
oils. It only grows in the tropics, where its cultivation can have disastrous impacts on
people and the environment. Africa, Malaysia, and Thailand are major producer of
palm oil. Palm oil is used in around 50% of products. Consumers purchase and use on
a daily basis. Palm oil is extensively used to manufacture biofuel and biodiesel. Palm
is also used as feed for livestock commonly known as palm kernel cake (PKC) which a
by-product of palm kernel oil and is considered as medium grade protein feed (http;//
[Link]/[Link]). Malaysia is larger producer of
palm oil.

BIBLIOGRAPHY
1. BIS (IS 14309, 1995)
2. [Link]
3. http;//[Link]/[Link]
4. Lusas EW, Rhee KH. “Animal and vegetable fats, oils and waxes” in Riegel’s Handbook
of Industrial Chemistry, 1997 p. 2734. Ninth Edition edited by Kent, JA. CBS Publishers &
Distributors: New Delhi.
5. Mehta. “India’s Demand supply of edible oils with special reference to scope for sustainable
Palm oil in India Workshop organized by Global Canopy programme and UN-ORCID, Jakarta,
Indonesia Feb 17, 2014.
6. Minstry of Agricuture, Govt of India, March 2014.
7. O’Brien RD. “Fats and oils” CrC Press Second edition, 2004.
8. Singh SP. Former director BL Agro Private communication.
12
Explosives and
Miscellaneous Chemicals

12.1 INTRODUCTION
Explosives are reactive substances containing huge amount of potential energy which
can produce explosion. Under the influence of thermal and mechanical shock, explosive
decomposes rapidly and spontaneously with the evolution of great deal of heat and
much gas at high temperature and pressure. Use of explosives has been reported since
ancient time and use of black powder has been reported in ninth century in China.
However, extensive use of explosive started with the development of nitroglycerine
which was developed in 1847. Due to unstable nature, use of nitroglycerine as explosive
has been banned and was replaced with nitrocellulose, smokeless powder and gel lignite.
Development of trinitrotoluene (TNT) took place during World War I. Availability of
toluene from coke-oven plant and later from catalytic reforming process gave significant
growth of TNT explosive. With development of mining industry and infrastructure
development, use of explosive also increased in industrial sectors like mining of coal,
iron ore, limestone and tunneling. Some of the important industrial uses of explosive
are hydroproject, road and rail projects, controlled demolitions underwater trenching,
oil well perforations, etc. (Kannan SV. “ Status of Explosive Industry in India” Chemical
Industry Digest Annual—January 2003, p.109).

12.2 PROFILE OF INDIAN EXPLOSIVE INDUSTRY

Manufacture of first civilian explosive started in India in 1955 with setting of ICI first
NG based plant in Bihar. Subsequently, Indian Detonators Ltd unit was started in 1954
with a capacity of 192 million tons per annum. Slurry-based explosive set by IBP and
Karnataka Explosives Ltd. Premier Explosives Ltd was set up in 1980 with manufacture
of PETN, detonating fuse and pentolite booster in 1986 and detonator unit in 1989. Since
then a large numbers of detonating fuse and detonator units have been set up in India.
With the development of indigenous technology and availability of raw materials from
chemical industries large number units have been set up to manufacture explosive and
accessories.
Indian explosive industry encompassed the activities related to the manufacturing
and selling of industrial explosives gun powder, bulk’ cartridge and ANFO based
explosives segments of nitrate mixture, nitro-compound including PETN and boosters
explosive accessories, such as detonators, detonating fuse and safety fuse. Mining
industry consume major portion of industrial explosive. Coal mining is the largest
consumer of explosive.
186
Explosives and Miscellaneous Chemicals 187

There are 113 explosive plants and 118 site mixed explosive plants in medium and
small sectors engaged in production of explosives. The most commonly used terms in
explosive are given in Table 12.1, and production of different types of explosives in
India are shown in Table 12.2.

Table 12.1: Commonly used terms in explosive

Deflagration An explosive reaction such as rapid combustion that moves through
an explosive material at a velocity less than the speed of sound in
the material
Detonator A tubular device one end of which is closed and the other left open
for insertion of safety fuse for the initiation of explosion within tube
or fitted with wires or other device for that purpose and sealed
Detonating fuse A cord containing a center core of the explosive authorized by chief
controller which is used to maintain high explosive charges and
transmit explosion from one explosive charge to another
Propellant An explosive that normally functions by deflagration and is used for
propulsion purpose
Safety fuse Fuse for igniting charges of other explosives which burn and does
not explode and which does not contain its own means of ignition
Ammonium nitrate fuel oil Mixture of ammonium nitrate and fuel oil which is not cap sensitive
explosive (ANFO) and does not include emulsion explosive or site mixed explosive
Emulsion explosive Explosive material in the form of emulsion
Slurry explosive An explosive material in form of slurry containing oxidizer, fuel,
thickner and water
Non-explosive emulsion Water in oil emulsion or a slurry matrix which is neither cap sensitive
matrix nor boost sensitive
Gun powder Explosive containing a mixture of inorganic nitrate charcoal and sulfur
High explosive Characterized by a very high rate of reaction
Permitted explosive Explosive which is permitted by director general of mines, safety to
be used in underground coal mines
Site mixed explosive An explosive charge formed in the borehole
(SME)
Plastic explosive Explosive material in Flexible or elastic sheet form with formulated
with one or more high explosive in thgeir pure form and have vapor
pressure less than 10–4 Pa ata temperature of 25ºC and is formulated
with a binder material and as a mixture, malleable or flexible at normal
room temperature
UN number Four digit number assigned
Safety management plan The comprehensive plan for ensuring and managing safety in an
explosive manufacturing unit
Safety distance Distance necessary to be kept between any licensed factory shed,
magazines, store house or other licensed premises and protected
works
Magazine A building or Structure (other tha an explosive manufacturing unit
Source: The Explosive Rules, 2008 and Ministry of Commerce and Industry, New Delhi.
188 Chemical Process Technology

Table 12.2: Production of different types of explosives in India

Description Annual installed capacity Production 2013–14
Gun powder metric tons 1599.55 549
Cartridges, site mixed metric tons 580386 269999
1350385 519878
Nitroglycerine Prohibited since 1/4 2004
Booster and pentaerythritol tetranitrate 16418.67 6186
(PETN) (metric tons)
Safety fuse (million meters) 268.29 74
Detonators (million meters) 576.2 427
Detonators million no. 969.05 1031

Classification of Explosive
Explosive are classified based on physical state, by speed or velocity at which they
expand, by sensitivity.
Physical state: Solid, liquid, gas.

Composition: Single explosive compound or mixture of explosive compounds with or

without non-explosive substances.
Velocity: Low explosive, high explosive

Sensitivity: Primary, secondary, and tertiary explosive.

High explosive: It undergoes detonation (i.e. an explosive process of high speed involving
a sustained shock wave) at a rate of 2000– 9000 m/s. It is primary or secondary.
Reaction front: Shock phenomenon

High explosive
|
| |
Primary (Initiating Secondary explosive (or
explosive or initiators) non-initiating explosives)

Primary explosives: Primary explosives are very sensitive to heat, impact, friction and
hence are used to cause the explosion of less sensitive explosive. Initiating explosives
are generally used in primers, detonators and percussion cap.
N O–N=C
Lead azide Pb (– N ) , mercury fulminate ( Hg ), lead styphnate (lead
    N 2 O–N=C
trinitroresorcinate), diazonitrophenol, tetrazine.
Secondary explosives (Non-initiating explosives): They are not sensitive enough to be
detonated by impact or friction or heat: Dinitrotoluene (DNT), trinitrotoluene (TNT),
pentaerythritol tetranitrate (PETN), research development explosive (RDX) cyclonite,
and picric acid.
Low explosives: Low explosives undergo into combustion at low rates, which undergo
auto-combustion at rates 10–2 m/s, and also called deflagrating (or simple purning
explosive). Reaction front is flame.
Explosives and Miscellaneous Chemicals 189

Booster high explosives: These are insensitive to both mechanical shocks flame but explode
with great violence when set off by an explosive shock.
Pyrotechnics: Mainly used for intense light and smoke.
Screening smoke: White phosphorus, hexachloroethane C2Cl6, SO3 + chlorosulfonic acid.
Propellants: Which on deflagration (burning) generate hot gases at predetermined
controlled rates and thus provide the working fluid for driving projectiles. Liquid
(LOX) or solid (NC).
Black powder: KNO3, charcoal, sulfur 75 : 15 : 10.
Nitroglycerine-based explosive: Dynamite is mixture of highly sensitive nitroglycerine
with saw dust, powder silica, diatomonaceous earth.
Nitrocellulose explosive: Smokeless powder, cordile.
Ammonium nitrate-based explosive: Ammonium nitrate and fuel oil (ANFO), AN, fuel
oil 94 : 5, slurry explosive, slurry-blasting agent (SBA).
Acetone peroxide
TNT
RDX, PETN, HMX: They are very powerful explosives.
Arm strong mixture: Mixture of potassium chlorate and red phosphorus.
Uses
1. Industrial explosive, used for this purpose, such as mining of coal, mineral ores, etc.,
destruction of building
2. Military explosive used for destruction for assisting in military operation including,
identification signaling, etc. in warfare.
3. A typical explosive consists of explosive base and combustible, oxygen carriers,
antacids, absorbents.
Properties of explosive: Some of the important properties of explosive are oxygen balance,
sensitivity to impact and heat, stability to storage, shatterability (brisance) explosion
temperature, hot oil explosion, velocity of detonation (confined and unconfined),
detonation violences, explosion strength, water resistance, detonation pressure, weight
strength, bulk strength.
Characteristics of explosives: Four basic steps are involved:
• Ignition by shock impact, friction or combination of these conditions
• Rapid decomposition in a detonation
• Release of heat and large quantity of gases
• Rock fragmentation, displacement, ground vibration, air blast by energy released
by the detonation.
Important explosives
• Lead styphnate (2,4,6 trinitroresuccinate)
190 Chemical Process Technology

• Diazodinitrophenol (DDNP) C6H2N4O5 made by diazotization of picramic acid

NH2(NO2)2C6H2OH with sodium nitrite and hydroxide.

• Tetrauazene C6H8ON10

Nitroglycerine and Dynamite

CH2ONO2

CH2ONO2

CH2ONO2

Nitroglycerine is the first explosive employed on large scale. It is made by nitration

of glycerine using mixed acid (40% HNO3 and 59.5% H2SO4), 0.5% H2O in agitated
reactors at low temperature (5–10ºC). After the nitration nitroglycerine is separated
from the spent acid. Nitroglycerine is further washed with warm water and 2% sodium
carbonate solution to ensure complete removal of acids.
Originally dynamite was manufactured from nitroglycerine by absorbing nitro­
glycerine into clay. However, now the dynamite is made by absorbing nitroglycerine
in wood floor, ammonium nitrate or sodium nitrate. Various types of dynamite are
straight dynamite, ammonia dynamite, straight-gelatin dynamite, ammonia-gelatin
dynamite, semi-gelatin dynamite, permissible dynamite, etc. (Chemical Explosive
and Rocket propellant, WB Sudweeks and Rocket Propellants. Clark GM, Chen FM.
p.1186 Riegel’s Handbook of Industrial Chemistry” Ninth edition, Edited by Kent, JM.
CBS Publishers & Distributors 1997). (Explosives, Propellants and Toxic Chemical
Agents” Chapter 22, p.389. Shreve’s Chemical Process Industries, Fifth edition Mcgraw
Hill Book Company, 1984).

Nitrocellulose (Gun Powder)

Nitrocellulose is made by nitration of cellulose in presence of mixed acid (nitric acid

and sulfuric acid). The process uses nitric acid to convert cellulose into cellulose nitrate
and water. The sulfuric acid acts as a catalyst to produce the nitronium ion, NO2.
3HNO3 + H2SO4 + C6H10O5 C6H7(NO2)3O5 + 3H2O = H2SO4

Nitrated cellulose is washed thoroughly by boiling water and again with water in a
beaker.
Explosives and Miscellaneous Chemicals 191

Trinitrotoluene (TNT)

Trinitrotoluene is made by nitration of toluene which obtained from catalytic

reforming of naphtha. Originally toluene was available from coke-oven plant. However,
with development of petrochemical industry, aromatic plants are the major source of
toluene.
The process of TNT manufacture consists of nitration of toluene in presence of
mixed acids (sulfuric acid and nitric acid) in a agitated reactor, removal of acid in
successive separation process. Finally, TNT is washed with water and sodium sulfate
solution. Three step are involved, i.e. nitration of toluene to mononitrotulene, nitration
of mononitrotulene to dinitrotoluene, and finally, nitration of dinitrotoluene to
trinitrotoluene.
Toluene mononitro toluene dinitrotoluene trinitrotoluene

Upon detonation, TNT decomposes as follows:

2C7H5N3O6 3N2 + 5H2O + 7CO + 7C

2C7H5N3O6 3N2 + 5H2 + 12CO + 2C

Pentaerythritol Tetranitrate (PETN)

PETN is made by nitration of pentaerythritol. Pentaerythritol is made by reaction

of formaldehyde with acetaldehyde which react by aldol condensation under basic
catalyst followed by a crossed Cannizzaro dispropornation.
192 Chemical Process Technology

Research Development Explosive (Cyclonite) RDX

RDX is made by nitration of hexaminethylenetetramine prepared from formaldehyde

ammonia. Reaction taking place in RDX preparation is given below:

High Military Explosive (HMX)

HMX: HMX is made by reaction of hexamethylenetetraamine and HNO3

Tetryl (trandimethyleaniline) (CH3)2NC6H7

Picric Acid (2,4,6, Dinitrophenol)

Explosives and Miscellaneous Chemicals 193

Picric acid is made by nitration of phenol

Nitroguanidine picrate

DIPAM (Dipiccrunide)

Black Powder: KNO3, charcoal, sulfur [Link]

Nitroglycerin-based explosive: Dynamite (NG, Kieselguhr 75:25), Gelatine dynamite

NG 75%, NaNO3 WM; Blasting gelatin NG: NC 92:8. Semi-gelatin NG, AN, WM, NC
([Link]); NG powder NG AN WM [Link]
Nitrocellulose explosive: Powder cordite

Chlorate and perchlorate based explosives:

TNT Explosive: ANATOLS (AN, TNT 80:20 OR 50:50), Baratols (Barium nitrate and
TNT) TNT powder (TNT 50:50%) AN, WM, AL, TETRYTOLS (TETRYL and TNT)
PENTOLITE (PETN, TNT 50:50%. Wax).
RDX composition (from nitration of hexamethylenetetraniline C6H6O6N6 cyclonite)
RDX-TNT-Wax (RDX, TNT 60:40 WAX) RDX-WAX (gly), PLASTIC EXPLOSIVE (PE),
(RDX Oil and Plasticizers 88:12), Torpex: RDX, TND and ALUMINUM
Aluminized compositions: AMMONIALS-(AN) TNT Al charcoal, [Link], MINULS-
AN, TNT, Al [Link] TITORAL-(TNT Al 80:20) TORPEXES WAX (RDX, TNT, Al,
[Link])
TETRYL 2,4,6, Trinitrophenyl (Methyl nitroamine ) used as base change in blasting
caps, booster explosive, as ingredient of binary explosives.
Explosive D: Ammomium picrate
PETN (Pentaerythritoltetranitrate) (CH2ONO 2) 4 used in detonation fused and
commercial blasting caps. Booster explosive, blasting charge made by reaction of
pentaerythritol with nitric acid.
TOXIC chemical weapon: These includes those substance which by their chemical
action produce powerful physiological effects.

Name action Rate of action Physiological

Diphosgene (Cl COOCCl3) Immediate 3 hours Damages lungs
Sarin CH3 (C3H7O) FPO breath and death Very fast Less action
Tabun (CH3)2N(C2H5O) CNPO and death Very fast Less action breath
194 Chemical Process Technology

BIBLIOGRAPHY
1. Chemical Explosive and Rocket propellant, WB Sudweeks and rocket propellants. Clark
GM, Chen FM. p. 1186 “Riegel’s Handbook of Industrial Chemistry” Ninth edition Edited by
Kent, JM. CBS Publishers & Distributors 1997.
2. Explosives, Propellants and Toxic Chemical Agents” chapter 22, p. 389. Shreve’s Chemical Process
Industries Fifth edition Mcgraw Hill Book Company, 1984.
3. Kannan SV. “Sattus of Explosive Industry in India” Chemical Industry Digest Annual-January
2003, p. 109.
4. The explosive rules, 2008 and Ministry of Commerce and Industry, New Delhi.
13
Metallurgical Industry in India

13.1 INTRODUCTION
Metal industries are the indispensible part of an economy and have played important
role in the infrastructure development and material development in chemical process
industries. They are the measure of the industrial development of a country. Iron and
steel sector was the main supplier of many organic and inorganic chemicals before
coming of the petrochemical industry through coke-oven plants. Coke-woven plants
manufacture some of the important fertilizers like ammonium sulfate and ammonium
nitrate and calcium ammonium nitrate. Iron, copper and zinc industries employing
pyrite ore produce sulfuric acid. Development of the various materials like stainless
steel especially high nickel alloy, steel alloy and some of the metal alloys like high
silicon cast iron Durimet, nickel-molybdenum and nickel-molybdenum-chromium
alloys, copper and its alloys Monel metal Inconel, etc. have been playing important
role in providing material of construction for highly corrosive and high temperature
application. Various precious and refractory metals are important constituent of many
catalysts, alloys and refractories.
Metals have been broadly classified as ferrous and nonferrous metals. Some of the
other class of metals may be precious metals, refractory metals, alkaline earth metals.
Based on the process, metallurgical process may be divided into primary metallurgical
and secondary metallurgical process. Ores of the various metal are available either in the
forms of sulfide, oxide, and native. Copper, lead, and zinc are predominantly present
in the form of sulfide. Iron ores are present in the oxidized form. Some of the metals
like gold are present as native.
Ferrous metals: Ferrous metals are those which contain iron with small amounts of the
other metals and element to give specific required properties. Various metals are mild
steel, cast iron, high tensile steel, stainless, high speed steel, high carbon steel, and
medium carbon steel.
Nonferrous metals: Nonferrous metals primarily do not contain iron as principle; however,
they may contain small amount of iron also. Some of the important nonferrous metals
are aluminum, copper, zinc, lead, cadmium, molybdenum, cobalt, and mercury.
Precious metals: Various precious metals are like platinum, gold, silver, palladium,
rhodium, iridium, ruthenium, and osmium.
Refractory metals: Various refractory metals are chromium, manganese, tungsten,
vanadium, molybdenum, titanium, tantalum, niobium, and zirconium.
195
196 Chemical Process Technology

Alkali and Alkali earth metals

Metallurgical processes: Metallurgical processes have been classified as primary
metallurgical process and secondary metallurgical process. Primary metallurgical
process involves the extraction of metals from ore and minerals. Secondary metallurgical
process involves processing ore after reduction, scrap salvage and ingots.
Contribution and rank of India in world production of important minerals and metals
in 2010 is given in Table 13.1.

Table 13.1: Contribution and rank of India in world production of important minerals and metals
Production 2010
Minerals Unit capacity India’s rank, 2010
World India
Bauxite 000 tons 2,19,000 12,641 6th
Iron ore Million tons 2,611 208 4th
Manganese ore 000 tons 42,800 2,881 5th
Aluminum 000 tons 41,500 1,621 6th
Copper (refined) 000 tons 19,000 512 10th
Steels (crude/liquid) Million tons 1,418 70 4th
Lead (refined) 000 tons 9,700 57 25th
Zinc (slab) 000 tons 12,9000 740 3rd
Chromite 000 tons 30,000 4,262 3rd
Source: Annual Report 2012–13, Ministry of Mines, Government of India.

13.2 IRON AND STEEL

Iron ore is vailable in the form of hematite (Fe2O3) or magnetite ([Link]). Iron ore
is also available in the form sulfide (pyrite FeS2) and carbonate like siderite (FeCO3).
India is the fourth largest producer of crude steel and second largest producer in the
world. India is the largest producer of direct reduced iron or sponge iron. Crude steel
capacity in the country is 99.57 million tons in 2013–14 as against 97.02 million tons in
2012–13. Per capita consumption of steel in the country has risen from 45 kg in 2008–9 to
about 60 kg in 2013–14. Steel sector contributes nearly 2% of the country’s GDP. India’s
industrial development began with the setting of Tata Iron and Steel at Jamshedpur in
[Link] came the Burnpur steel plant and Bhadrawati steels plant in 1919 and 1923,
respectively. There are seven integrated steel plant under Steel Authority of India
Limited, Bhilai, Durgapur, Rourkela, Bokaro, and Burnpur. There are about 1800 steel
re-rolling mills. In 2011, the Indian steel sector total market was US$ 57.8 billion, while
export of steel has crossed 7 million tons. Presently, steel industry employs around
5 lakh people. India’s steel production was 78.42 million tons in 2012–13. Crude steel
capacity and production in 2012–13 was 97.02 and 78.42 million tons, respectively. World
crude steel production was 1607 million tons during 2013. Chinese crude production
is about 779 million tons. In 2012, this sector accounted for 72% of of Asian and 48% of
world crude production (Figs 13.1 and 13.2) (Annual Report 2013–14, Ministry of Steel,
Government of India).
Metallurgical Industry in India 197

Fig. 13.1: Global per capita consumption of steel (in kg)

Fig. 13.2: Crude steel capacity and production

Process of Manufacture of Iron and Steel

The principal raw materials for an integrated steel plant are iron ore, limestone, and
coal (or coke). These materials are charged in batches into a blast furnace where the iron
compounds in the ore give up excess oxygen and become liquid iron. At intervals of a
few hours, the accumulated liquid iron is tapped from the blast furnace and either cast
into pig iron or directed to other vessels for further steel-making operations. Historically,
the Bessemer process was a major advancement in the production of economical steel,
but it has now been entirely replaced by other processes, such as the basic oxygen
furnace and LD converters and EAF route.
During steel-making, impurities such as nitrogen, silicon, phosphorus, sulfur and
excess carbon are removed from the raw iron, and alloying elements, such as manganese,
nickel, chromium and vanadium are added to produce different grades of steel. The
iron and steel making process may be divided into seven different steps:
• Coke making (Conversion of coal into coke)
• Sinter making (Conversion of iron ore into sinter)
• Iron making (Conversion of ore to hot metal or liquid iron)
• Steel making (Conversion of hot metal to liquid steel)
• Casting (Solidification of liquid steel into blocks/ingots/slabs)
• Rolling (Reducing size of blocks/ingots/slabs)
• Finishing (getting finished shape and desired property of steel).
198 Chemical Process Technology

The interrelation of these operations is depicted in a general flow diagram of the iron
and steel industry in Figure 13.3.
Coke is produced in coke-oven batteries by the process of indirect heating to around
1000–1100ºC in the absence of air. Coke making process is multistep complex process
and variety of solid liquids and gaseous products are produced which contain coke and
many valuable products like coke-oven gas, coaltar, light oil, and aqueous solution of
ammonia and ammonia salt.
In the process of converting coal into coke, the volatile matter in the coal is vaporized
and driven off. This volatile matter leaves the coke-oven batteries as hot, raw coke-oven
gas. After leaving the coke-oven batteries, the raw coke-oven gas is cooled and sent to
by-product plant to recover by-product coal chemicals and to store the gas so that it
can be used as a fuel gas.

Fig. 13.3: Schematic process flow of a typical Integrated Iron and steel plant.
Source: Singh S. Private communication

Coke-oven by-product is an energy rich fuel with a calorific value of around 4000–
4200 kcal/Nm3 which is being distributed to various shops of a steel plant to fulfill their
thermal energy requirement.
During the process of sinter making, a shallow bed of fine particles is agglomerated by
heat exchange and partial fusion of the quiescent mass. Heat is generated by combustion
of a solid fuel and mixed with the bed of fines being agglomerated. The combustion
is initiated by igniting the fuel exposed at the surface of the bed after which a narrow,
high temperature zone is caused to more through the bed by an induced draft applied
Metallurgical Industry in India 199

at the bottom of bed. The bonding is affected by a combination of fusion, grain growth,
and slag liquidation. The generation of volatiles from the fuel and flux stone creates
a frothy condition and the incoming air quenches and solidifies the rear edge of the
advancing fusion zone. The product ‘sinter’ consists of a cellular mass of ore bonded
in a slag matrix.
In sintering process, fine grain raw material processed into coarse grained iron
ore sinter for charging the blast furnace. In sintering process, meticulously prepared
mixtures are created consisting of fine ore, concentrates, and extras and under sizes
arising from screening lumpy burden components at the blast furnace. Ferriferous
fine grain discharges from the production chain of the entire steel works are also put
into the mixtures. By igniting suitable fuel, such as mixed gas (mixture of BF gas and
CO gas at certain ratio), iron ore sinter is produced by down draft process. Normally,
coke breeze from screening lump coke at the blast furnace is used as fuel. Fine-crushed
limestone is traditionally used as a flux in the sinter plant, because it plays a vital role in
the formation of slag in the subsequent blast furnace process. Alternatively, quicklime
can be used to increase sinter plant production.
Iron is produced in blast furnaces by the reduction of iron oxide with coke and hot
air also known as hot blast. The large, refractory lined furnace is charged through its
top with iron (as ore, pellets, and/or sinter), flux (as limestone, dolomite), and coke
for fuel. Iron oxides, coke and fluxes react with the hot air to form molten reduced iron
(known as hot metal) and slag. The molten iron and slag collect in the hearth at the
base of the furnace. The by-product gas, also known as blast furnace gas, is collected
through off takes located at the top of the furnace and is recovered for use as fuel with
a calorific value in a range of 750–900 kcal/Nm3.
This by-product gas is cleaned and cooled in either water-based scrubbers in
combination with BF top pressure controlling mechanism (either septum valve or
through AG element) and distributed to various furnaces to be used as fuel. Liquid
metal from blast furnaces is being transported to the steel making shop through ladles
(open or close type/torpedoes) where it is being heated by burning of CO gas generally
in mixers before taking it for steel making.
Today there are two major commercial processes for making steel, namely basic
oxygen steel- making, which has liquid pig-iron from the blast furnace and scrap steel
as the main feed materials, and electric arc furnace (EAF) steel-making, which uses
scrap steel or direct reduced iron (DRI) as the main feed materials.

Basic Oxygen Furnace

The most commonly applied process for steel-making is the integrated steel-making
process via the blast furnace—basic oxygen furnace (BOF).
In the BOF, the iron is combined with varying amounts of steel scrap (<30%) and
small amounts of flux. A lance is introduced in the vessel and blows 99% pure oxygen
causing a temperature rise to 1700ºC. The scrap melts, impurities are oxidized, and the
carbon content is reduced by 90%, resulting in crude steel which goes for secondary
steel-making processes where the properties of steel are determined by the addition of
other elements, such as boron, chromium and molybdenum, amongst others, ensuring
the exact specification can be met. Basic oxygen furnaces currently produce about 70%
of the world’s steel. A further 29% of steel is produced in electric arc furnaces.
200 Chemical Process Technology

Electric Arc Furnaces

Electric arc furnace (EAF) process, or mini-mill, does not involve iron-making. It reuses
existing steel, avoiding the need for raw materials and their processing. The furnace
is charged with steel scrap. It can also include some direct reduced iron (DRI) or pig
iron for chemical balance.
The EAF operates on the basis of an electrical charge between two electrodes providing
the heat for the process. The power is supplied through the electrodes placed in the
furnace, which produce an arc of electricity through the scrap steel (around 35 million
watts), which raises the temperature to 1600ºC, melting the scrap. Any impurities may
be removed through the use of fluxes and draining off slag through the tap hole.

13.3 ALUMINUM
Indian aluminum industry started production of aluminum in 1943 and became self-
sufficient in 1989. Per capita consumption of aluminum in India is 1.4 kg against 6.8
kg in Brazil, 22.8 in USA, 27.6 in Japan and 38.2 in Germany. Even if India reaches half
of the world average by 2020 it would imply aluminum consumption of 5.5 million
tons to 3.2 times the current level. Bauxite reserve and aluminum production in India
is 900 million tons. India has 3.1% of the world bauxite reserve and produces 3.7%
of world alumina and 3.39% of world aluminum. Indian expected capacity additions
by 2017 is about 2.9 million tons, and most of the projects are likely to come in the
eastern and central India. Aluminum market is still evolving, and construction and
transport sector is likely to have more impact: Present share of electrical power
sector 48%, transport 15%, construction 13%, packaging 4%, consumers and durable
7%, and machinery and equipment 7%. Expected alumina and aluminum capacity
addition by 2017 is 9 million tons and 2.9 million tons, respectively. With expected
growth in packaging, electrical, automobile and construction increase in demand
of aluminum is expected.

Process of Manufacture of Aluminum

Major source of aluminum is alumina which is produced from bauxite. One ton of
alumines of alumina is produced from 4 tons of bauxite.

Raw material for Aluminum

Per ton of aluminum
Bauxite: 4 kg, aluminum oxide: 1.93 kg,
Carbon: 0.415, aluminum fluoride 20 g, cryolite: 2 g
Energy: 13.460 kWh.
The process of alumininum manufacture involves digestion of bauxite, clarification,
precipitation, calcination of aluminum hydroxide to produce alumina, electrolysis of
alumina using cryolite to produce aluminum.
The process of aluminum manufacture invoves two step: Production of alumina
from bauxite and production of aluminum from alumina by reduction. Alumina
from bauxite is made by digestion of bauxite with caustic soda which dissolves
alumina, and the impurities are seprated as red mud by filtration. Alumina is further
seperated by precipitation at low temperature and precipates. Filteration of alimina
Metallurgical Industry in India 201

is done by separation of red mud containing iron, unreacted caustic caustic and
other impurities.
Liquid aluminum is made from alumina by electrolytic reduction of alumina dissolved
in cryolite (NaAlF3) using carbon anode.
2Al2O3 + 3C Al + 3CO2
Process of manufacture of aluminum is shown in Figure 13.4.

Fig. 13.4: Process of manufacture of aluminum

13.4 ZINC
As per US geological survey, global zinc mine production in 2013 was 13.5 million tons
while refined zinc production was 13.5 million tons. Consumption of the metal was
about 12.9 million tons. India zinc production was 0.8 million tons. Hindustan Zinc
and Vedanta Resources are the major player in zinc production. China is the world top
zinc producer with production of 5 million tons. Identified world resources of zinc is
about 1.9 billion tons. Hindustan Zinc Ltd., which was established in 1966 is the India’s
largest and world second largest producer of zinc and lead and is engaged in zinc and
lead mining and smelting (Table 13.2).
Largest consumption of zinc is in the corrosion protection in galvanizing, i.e.
in coating of steel. Some of the other uses of zinc are in brass as for alloying with
copper, two-die castings, rolled zinc, zinc oxide which is used in rubber product
and zinc chemicals, as anode material in batteries. Alloyed zinc is used in pipes,
instrument, valves, etc.
202 Chemical Process Technology

Table 13.2: World zinc resources (2011), 000 tons of contained zinc metal
Country Reserves Reserve base
Australia 53,000 1,00,00
China 42,000 92,000
United States 12,000 90,000
India 11,000 37,000
Kazakhstan 16,000 35,000
Canada 6,000 30,000
Mexico 15,000 25,000
Peru 23,000 23,000
Other countries 72,000 50,000
World total 2,50,000 4,80,000

Process of Manufacture of Zinc: Zinc ore is first concentrated by froth flotation process.
Zinc in the form of sulfide is first roasted to seperated sulfur in the form of SO2 which
is utilized production of sulfuric acid. Different types of roaster being used are multiple
hearth roaster, suspension roaster, and fluidized bed roaster. After roastering, zinc is
obtained in the form of zinc oxide.

13.5 COPPER
Copper is extensively used in the industry. It has a light rose color. It has melting point of
1083ºC. Because of high heat conductivity, copper is commonly used in heat exchangers,
coolers, radiators, internal combustion engines, geyser and other similar equipments.
It is also very commonly used in alloy and as catalyst in chemical process industries.
Copper–zinc alloys are called brass, while copper–tin alloys are known as bronze.
As per International copper study group, world mine production of copper is
18 million tons, while world refined production is 21 million tons in 2013. World apparent
usage of copper is about 21.2 million tons. India’s copper ore reserve contributes
about 2% of world reserves. India is fourth in smelter production and 8th in refined
consumption. Hindustan Copper Limited (HCL) is the major producer of copper in
India. It has 4 mines, 2 smelters plants and 1 wire rod plant. HCL is to enhance its mine
capacity from 3.4 million tons to 12.4 million tons by 2017. HCL Khetri copper belt
has 4 reserves at Khetri, Kolihan, Banwas, and Chandmari with geological reserves of
94.5 million tons @1.25% Cu; Singhbhumi copper belt has 4 mines at Surda, Kendadih,
Chapri-Sideswar, and Rakha with geological reserves of 197 million [email protected]%Cu. HCL
Malankhand copper belt has reserves of 331 million tons.
The most common copper ore is in the form of sulfide, while copper is also present
in the form of carbonate ore. The process of production of copper involves mining and
crushing of ore, grinding, concentrating the ore using flotaion, leaching, electrowinning,
smelting, and electrorefining
The first step in the manufacture of copper is the concentration of copper ore by
floatation process as the copper ore contains only small amount of copper. Dirt,
clay and other non-copper-bearing materials are removed by flotation process. In
the floatation process, the ore is fnely crushed in crusher, mixed with water and
further crushed in rod mill and ball mill and send to floatation cell after mixing
Metallurgical Industry in India 203

with chemical to enhance floatation. The resulting copper concentrate ore containing
about 25–35% copper; along with various sulfides of copper it is further procesed
after drying.
After removal of impurities, the copper concentrate is fed to the roaster furnace
which may be fluidized bed or in multihearth furnaces. Roasted copper along with
iron is fed to furnace along with silica as flux utilizing oxygen. Copper concentrate and
the flux in the form of melt collect in the bottom. Iron combine with the flux to form
slag and separated. Sulfur combines with air is forming SO2 which is further utilized
for manufacture of sulfuric acid. During roasting of copper ore, a number of reactions
takes place which are given below:
FeS2 FeS + S
2CuS Cu2S + S
CuFeS2 Cu2S + FeS + S
S = O2 SO2
FeS + 3O2 2FeO + 2SO2
2CuS + 3O2 2Cu2O + 2SO2
Cu2S + 3O2 2CuO + 2SO2
Cu2O + FeS Cu2S + FeO
2FeS + SiO2 + 3O2 2FeO.SiO2 + 2SO2
2Cu2O +2FeS + SiO2 2FeO.SiO2 + 2Cu2S
Cu2S + 2CuO 6Cu + SO2

The molten material from the furnace called matte and contains concentrated
copper sulfides and iron sulfides which contain about 60% of [Link] molten matte
containing copper and iron sulfide is fed to second where additional silica flux is added.
Remaining iron combines with silica and separated as slag while the molten material
containing concentrated copper is further processed to get pure carbon by electrolytic
and refining process (Fig. 13.5). After electrorefining the molten copper is casted into
ingots, cakes, billets, or rods.

Fig. 13.5: Process of copper manufacture

204 Chemical Process Technology

13.6 LEAD
Lead is commonly available together with zinc in ore with other metals, such as silver
and cadmium. Primary production of lead is abot 50% while rest comes from recycling
of seconadry sources. Lead demand in india was 410,000 tons in 2011–12. India’s
primary lead production during 2011–12 was 92098. Lead consumption is linked to
automobile consumption in any country. About 75% of lead consumption in India is in
the mnaufacture of battery sector while 20% in alloys and chemical and balance 5% is
in cables and other areas [Pugazhenthy, 2013]. Lead is used in batteries for insulation
against radiation. Lead mine production in India is growing steadily at an annual growth
rate of 8% (Tables 13.3 and 13.4).

Table 13.3: World Lead resources (2011), 000 tons of contained zinc metal
Country Reseves Reserve base
Australia 27,000 59,000
China 11,000 36,000
United States 7,000 19,000
Russia 9,200 11,000
India 2,600 7,000
Poland 1,500 5,400
Canada 650 5,000
Peru 6,000 NA
Mexico 5,600 NA
Other countries 8,000 33,00
World total 80,000 1,80,000
Source: Pugazhenthy Metal world, Jan. 2013, p.42.

Table 13.4: Trend in world production and use of lead in tons

Mine Metal
2009 3,810,000 9,242,000
2010 4,161,000 9,850,000
2011 4,636,000 10,598,000
2012 4,994,000 10,212,000
2013 5,313,000 10,593,000
Source: International Lead and Zinc Study Group (ILZSG).

Galena is the most important ore and major portion of lead is manufactured from
galena. Other source of lead is cerussite.
Various steps in the process of lead production are concentration of ore using flotation
process, filtering, roasting of the ore to get lead oxide which is further processed to get
lead. The lead oxide is reduced to lead in blast furnace which is further refined. Refined
lead is casted into blocks.
Metallurgical Industry in India 205

BIBLIOGRAPHY
1. Annual Report 2012–13. Ministry of Mines, Government of India.
2. International Lead and Zinc Study Group (ILZSG)
3. Pugazhenthy Metal World Jan 2013, p.42.
4. Singh S. Private communication.
5. [Link]
14
Leather Industries

14.1 INTRODUCTION
Use of leather has been reported since prehistoric period, and with the advancement
of civilization, there has been continuous development and increase in consumption of
variety of leather goods. Although tanning is the integral part of leather manufacture,
both tanned and untanned hides and skins have been used. Leather which is produced
from hides and skins is the intermediate product and finds application in manufacture
of large number of consumer products like shoe, clothing, leather goods, furniture,
and large number of other consumer products. Leather industry is one of the highly
polluting industries and the tanning processes generate huge amount of water containing
toxic chemicals and odor. Tanning is the intermediate process during manufacture of
leather, and there has been continuous development in tanning process to meet the
environmental challenges arising from large-scale pollution.

14.2 PROFILE OF LEATHER INDUSTRY

Indian leather industry is one of the oldest industries. However, the leather industry
has undergone tremendous growth during last three decades. India has become major
exporter of leather, and a larger number of value-added products are generating huge
foreign exchange as well as employment. Indian leather industry itself employs more
than 2.5 million people. Different sector of leather industry includes flaying, curing
and carcass recovery, tanning and finishing, footwear and footwear components, full
shoe as well as shoe uppers, chappals and sandals, leather goods and garment, and
industrial gloves and saddler. Total value of leather and leather products export and
internal market was estimated to be US$ 8 billion in the year 2008. The major tanning
industry are located in Tamil Nadu, Andhra Pradesh, Uttar Pradesh, Punjab, Karnataka,
Rajasthan, and West Bengal. About 75% of tanneries are located in cottage and small
sector, 20% in the medium and about 5% only in the medium/large sector.
The top Indian leather exporters are Tata Internationals, Florind Shoes Ltd., Farida
Shoes Ltd., Miza Tanners, Hindustan Levers, Super House Leather Ltd., RSL Industries,
and Presidency Kid Leather Ltd.
According to Omicra Credit Rating Agency of India (ONCRA), India’s export of
leather and leather products has increased from 3548 million US$ in 2007–08 to 4868
US$ in 2011–12 with percentage growth of 15.99–22.68 during this period. India is the
206
Leather Industries 207

second largest producer of footwear after China accounting for 13% of overall global
footwear production of 16 billion pairs. India’ export of leather and leather products to
the European Union touched US $316.52 (ONCRA “Emerging Trends: Indian Leather
Industry”).
Leather Manufacturing Process: Hides and skins are the source of leather. Generally, skin
of large animals is called hides while skin of smaller animals like goats and sheep are
called skin. Hides and skins of slaughter house contain about 60–70% moisture and
are liable to bacterial attack and need to be processed. The process steps involved in
processing of hides and skins are:
Pertaining process: Preservation of hides and skins storage after slaughter house to
avoid decaying by microbial action curing is employed.
Tanning process: Removal of hairs, nails, keratinous matters, soluble proteins, etc.
Tanning process uses chromium tanning.
Post-tanning process: Finishing and drying process.
The process of leather manufacture is given in Figure 14.1.

Fig. 14.1: Processing of hides and skins

Pertaining process: Raw skins and hide contains water, protein, and fat. To avoid microbial
degradation, the removal of moisture is very important step in preservation and storage
of raw hides and skins. Various steps in pertaining operation are dehydration of raw
hides and skins for removal of moisture using salt. The raw hides and skins are then
sorted to several grades based on weight and size and quality. After sorting, the hides
and skins are trimmed and send for curing and storing. Purpose of curing is to prevent
the decompositions of hides and skins. The process involves salting and drying. The
hides and skins are stored in ventilated air or air conditioned or cooled area. The hides
and skins after curing are sent to soaking section from the storage. The process of
soaking involves removal of salt used during curing and other unwanted materials.
The process of soaking involves dirt soaking using water for removal of unwanted
material, main soaking and final soaking. Soaking also remove nonstructural proteins
and fats. The process of main soaking involves rehydration using water, non-ionic
wetting agents and preservatives. Final soaking involves washing using water. The
other steps involve in pertaining operation are liming which involves dehairing and
reliming to open the fibrous structure. The other steps involve are fleshing, deliming,
208 Chemical Process Technology

and finally, pickling which adjust the required pH for tanning and prevent swelling
of the leather. The pickling bath consists of water, formic acid, and sulfuric acid. The
composition depends upon thickness of the hides and skins.
Tanning: Tanning industry is one of the highly polluting industries and considerable
impact on environment is in the form of air pollution especially odor, and contamination
of ground water and surface water due to presence of high BOD, COD, heavy metal,
etc. Tanning process involves converting hides and skins into leather useful for the
manufacture of various leather goods as untanned hides and skins are utilizable and
susceptible to microbial attack. Tanning leather involves a process which permanently
alters protein structure of skin so that it cannot ever to raw hid (Sathiyamoorthy et al.,
2013). Two types of tanning process used are chrome tanning and vegetable tanning.
Due to hazards of chromium tanning new eco-friendly tanning processes are getting
importance.
Chrome tanning: Chromium tanning is the most commonly used process as it is quick
and cheap as compared to vegetable tanning process. The process of tanning of
hides and skins in rotating drum containing chrome tanning bath contains chromium
sulfate 7–10% and sodium sulfate 25–30%. After tanning process is completed which
requires about 8–10 hours, pH is increased to 3.8–4.0 using sodium carbonate or
sodium bicarbonate. The process is called basification. The process helps in binding
chromium to the collagen. Chrome tanning process produces leather with better color
stability and cheap. Although chrome tanning is very commonly used process, it is not
environment-friendly.
Vegetable tanning: Vegetable tanning is environment-friendly and free from the
chromium hazards as only natural ingredients are used. In vegetable tanning plant
extracts like tannin or tannic acid extracted from tree bark is used as tanning material.
It requires longer time for tanning and is used for products like shoe sole, luggage,
leather belts, etc. Vegetable tanning process is slower as compare to chrome tanning
process. The process is more expensive as compared to chrome tanning and takes
longer time.
Post-tanning process: Post-tanning operation called slamming involves removal of
excess moisture by mechanical operation. The other post-tanning operation involves
silting, shaving and trimming, rechroming to improve chrome content of the leather,
semi-chroming in case of vegetable tanning, neutralization to maintain pH around
4.5–6.0. Neutralization process is followed by dyeing, fat-liquoring and drying and
final finishing. These processes include the dyeing of the leather depending on end
use, softening of leather, and imparting softness to the leather.
Environmental issues associated with leather manufacture are waste water generation,
air emissions, solid waste generation, discharge of hazardous materials, etc.
Eco-friendly tanning processes: Due to hazards in chromium tanning, new eco-friendly
tanning processes are getting importance. Greener approach to leather tanning process
has been reported by Krishna Murthy, et al. 2013 using D-lysine aldehyde as novel
tanning agent and by Sathiyamoorthy, et al. 2013.
Leather Industries 209

BIBLIOGRAPHY
1. “Indian leather industry”[Link]/Publication/Indian%20Leather%[Link]
2. ONCRA “EmergingTrends: Indian Leather industry” [Link]/images/pdf/.../Leather-
[Link]-2014.
3. Sathiyamoorthy, Sevi S, Mekonnen D, Habtama S. “Preparation of ecofriendly leather by process
modification to make pollution free tanneries” Journal of Engineering, computers and applied
sciences Volume 2, No. 5 May, 2013.
4. Technical EIA guidance Manual for Leather/Skin/Hide processing industry Ministry of
environment and forests Govt. of India
5. [Link]/[Link]?pid=96
6. [Link]/[Link]
15
Coal and Coal as
Chemical Feedstock

15.1 INTRODUCTION
Coal can serve a potential source of synthetic fuel, a source of power production, coke
production and large number of chemicals which are now being derived from petroleum
and natural gas. Coal is the largest source of energy all over the world. Some of the recent
developments in utilization of coal are coal gasification, coal to synthesis gas, coal to
oil through FT synthesis, coal to methanol, coal to plastic; these are some of the future
technologies which are likely to play important role in providing alternate feedstock for
chemical industries. Coal is the most important and abundant fossil fuel in India and
accounts for 55% of country’s energy need. The country’s Industrial heritage was built
upon indigenous coal (Annual Report, Ministry of Coal, Government of India, 2020).

15.2 COAL ORIGIN AND COMPOSITION

Coal is carbonaceous solid black or brownish black sedimentary rock matter vegetation.
Biological changes originated from the accumulation of partially decomposed vegetation.
Biological changes and subsequent effects of temperature and pressure altered these
deposits to coal. Coal is composed of chiefly carbon and other elements like hydrogen,
sulfur, oxygen, nitrogen, moisture and noncombustible inorganic matters containing
silica, iron, calcium, magnesium, mercury, etc. Coal has a wide range of composition.
Typical composition of Indian coal and coal in other countries are given in Table 15.1.
The composition, sulfur content, mercury content and calorific value of the coal vary
widely from one coal reserve to another coal reserve. Coal may be hard or slightly softer
depending on the source.

Table 15.1: Composition of Indian coal and other countries

Details Indian coal Coal in other countries
Ash content 40–50% 1–16%
Sulfur 0.5% As high as 1.8%
Carbon 25–30% 53–57%
Hydrogen <3% 4–6%
Calorific value 2450–3000 5000–6400
Source: Visuvasam, et al. 2005.
210
Coal and Coal as Chemical Feedstock 211

15.2.1 Coal Resources

Category of coal resources are based on degree of assurance, i.e. (i) coal reserves—
proved, indicated, inferred or (ii) depth range. Proved reserves are those resources
which have been reliably estimated and can be recovered economically. Indicated
reserves are the coal resources which are based on combination of direct measurement
and reasonable geological assumptions. Inferred coal resource is based on the assumed
continuity of coal beds. Depth range determines the economy of extraction and a cope
of exploration.

15.2.2 Coal Reserves

World’s proven coal reserves are estimated at about 860 billion tons which is expected to
last up to 120 years at the current level of production. The global coal reserves consist of
53% anthracite and bituminous coals, 30% sub-bituminous, and 17% lignite (BP Statistics
2011, EIA, US Departments of Energy). Largest coal reserves of coal are in China, USA,
Russia, Australia, and India. India has the fifth largest coal reserves in the world of the
total reserves, nearly 88% are non-coking coal reserves while tertiary coals reserves
account for a meager 0.5% and the balance is coking coal. Coal resources in India as
on April 1, 2011 is given in Table 15.2. Coal reserves of India up to the depth of 1200
meters have been estimated to be 276.81 billion tons as on April 1, 2010. Projected coal
demands in upcoming year are mention in Table 15.3. Coal deposits are chiefly located
in Jharkhand, Odisha, Chhattisgarh, West Bengal, Madhya Pradesh, Andhra Pradesh,
and Maharashtra. Details of state-wise coal resources in India are shown in Table 15.4.
Table 15.5 gives detail of coal resources in sedimentary rocks. Lignite reserves in the
country have been estimated around 39.90 billion tons as on March 31, 2010. Major
deposits are in Tamil Nadu. Details of coal letter of assurance and status of CBM blocks
are given in Tables 15.6 and 15.7, respectively.

Table 15.2: Coal Resources in India

Resources in million tons Proved Indicated Inferred Total
Coking coal 17,669 13,703 2,102 33,474
Non-coking coal 95,739 12,368 31,488 250,895
Tertiary coal 594 99 799.49 1,493
Total 114,001 137,471 34,389 285,862
Source: Geological Survey of India cited from emerging opportunities and challenges coal sector
WEC-JMC 23 January, 2012.

Table 15.3: Coal demand projections (million tons)

Plan Period Power Non-power Total
11th 2011/12 436 164 627
12th 2016/17 603 221 824
13th 2021/22 832 299 1131
14th 2026/27 1109 408 1517
15th 2031/32 1475 562 2037
Source: Geological Survey of India cited from emerging opportunities and challenges coal sector
WEC-JMC 23 January, 2012.
212 Chemical Process Technology

Table 15.4: Distribution of coal resources (million tons)

State Proved Indicated Inferred Total
Andhra Pradesh 9,194 6,738 2,985 18,927
Arunachal Pradesh 31 40 19 90
Assam 348 36 3 387
Bihar – – 160 160
Chhattisgarh 10,910 29,192 4,381 44,483
Jharkhand 39,480 30,894 6,338 76,712
Madhya Pradesh 8,041 10,295 2,645 20,981
Maharashtra 5,255 2,907 1,992 10,154
Meghalaya 89 17 471 577
Nagaland 9 – 13 22
Odisha 19,944 31,484 13,799 65,227
Sikkim – 58 43 101
Uttar Pradesh 866 196 – 1,062
West Bengal 11,653 11,603 5,071 28,327
Total 1,05,820 1,23,470 37,920 2,67,210
Source: Geological Survey of India cited from emerging opportunities and challenges coal sector
WEC-JMC 23 January, 2012.

Table 15.5: Coal resources in sedimentary rocks (million tons)

Formation Proved Indicated Inferred Total
Gondwana coals 1,05,343 1,23,380 37,414 2,66,137
Tertiary coals 477 90 506* 1,073
Total 1,05,820 1,23,470 37,920* 2,67,210
*Includes 456 million tons of inferred resource established through mapping in north-eastern regions.

Table 15.6: Coal letters of assurance (LOA)

Name of sector Number approved Quantity approved (MTPA)
Power utilities 15 57
Captive power plants 224 42
including cement CPPs
Independent power producers 12 24
Cement plants 72 21
Sponge iron units 236 17
Total 559 161
Source: Annual Report 2007–08 Ministry of Coal, Government of India.
Coal and Coal as Chemical Feedstock 213

Table 15.7: Status of CBM Blocks

Block awarded 3
Under round I 5
Under round II 8
Under round III 10
Total 26
Area awarded ([Link]) 13,600
Total CBM resources (BCM) 1,374
CBM Wells drilled 210
Expected production potential (MMSCMD) 38
Approved gas sale price ($/MMBTU) 6.79
Sources: India Exploration and Production Activities, 2007–08.

15.2.3 Coal-bed Methane (CBM)

Coal-bed methane is an environment-friendly clean fuel similar to natural gas.
Preliminary activities related to exploration of CBM in India started in early 1990s, and
till 1997, the Ministry of Coal had allotted some coal-bearing areas for CBM exploration.
In India, 33 CBM contracts were signed for explorations of CBM gas. In July 1997,
Ministry of Petroleum and Natural gas was made administrative ministry. As of now
about 250 BCM reserves have been established in 5 CBM blocks. CBM gas production
is about 2 lakh cubic meter per day (Annual Report 2011–12, Ministry of Petroleum and
Natural Gas, Government of India).

15.2.4 Coal-production and Consumption

The global coal production in 2011 was 7 billion tons of which China accounted for
approximately half of the production and consumption. Total coal production in
India during 2009–10 was 532.29 million tons. Lignite production in 2009–10 was
23.95 million tons. Coal production trend during 2010–2019 is shown in Table 15.8.

Table 15.8: Coal-production trend during 2010–2019

Year Production in million tons
2010–11 532.69
2011–12 539.95
2012–13 556.40
2013–14 565.00
2014–15 609.18
2015–16 639.23
2016–17 657.87
2017–18 675.40
2018–19 730.35
Source: Annual Report, Ministry of Coal 2019–20.
214 Chemical Process Technology

15.3 TYPES OF COAL

Coals are classified into various grades based on the composition and calorific value and
degree of coalification that has occurred during its formation. Coal may be also classified
as hard or soft coal, low sulfur or high sulfur coal. Coal may be also classified in rock
types based on petro-logical components known as maceral. Based on maceral content,
coal may be classified as clarain, durian, fusain and vitrain [[Link]
com/EBchecked/topic/1703417/coal- classification]. Classification of different type
of coal is mentioned in Table 15.9. Ultimate analysis of non-coking (thermal) coal from
three power stations (Kahlgaon, Simhadri, and Sipat) along with analysis of Ohio coal
in the United States and Long Kou coal from China is shown in Table 15.10.

Table 15.9: Classification of different type of coal

Types of coal Description
Peat Peat is the precursor of coal formed
Lignite With further increase in temperature during coal formation peat is converted
to lignite. Lignite is considered as immature coal. Lignite is brown colored,
soft, low-calorific value coal. It is compact in texture.
Sub-bituminous Sub-bituminous coals are black colored and are more homogeneous in
appearance and their properties range from lignite to that of bituminous coal.
Bituminous coal Bituminous coal is usually black, with higher carbon content and calorific value
Anthracite coal Anthracite is highest rank coal is a harder, glassy black coal with highest
content of carbon and calorific value. Anthracite coal is best suited for making
metallurgical coke, for gasification to produce synthesis gas and for combustion
as fuel for power generation. The ash content is low.
Graphite Graphite is the highest rank and is difficult to ignite
Source: [Link]

Table 15.10: Typical coal characteristics in selected Indian power plants, as

compared to selected Chinese and US coals
Details (%) Kahalgaon Simhadri Sipat US (Ohio) China (Long Kou)
Carbon 25.07 29.00 30.72 64.2 62.8
Hydrogen 2.95 1.88 2.30 5.0 5.6
Nitrogen 0.50 0.52 0.60 1.3 1.4
Oxygen 6.71 6.96 5.35 11.8 21.7
Moisture 18.5 15.0 15.0 2.8 11.0
Sulfur 0.17 0.25 0.40 1.8 0.9
Ash 46.0 46.0 45.0 16.0 7.7
Calorific value, kcal/kg 2450 2800 3000 6378 6087
Source: Visuvasam et al., 2005; Ananth, 2008.

Selection of coal for various applications depends on its composition and carbon
content, calorific value, moisture content, ash content, composition of ash, fusion
temperature of ash, coking quality, sulfur content.
Coal and Coal as Chemical Feedstock 215

15.4 ASSESMENT OF COAL QUALITY

Coal quality plays an important role in its efficient utilization as fuel and for gasification.
It should have high calorific value, high carbon content with low ash content, low
sulfur, low moisture, low cost. The quality of coal depends upon it rank. The coal rank
is arranged in ascending order:
Lignite Sub-bituminous coal Bituminous coal Anthracite
Coal quality can be assessed by proximate, ultimate analysis and calorific value of the
coal. Proximate analysis involves determination of moisture, volatile matter, ash and fixed
carbon. Ultimate analysis involves determination of carbon and hydrogen, nitrogen, sulfur,
and oxygen. Calorific value is represented as higher calorific value (HCV) or gross calorific
value (GCV) and lower calorific value (LCV) or net calorific value (NCV). Another term
used to express energy content is useful heating value (UHV). UHV is defined as UHV
kcal/kg = [8900–138 × (percentage of ash content + percentage of moisture content)].
15.4.1 Coal as Fuel
Coal accounts for 53% of the commercial energy sources in India which is high compared
to the world average of 30%. The 11th plan projected India’s coal demand to grow at 975
per annum against 5.7% during 10th plan almost twofold increase. The coal consumed
by commercial sectors in India are 72% for power, 14% for steel, 9% for cement and
9% for others. Allocation of coal blocks to private companies are given in Table 15.11.

Table 15.11: Allocation of coal blocks to private companies

Sector/end use Blocks Geological reserves (MT)
Power 20 2,702
Iron and Steel 47 6,703
Small and Isolated 2 9
Cement 3 232
Ultra/mega power project 7 2,607
Total 79 12,254
Source: Annual Report 2007–08, Ministry of Coal, Government of India.

15.4.2 Coal as Chemical Feedstock

Coal originally was utilized as fuel. Many of the petrochemicals now derived from
petroleum and natural gas was referred as coal chemicals. With starting of coke-oven
plants, it became source of organic and some inorganic chemicals. Coal tar from coke-
oven plants continues to be a source of aromatics, naphthalene and other valuable
aromatics like pyridine, picoline, quinoline. Before the coming of petrochemical
production, a large number of organic chemicals was produced from acetylene produced
from calcium carbide route in which coal was a important feed. Various coal chemicals
derived from coal is given in Figure 15.1.
China has come in a big way for production of chemicals from coal because of the
huge coal reserves. With the rising cost of crude oil and dwindling crude oil reserves,
coal has again received attention all over the world to utilize coal as an alternative
source of chemical feedstock. Various routes for production of organic and inorganic
chemicals from coal are:
216 Chemical Process Technology

Fig. 15.1: Coal as chemical feedstock (Source: Mall 2013)

• Coal carbonization and coal tar distillation

• Coal gasification and use of synthesis gas as feedstock for ammonia production
• Coal liquefaction by hydrogenation
• Coal to methanol technology
• Coal to olefin technology
• Coal to plastic technology
• Acetylene from calcium carbide made from lime and coal.

Coal Carbonization and Coal Tar Distillation

Coal carbonization and coal tar distillation is integral part of coke-oven nits in steel
plant for production of coke where large number of chemicals like ammonia, naphtha,
aromatics, etc. are produced. Benzene, toluene, xylenes, etc. were earlier produced from
coal tar distillation obtained from coke-oven plant.

Coal-based Power Generation

Coal gasification and use of synthesis gas as feedstock for ammonia production: Partial oxidation
of coal is used for production of synthesis and ammonia. CO from partial oxidation is
converted to CO2 which is used for urea manufacture. Synthesis gas CO + H2 is used
as chemical feedstock for production of large number chemicals.

Coal Liquefaction by Hydrogenation

Coal can be converted to naphtha by direct or indirect liquefaction. Coal can be also
converted into naphtha via FT process.
Coal and Coal as Chemical Feedstock 217

Coal to Methanol Technology

The process involves the production of synthesis gas from coal via partial oxidation
followed by conversion of synthesis gas to methanol.
Coal to Olefin Technology
Methanol can be converted to dimethyl ether, which can be used as a gasoline blend
or converted to olefin through olefin synthesis reactions.
Coal to Plastic Technology
Olefin produced from the coal route can be used for the manufacture of plastic. Coal
gasification and production of fuel from FT process getting significant attention.
Coal gasification and production of synthesis gas is now considered to be a major
potential on purpose source of commodity petrochemicals. The cost of coal and higher
cost of chemicals derived from coal has been major constraint in its utilization as a
substitute for petroleum and natural gas.

15.5 COAL CARBONIZATION AND COKE-OVEN PLANT

Coal carbonization is used for processing of coal to produce coke using metallurgical
grade coal. Coal carbonization involves heating of coal in the absence of air. Coke
making process is multistep complex process and variety of solid liquids and gaseous
products are produced which contain many valuable products. Various products
from coal carbonization in addition to coke are coke-oven gases. coal tar, light oil,
and aqueous solution of ammonia and ammonia salt. Coke-oven gases are about
310–340 m3 per ton of dry coal which contains gaseous products, coal tar vapors, light
oil and water (Mukhulyonov, et al. 1974). With the development of steel industry there
has been continuous development in coke-oven plant since latter half of nineteenth
century to improve the process conditions, recovery of chemicals and environmental
pollution control strategies and energy consumption measures.
Carbonization can be carried out at low temperature or high temperature. Low
temperature carbonization is used to produce liquid fuels while high temperature
carbonization is used to produce gaseous products (Trodakar and Belgaonnkar, 1991).
Low temperature carbonization (450–750ºC): In low temperature carbonization quantity of
gaseous product is less while liquid products are large.
High temperature carbonization (above 900ºC): In high temperature carbonization, the yield
of gaseous product is more than liquid products with production of tar relatively low.
The potential availability of chemicals from high temperature carbonization (>900ºC)
and low temperature carbonization (450–750ºC) .

15.5.1 Coke Oven Plant

Due to the development of iron and steel industry coke-oven plant has become an
integral part of iron and steel industry. Due to increasing demand of iron and steel,
there has been a considerable increase in the coke-oven capacity which resulted increase
output of coal chemicals.
Two types of coke manufacturing technologies use are:
• Coke making through by product recovery
• Coke making through non-recovery/heat recovery.
218 Chemical Process Technology

In India, building of coke-oven batteries was initiated in the beginning of the ninth
century, now about 3000 ovens are in operation/construction in the coke-oven plant.
By the year 2011–12, the world coking coal requirement will be about 433 million tons
in which India’s requirement is estimated to about 54 million tons. By-product from
coal gasification plant includes coke, coal tar, sulfur, and ammonia. Coal tar distillation
produces tar, benzol, cresol, phenol, and creosote.
Coking Coals: Blast furnace requires coke of uniform size, high mechanical strength, and
porosity with minimum volatile matter and minimum ash. Coking coal may be divided
on the basis of their coking properties: prime coking coal, medium coking coal, semi
coking coal. The prime coking coal produces strong metallurgical coke while coals of
other groups yield hard coke only. Concentration of moisture ash, sulfur and sometime
phosphorus and ash fusion temperature are important in determining the grade of
coking coal since they influence the quality of coke produced. Low moisture, ash, sulfur
and phosphorus content in the coal are desirable for production of good quality coke.
The desired analysis of typical coal charge to coke oven is:
• Ash content : 16% ± 0.5%
• Moisture : 6–7%
• Volatile matter : 22–25%
• Fixed carbon : 58–60%
• Sulfur : 0.56%
• Phosphorus : 0.09%
Some of the other factors affecting quality of coke are rank of coal, particle size,
bulk density, weathering of coal, coking temperature and coking rate, soaking time,
quenching practice.
Coke-oven Plant: Various sections in coke-oven plant are given in Table 15.12.

Table 15.12: Various sections in coke-oven plant

Coal handling plant and coal To prepare coal blend suitable for carbonization various steps
preparation section involved are: unloading and storage of coal, blending of coal of
various grade, coal crushing and transport to coal storage tower
Partial briquetting To prepare briquette of coal to charge along with coal into the
coke oven
Coke-oven batteries To convert coal into coke by carbonizing coal in absence of
air. The process steps involved are coal charging and coal
carbonization.
Coke-sorting plant Crushing and sorting of coke to suitable size for use in blast
furnace. The steps involved are coke pushing, coke quenching,
coke crushing/screening.
Coke-oven gas recovery Collection and cleaning of coke-oven gas and recovery of by-
products. This involves gas cooling, tar recovery, desulfurization
of coke-oven gas, recovery of ammonia, recovery of light oil.
Ammonia recovery and Recovery of ammonia and neutralization with sulfuric acid or
ammonium sulfate pro­duc­tion nitric acid in case of ammonium nitrate/calcium ammonium
nitrate
Waste-water treatment Treatment of phenolic waste water
Coal and Coal as Chemical Feedstock 219

15.5.2 Coal Handling Plant and Coal Preparation Section

Coal needs to be stored at various stages of the preparation process, and conveyed
around the coal preparation section. Crushing and screening are the important part
of coal handling plant. Crushing reduces the overall size of the coal so that it can be
more easily processed and handled. Screens are used to range the size of coal. Screens
can be static, or mechanically vibrated. Dewatering screens are used to remove water
from the product.
Partial briquetting: Briquettes of low grade coal are prepared using a binder (pitch/
pitch+tar) up to 2–3.0% of charge. This partial briquette of coal is charged with coal
into coke oven which significantly improves the quality of coke.
Coke-oven batteries: Coke oven plant consists of coke-oven batteries containing number
of oven (around 65 ovens in each battery). The coal is charged to the coke oven through
charging holes. The coal is then carbonized for 17–18 hours, during which volatile matter
of coal distills out as coke-oven gas and is sent to the recovery section for recovery of
valuable chemicals. The ovens are maintained under positive pressure by maintaining
high hydraulic main pressure of 7 mm water column in batteries. The coking is complete
when the central temperature in the oven is around 950–1000ºC. At this point, the oven
is isolated from hydraulic mains and after proper venting of residual gases, the doors are
opened for coke pushing. At the end of coking period the coke mass has a high-volume
shrinkage which leads to detachment of mass from the walls ensuring easy pushing.
The coke is then quenched and transferred to coke sorting plant.
The control of oven pressure is quite important because lower pressure leads to air
entry while higher pressure leads to excessive gassing, leakage of doors, stand pipe,
etc. Proper leveling of coal is important and care is taken so that free board space above
(300 mm) is maintained to avoid choking.
Coke-oven plants are integral part of a steel plant to produce coke, which is used as
fuel in the blast furnace. Coke-oven plant produces important by-product coal chemical
tar, ammonia, crude benzoyl which is fractionated to produce aromatics–benzene
toluene, xylene. Typical flow diagram of coke-oven plant is shown in Figure 15.2. Coke-
oven plant consists of the following sections.
Coke-oven
Coke ovens are used to convert coal into coke by carbonizing coal in absence of air and
there by distilling the volatile matter out of coal. Coke is taken as product which is use
as fuel and as a reducing agent in smelting iron ore in a blast furnace and coke oven
gas as byproduct is treated for recovery of coal chemicals. The coke oven temperature
is keep as high as 2000ºC. Crushing and screening of coke is done to obtain suitable size
for use in blast furnace. Typical analysis of blast furnace coke is given in Table 15.13.

Table 15.13: Typical analysis of blast furnace coke

Sr. no. Parameter Value (%)
1 Moisture 3.5–6
2 Ash 15.5–17.0
3 VM <1.00
4 Sulfur 0.65
5 Fixed carbon 79–81
Source: Mall, 2013.
220 Chemical Process Technology

Fig. 15.2: Flow diagram of coke-oven plant

Coke-oven Gas Plant

Coke-oven gas is produced during the process of coking of coal are used in coke-oven
gas plant for the recovery of various valuable chemicals like tar, ammonia and benzoyl.
Typical analysis of coke-oven gas is mentioned in Table 15.14. These chemicals are
recovered and gas is cleaned. This comprises the following sections.
By-product from Coke Oven Plant
The high temperature carbonization is used for production of coke for use in blast
furnace. Various by-products obtained from coal carbonization are crude tar, crude
benzoyl, and ammonia. Typical yield of some important by-products are: Tar 3.2%,
ammonium sulfate 1.1%, crude benzoyl 0.9%.
Gas Condensation Section
Coke oven gas containing water vapors and chemical products of coking (tar, ammonia,
benzoyl, etc.) at temperature about 750–800ºC from the coke-oven plant is cooled to
temperature of 80–82ºC. During gas cooling, 65–70% of the tar is condensed. Further
Coal and Coal as Chemical Feedstock 221

cooling of gas, the water vapors and the remaining part of the target condensed along
with some ammonia and other chemicals.
Table 15.14: Typical analysis of coke-oven gas
Methane 26.0%
Hydrogen 56.5%
Hydrocarbons 2.3%
Carbon monoxide 8.5%
Carbon dioxide 3.0%
Oxygen 0.4%
Nitrogen 3.3%
Density 0.4848 kg/m3
Calorific value 4300 kcal/m3

Ammonium Sulfate Plant

The gases from exhaust goes to ESP where tar is separated and the tar free gases goes
bubbled through dil. solution of sulfuric acid in saturators. Ammonia is absorbed by
sulfuric acid and ammonium sulfate is formed. One ton of coal yields about 0.3 ton tar
and 5–8 g ammonia per m3 of gas.
Benzoyl Recovery Section
The gases from saturator goes to series of coolers and then to benzoyl scrubbers where
benzoyl is scrubbed with wash oil. Benzoyl crude oil goes to benzoyl recovery section
where benzoyl is removed and the wash oil after treatment is sent to the scrubbers.
Crude benzoyl thus recovered goes to benzoyl rectification plant. Light crude benzoyl
contains low boiling sulfur compound, BTX, solvents, still bottom residue. Benzoyl after
washing and neutralization with caustic soda is send to benzoyl column for fractionating
into different fractions. Various products of coke oven and after distillation of benzoyl
are given in Table 15.15.

Table 15.15: Various products of coke oven and distillation of benzoyl

Coke 76%
Tar productions 3.3%—pitch, PCM, anthracene oil, naphthalene, road tar, cresolate,
sodium phenolate, dephanelized oil, other oil
Ammonia 0.28%—used for production of ammonium sulfate
Crude benzoyl 0.85%—benzene toluene, xylene, still bottom, solvent oils
Coke-oven gas For industrial use as fuel
Moisture and other losses 5.04%

Coal Tar Distillation

Coal tar is produced as result of high temperature carbonization and is a viscous dark
brown product with characteristic odor and consists of about 300 different products.
Some of the major constituents are the aromatics and heterocyclic compounds: benzene,
toluene, xylene, phenol cresol, naphthalene, anthracene, phenanthrene, pyridine,
carbazole, coumarone, etc. Typical composition of coal tar is given in Table 15.16.
222 Chemical Process Technology

Table 15.16: Typical component of coal tar

Constituents Content (%)
Naphthalene 5–10
Phenanthrene 4–6
Carbazole 1–2
Anthracene 0.5–1.5
Phenol 0.2–0.5
Crezol 0.6–1.2
Pyridine compounds 0.5–1.5
Source: Mukhulyonov, et. al. 1974.

The tar distill unit consists of:

• Distillation section
• Fractional crystallization and washing section
• Combustible mixture preparation section
• Phenol rectification section
• Dolomite tar preparation unit
• Extra-hard pitch preparation.
Tar containing around 5% moisture is first dehydrated before distillation. The
dehydrated tar is heated to 375–400ºC using superheated steam to drive out the flashed
vapor and the residue is taken as pitch. The oil vapor is sent to anthracite column for
anthracite recovery while the vapor is sent to other column for recovery of various frac­
tion light oil, phenol, naphthalene and heavy oil fraction. Naphthalene fraction is sent
to crystallizer to separate naphthalene. Phenol is recovered from various fractions by
treating with a sodium hydroxide to form sodium phenolate which is reacted with CO2
to release phenol. Pyridine is recovered by washing different fraction with sulfuric acid.
Cleaner Technologies in Coke-oven Plant
Coke-oven plants are one of the highly polluting industries. Continuous development
has been there to reduce the pollution load and energy consumption. Some of the
cleaner technology are modified wet quenching, coke dry quenching, coal moisture
control, high pressure ammonia aspiration system, modern leak proof doors, advance
technologies for desulfurization of coke-oven plant.

15.6 GASIFICATION OF COAL, PETROCOKE AND BIOMASS

Gasification of coal, petrocoke, biomass and other carbonaceous materials to produce
synthesis gas has gained significant economic and environmental importance in the
recent years. Although the technology of gasification or partial oxidation of heavy
feedstock is quite established for over half century; however, the technology of
gasification has undergone continuous developments over the years to tackle higher
ends of refinery bottoms, petrocoke, coal and biomass (Sukumar and Nair, 2010).
Gasification of coal to produce coal gas goes to the end of 18th century when coal
gas was used for heating and lighting. History of gasification is given in Table 15.17.
However, with the availability of natural gas and petroleum products at cheaper rate,
the interest in coal gasification dwindled. However, due to increasing cost of oil and
Coal and Coal as Chemical Feedstock 223

gas and the availability of petrocoke, a look for alternative feedstock for gasoline and
petrochemical, interest was renewed in coal gasification. Coal gasification is now used
by surface and underground gasification. Gasification of biomass is also getting interest
during recent years because of availability of biomass in abundance.

Table 15.17: History of gasification

Period Technology
Before 1700 Major fuels were wood and charcoal
1700–1750 Industrial revolutions—coal as fuel
1800–1900 Coal pyrolysis—town gas supply, water gas, producer gas
1920 Cryogenic air separation—oxygen replaces air
1926 Winkler fluidized bed gasifier
1931 Lurgi moving bed gasifier
1940 Koppers–Totzek entrained flow gasifier
1950s Texaco and Shell develop oil gasification
1970s Oil crisis
1973 Texaco develops slurry process for coal gasification
1974 Shell and Koppers–Totzek pressure gasification JV
1981 High temperature Winkler gasification
1984 Lurgi slagging gasifier (together with British gas)
1999 Shell/Krupp–Uhde develop pressurized entrained; Flow (PRENFLO) gasifier
Beyond 2000 Shell gasification, GE Quench/PHR/FHR, Siemens, Chinese, GPE, Plasma,
Headwaters
Source: Parthasarthi, 2009.

India has estimated coal reserves of 253 billion tons and lignite around 28 billion
tons. Indian coal is mainly non-coking anthracite and bituminous in nature with ash
content of over 35%. Gasification of coal offers as promising source of chemicals as well
liquid fuel. The gasification of coal involves the conversion of coal to high content gas
(CO and H2).
Gasification technology offers the cleanest and most efficient way to convert low and/
or negative value carbon-based feedstock to synthesis gas. Indian context of gasification
is given in Table 15.18. Synthetic gas can ultimately replace natural gas for industrial
uses, electrical power generation and basic raw material to produce chemical and fuel
oil. Commercial success of gasification technology will depend on the advancement of
technologies, such as:
• Low-cost oxygen production
• Synthesis gas clean-up
• Cost effective separation of hydrogen from C2
Gasification is the process of converting organic part of solid fuel to combustible
gases of high heat value by interaction with steam and oxygen. Gasification converts
the low value fuel to high heat value gas. Typical gasification flow diagram is shown
in Figure 15.3.
224 Chemical Process Technology

The feed for gasification can be:

• Gas (e.g. natural gas)
• Liquid (e.g. light or heavy oils)
• Solid (e.g. petroleum coke, coal, lignite or biomass).

Table 15.18: Gasification—Indian context

1940s Wood gasification Wood FACT, Cochin
1945–1950 Lurgi fixed bed Coal Sindri
Winkler fluidized bed Lignite Neyveli
1960s
Texaco Naphtha FACT, Cochin
Krupp–Koppers entrained bed Atm. Coal Ramagundam,Talcher
1970s
Shell Fuel oil Sindri
Shell Fuel oil NFL, Bhatinda, Panipat, Nangal
1980s
Texaco Fuel oil GNFC, Bharuch
Source: Parthasarthi, 2009.

Fig. 15.3: Typical flow diagram of gasification process and its products

15.6.1 Underground Coal Gasification (UCG)

Under the process of UCG, gasification of coal happens in situ by controlled burning.
About 350 m3 of gas can be produced per ton of coal. By-products of significant
importance are hydrocarbon, phenols, anhydrous ammonia, and clean water. In
UCG overcomes hazard of underground and open cast mining and ash/slag removal
is not required as they remain in the cavities. Some of the advantages of UCG are
tapping of energy from vast coal reserves which are not economically viable to mine,
increased worker safety, low environmental impact, increased worker safety, etc.
(Sawhney, 2008).

15.6.2 Surface Gasification

Surface gasification involves reaction of coal with hot steam and controlled amount of
air or oxygen under high temperature and pressure. It produces synthetic gas which
can be used as the substitute of natural gas, for power generation using low BTU gas
as fuel, manufacture of chemicals and fertilizer and conversions to liquid fuel by
GTL liquid.
Coal and Coal as Chemical Feedstock 225

15.6.3 Process Steps in Gasification

Various process steps involved in gasification are:
Feed preparation: Wet feed system or dry feed system may be used in gasification. Wet
feed system employs grinding and slurring with water and pumping to gasifier while dry
system consists of grinding of the feed and employs lock hopers to pressurize the feed
Gasification: Gasification is carried out at temperature between 900–1100ºC. Carbon
reacts with oxygen and steam to raw synthesis gas (CO and H2) and some minor by-
products which are removed to produce clean synthesis gas which can be used as fuel,
for generation of steam and electricity, or may be used as chemical feedstock.
Synthesis gas cooling: High temperature syn gas produced from gasification is cooled.

Air separation unit: The process produces oxygen for gasification. The process is based on
cryogenic separation of air. The process involves liquefaction of air and fractionation
to get oxygen, nitrogen and other gases.
Acid gas removal: This involves removal of impurities like H2S, COS, NH3 and HCN by
absorption using various commercial solvent like mono-ethanol amine (MEA), methyl
diethanol amine (MDEA), methanol rectisolvent and selexol (Handa and Ganesh, 2011).
The solvent is regenerated by stripping the acid gases and recycle.
Slag handling system: The gasifier may be either slagging or nonslagging.

15.6.4 Gasification in Petroleum refinery (Handa and Ganesh, 2011)

With increasing use of heavier crude and processing of heavy residue has resulted
in increased production of tar, petrocoke and asphalt by various residues upgrading
technologies processes like visbreaking, coking and de-asphalting. These residues can be
gasified for production of hydrogen, synthesis gas, electricity, ammonia and chemicals.
During recent years, petrocoke gasification is getting interest by petroleum refiners for
production of synthesis gas which can be further processed to separate hydrogen or
can be used for production of useful chemicals.

15.6.5 Gasifier Configurations

Various types of gasifier used are mentioned in Table 15.19 and shown in Figure 15.4.

Table 15.19: Various types of gasifier

Fixed-bed gasifier Fixed-bed gasifier involves an upward flow of reaction gas through a
relatively stationary bed of hot coal. The gas velocity is low.
Moving-bed gasifier Moving-bed gasifier operates counter currently where the coal inters the
gasifier at the top and moves downward and slowly heated with the product
gas. Gasification takes place in the gasification zone.
Fluidized-bed gasifier, Fluidized-bed gasifier operates at higher gas velocities than fixed bed and
e.g. Winkler/KBR/U- uses smaller particle. The gasifier operates at atmospheric pressure and
GAS moderate and uniform temperature.
Entrained flow Entrained bed operates with parallel flows of reaction gas and pulverized
gasifier coal which minimizes the reaction time and maximizes throughput of
product. The residence time is few seconds. Ash is removed as molten slag.
Source: Vorres, KS. “Coal gasification” Encyclopedia of Chemical Technology vol 6, p.760.
226 Chemical Process Technology

Fig. 15.4: Various type of gasifier commonly used (Source: Parthasarathi, 2009)
Coal and Coal as Chemical Feedstock 227

15.6.6 Gasification Reactions

CnHm + n/2O2 nCO + m/3H2 (l < n < 4)

Where for gas as pure methane m = 4 and n = 1 hence m/n = 4

For oil m/n  2 hence m = 2, n = 1
For coal m/n  1 hence m = 1, n = 1
It is exothermic and produces a gas containing mainly CO and H2. The raw synthesis
gas contains small quantities of CO2, H2O and H2S and impurities, such as CH4, NH3,
COS, HCN, N2, argon and ash, the quantities being determined by the composition of
the feedstock, the oxidant and actual gasification temperature (1300–1400ºC). A small
amount of unconverted carbon is also present and ranges from 0.5 to 1.0 by percent wt.
in liquid feedstock or 50–200 ppm wt. in gaseous feedstock. The various reactions can
be summarized as follows (Chemical Industry Digest. Annual-January 2010, p.148):
Combustion
C + 12 O2  CO, DH – 111 MJ/kmol
CO + 12 O2  CO2, DH – 283 MJ/kmol
H2 + 12 O2  H2O, DH – 242 MJ/kmol

Steam Reforming Reaction

CH4 + H2O  CO2 + 3H2, DH + 206 MJ/kmol

Boudourard Reaction
C + CO2  2CO2, DH + 172 MJ/kmol

Water Gas Reaction

C + H2O  CO + H2, CO + H2, DH + 131 MJ/kmol

Water Shift Reaction

CO + H2O  CO2 + H2, DH – 41 MJ/kmol

Methanation Reactions
C + 2H2  CH4, DH – 75 MJ/kmol

15.7 NEW GASIFIER DESIGNS (Parthasarthi, 2009)

15.7.1 GE Global/Unmixed Fuel Processor (UOP)

• Elimination of air separation unit (ASU)
• High temperature synthesis gas clean up
• Higher efficiency
• Lower cost

15.7.2 KBR Transport Gasifier (TRIGTM) (Parthasarthi, 2009)

• Low rank, high-ash, high-moisture coal compatible
• For power generation, air can be employed as the oxidant
• Lower cost predicted
228 Chemical Process Technology

• Higher availability predicted

• Non-slagging, and refractory issues should therefore be minimal
• Higher predicted efficiency
• Lower emissions (due to higher efficiency)
• Large scale up of the technology still required, by a factor of ~30
• By 2010, this technology will be operating at the scale of E-Gas which has >20 years’
experience already in 2007.
• Lower temperatures and short gas residence time may lead to some methane
formation, which is detrimental in chemical applications.
• Ash disposal problem if carbon conversion predictions are not met in commercial
apparatus.

15.7.3 Catalytic Coal Gasification–BluegasTM (Parthasarthi, 2009)

• Elimination of oxygen plant
• For SNG objective, little or no catalytic methanation required
• High thermodynamic efficiency potential
• Catalyst cost and recoverability
• Carbon conversion and methane production yields in the gasifier
• Cost of applying the catalyst effectively to the coal
• Inherently must be done in a fluidized bed which have not been scaled up to larger
capacities of entrained gasifier (yet)
• Interactions of catalyst with coal ash
• Separation costs of synthesis gas and methane—cryogenic process
• Excess steam requirements
• Unsuitable for chemical synthesis processes due to CH4 reforming requirement.

15.7.4 Coal Gasification in Fertilizer Industry

Coal gasification for production of synthesis gas and ammonia has being used many
part of the world where large quantity of coal is present. However, higher energy
consumption in coal-based ammonia plant has been major constrain. Relative energy
consumption per ton of ammonia is given below [Murthy and Patnaik, 2001].
Gas Naphtha Fuel oil Coal
1.1 1.15 1.45

There has been extensive research for improvement of coal gasification technology
to improve the efficiency and reduce the cost.

15.7.5 Rapid Thermal Processing (RTP™) Process for Conversion of Biomass to

Liquid Fuels
RTP™ is fully heat integrated technology that yields over 70% liquid products
from typical biomass feedstocks. It is a fast thermal process where biomass is rapidly
of heated in the absence of oxygen. The biomass is vaporized and the vapor cooled
to generate high yields of pyrolysis oil. Typical yield of various biomass is given in
Table 15.20. Chemical and biochemical conversion of biomass to biofuel is shown in
Figures 15.5 and 15.6, respectively.
Coal and Coal as Chemical Feedstock 229

Table 15.20: Typical yield of various biomass

Biomass feedstock Typical pyrolysis oil yield, wt% of dry feedstock
Hardwood 70–80
Softwood 70–80
Hardwood bark 60–65
Soft wood bark 55–65
Corn fiber 65–75
Bagasse 70–75
Waste paper 60–80
Source: Reno, et al. 2011.

Fig. 15.5: Chemical conversion route of biomass to bio-fuels

Fig. 15.6: Biochemical conversion route of biomass to bio-fuels

(Source: Hamelinck and Faaij, 2006.)

15.7.6 Co-gasification of Coal and Biomass for Methanol Synthesis

Co-gasification of coal and biomass combined with power and methanol production
can be of considered as a potential fuel-base for gasification and further production
of synthesis gas and methanol. Some of the advantage of integrated biomass-coal
co-gasification system is possible continuous operation of the coal gasification reactor,
lower costs of electric-energy production (Chemielniak and Sciazko, 2003).

BIBLIOGRAPHY
1. Ananth P, Chikkatur A. Resource and Technology Assessment of Coal Utilization in India.
Kennedy School of Government, Harvard University, Cambridge, MA, PEW Centre Global
Climate Change, 2008.
2. Annual Report, Govt. of India, Ministry of Coal, 2007–08.
3. Annual Report, Govt. of India, Ministry of Petroleum and Natural Gas, 2011–12.
4. Annual Report Ministry of Coal, 2019–20.
230 Chemical Process Technology

5. Austin GT. “Coal Chemicals” Shreve’s Chemical Process Industries, Fifth edition Edited by
George T Austin. McGraw Hill International editions; 1984, p.70.
6. BP Statistics EIA, US Departments of Energy 2011.
7. Chemical Industry Digest. Annual-January 2010, p.148.
8. Chemielniak T, Sciazko M. “Co-gasification of biomass and coal for methanol synthesis” Applied
Energy Vol. 74, 2003, p.393.
9. Furimsky E. “Gasification in Petroleum refinery of 21st century” Oil and Gas science and
Technology-Rev IFP, Vol. 54, No. 5, 1999, p.597.
10. Geological Survey of India cited from emerging opportunities and challenges coal sector WEC-
JMC 23 January, 2012.
11. Hamelinck, CN, Faaij APC. “Outlook for Advance Biofuels”, Energy Policy. 34, 2006, pp. 3268–83.
12. Handa SK, Ganesh C. “Gasification technology-status and challenges” Compendium of 16th
Refinery Technology meet on Feb 17–19, 2011 held at Calcutta, Organized by Centre for High
Technology and Indian oil Corporation, New Delhi.
13. [Link]
14. [Link] classificationIndia Exploration
and Production Activities 2007–08.
15. Mall ID. NPTEL lecture Organic Chemical technology NPTEL Web and Video Course IIT Roorkee
2013.
16. Mukhulyonov IU, Kuznetsov, D Averbukh, A Tumarkina E. Furmer “Chemical Technology”,
Mir Publishers Moscow, 1974.
17. Murthy GGK, Patnaik LN. “Coal gasification in fertliser industry—A future perspective.”
Chemical weekly, June 2001, p.163.
18. Parthasarthi Deb, “Clean coal technology Conference” November 10, 2009 PDU, Gandhi Nagar,
Gujarat.
19. Reno ME, Streff M, Hird A, Ray, A. “Conversion of biomass to fuel as an environmental impact
reduction opportunity for the pulp and paper Industry” In paper International, April–June 2011,
p.18.
20. Sawhney P. Meeting of Indo-US working group on Coal April, 2008.
21. Sukumarannair MP. “Harness gasification for integrated chemical complex” Chemical Industry
digest Annual–January 2010, p.144.
22. Tirodkar RB, Belgaonkar VH. “Use of chemicals derived from coal in surface coating industry”
Chemical Business No. 4, April 1991, p.35.
23. Tirodkar RB, Belgaonkar VH. “Use of Chemicals derived from coal in surface coating industry”
Chemical Business April 20–May 4, 1991, p.35.
24. Visuvasam D, Selvaraj P, Sekar S. 2005. “Influence of Coal Properties on Particulate Emission
Control in Thermal Power Plants in India” Second International Conference on Clean Coal
Technologies for Our Future (CCT 2005), Sardinia, Italy.
25. Vorres KS. “Coal gasification”, Encyclopedia of Chemical Technology.
16
Pulp and Paper Industry

16.1 INTRODUCTION
The history of paper making goes back to ancient time while first official report on
the manufacture of paper was reported in China in 105 AD. The knowledge of paper
manufacturing spread westward, along with the silk and trade routes, reaching India
is round 605 AD. Pulp and paper production has increased globally and will continue
to increase in the near future and is one of the largest manufacturing sectors in the
world. Per capita consumption of paper is sometimes yardstick for measurement of
industrialization. There are about 500 kraft mills and many thousands of other types of
pulp and paper mills all over the world. Pulp and paper industry is one of the oldest
industries in India. With a 20 mills and installed capacity of one lakh tons per annum
at the time of independence, the paper industry has made continuous strides and
now there are about 750 big and small paper mills in India and accounts 4% of world
production (Goyal, 2018).
There are about 7.0 billion people living on planet earth. Worldwide paper
consumption in this century has increased 4 times faster than population. Paper and
paperboard worldwide will reach 640 million tons in 2020 with world population of
8000 million people and per capita consumption of paper and paperboard of 80 kg.
There are about 500 kraft mills and many thousands of other types of pulp and paper
mills in the world. During 2010–2014, global pulp and paper production has grown by
7.6 million tons.
India is the fastest growing pulp and paper market in the world. Overall paper
demand is growing at a CAGR of 6.6%. The demand of paper is set to rise to 18.5 million
tons in 2018–19. The paper industry in India is classified under four segments: Printing
and writing, packaging paper and board, specialty papers and others, and newsprint
with over 750 mills. Wood accounts for 30–35% of raw material while wastepaper for
45–50% and agri residue for 20–22% (Goyal, 2018; Singhania, 2018).
An India ratings report estimates India’s per capita paper consumption at 11 kg
against 22 kg in Indonesia, 25 kg in Malaysia, 42 kg in China and global average of
56 kg and Asian average of 40 kg. India’s share in global paper manufacture is about
2.6%. Profile of Indian paper mills and world paper industry is given in Table 16.1A.
Early 1970s the share of wood, agricultural residues and wastepaper was 84%, 9%
and 7%, and presently, it constitutes 31%, 22% and 47% in comparison to globally 57%,
39% and 4%, respectively. Out of about 11 million tons paper production in 2011–12,
approximately 7.5 million tons is produced from agri residue and wastepaper and mainly
231
232 Chemical Process Technology

contributed by medium and small scale paper mills with 750 mills fragmented all over
the country and 50 mills having capacity of 50,000 or more ([Link] Smenventure.
com/grwth- paper-industry-India March 9, 2018).
India is projected that consumption and production of paper in next five years will
be increased up to 16.5% and 14.8%, respectively (Nair, 2012).
With the emergence of low-cost products, such as China, Indonesia, Vietnam and
Latin America, now Indian paper industry is more productive, more energy efficient
and more focused on high-performing quality, high-value products and services which
are environmentally sustainable.
The sustainable forestry shall significantly contribute to cutting the net increase of
carbon dixide to the atmosphere, besides adding to the economic value of indian forests
(IPPTA, 2014), (Table 16.1B).
At around 27%, India’s recycling rate is far off the achievable and far behind the
71.7% already achieved by European mills in 2012 (38% in 1990) (IPPTA, 2014).
More than 3 million tons of paper is sourced from outside country and another 4
million tons is collected every year within country. According to Report of Planning
Commission, the domestic production is protected to be 33.4 million tons by 2024–25
and out of which 17.8 million tons shall be produced by using recycled fiber leading to
requirement of 9.3 million tons of recycled fiber.
Printing and writing segment is expected to grow at a CAGR of 4.2% and reach 5.3
million tons by financial year 2019. Packaging paper and board demand is expected to
grow at a CAGR of 8.9% and reach 9.7 million tons during financial year 2019 while
newsprint requirement is expected to touch 2.7 million tons in the financial year 2019.

Table 16.1A: Profile of Indian paper mills and global competitiveness

Mills Capacity Kg/A/ Energy consump­ Water consump­
Profile
(number) (million tons) capita tion GJ/t of paper tion m3/t of paper
World 7.0 billion 9000 370 55 32.0–40.9 30–50
India 1.2 billion >660 9.5 8.3 51.6–80.0 80–150
Source: Eloranta, J. ‘Indian pulp and paper industry—challenges and opportunities” In paper
International, January–March 2010, p.12.

Table 16.1B: Advances in Indian paper industry (1950–2011)

Parameter 1950 1965 2011
Number of mills 17 52 759
Number of integrated mills 13 15 30
W&P paper production 0.4 lakh ton 1.53 lakh tons 3.9 million tons
(includes copier)
Newsprint – 0.3 lakh ton 0.79 million ton
Board 0.76 lakh ton 3.56 lakh tons 5.42 million tons
Speciality paper – – Not available
Total production 1.16 million tons 5.39 lakh tons 10.11 million tons
Biggest machine 35 tons/day 48 tons/day 500 tons/day
Century Paper Mills)
Contd...
Pulp and Paper Industry 233

Table 16.1B: Advances in Indian paper industry (1950–2011)

Parameter 1950 1965 2011
Per capita paper consumption 0.4 1.12 9.3
India, kg
Per capita paper consumption 17.17 19.95 47
world, kg
Per capita paper consumption 145.4 197 312
USA, kg
Raw material Wood and bamboo Wood and Wood, bamboo, agro
bamboo residue and RCF
Wood 3.0 lakh tons 16.1 lakh tons 9.0 million tons
Waste paper – 7.0 million tons (4 million
tons imported waste paper)
Agricultural waste 0.3 lakh ton 1.60 lakh tons 7.8 million tons
(local grasses) (local grasses)
Source: CPPRI IPPTA Vol. 26, no. 1, Jan–March, 2014; Courtesy: IPPTA.

Raw material and energy sources in Indian and European countries are given in
Figures 16.1 and 16.2. Specific energy consumption in Indian mills is higher than other
developed countries (Table 16.2).

Figs. 16.1 and 16.2: Raw material and energy sources (Source: Mall RC, Narayan Moorthy R.
“An overview of Indian pulp and paper industry” Green Solution Week Sweden, 2010)

Table 16.2: Specific consumptions: A comparison

Input per ton of product Indian mills European mills
Heat, GJ/t 15–30 4–8
Electricity, kWh/t (except pulp mill) 800–1500 400–800
3
Water, m /t 25–150 5–40
Chemical recovery, % 88–96 95–98
Source: Mall and Moorthy 2010.
234 Chemical Process Technology

The present demand of paper is estimated at 13.1 million tons with demand is
projected to boost to 23.5 million tons in 2024–25. India is the greatest growing of paper
industry in the World ([Link] [Link]/grwth-paper-industry-india
March 9, 2018).

16.2 TECHNOLOGICAL TURNING POINT IN THE INDIAN PAPER INDUSTRY

• Efficient management of depleting resources with sustainable forest productivity
through improved resource planning, better plantation technique, good harvest
management
• Conservation of natural resources
• Effective waste utilization and recycling of fiber
• Improved cleaning efficiency
• Better environmental management for reducing or eliminating toxicity
• Better fiber properties
• Improved runnability
• Improved product appeal (higher brightness).
• Odorless mill.

16.3 MAJOR CHALLENGES AND SHORTCOMINGS

• Low availability of forest raw materials and poor forest management
• Poor infrastructure
• Poor to non-existent commitment to innovation and obsolete technology existing in
many old mills
• Rising cost of inputs: Fibrous raw materials, chemical, labor, energy
• Uneconomic size and obsolete technology in many mills
• High cost of production with rising cost of raw materials whose cost is increasing
• Innovation in agro-based mills
• Poor productivity and instrumentation
• Poor recycling of waste paper which is much less to world average
• Recovery of chemicals from agro-based black liquor
• Decolorization and detoxification of waste water
• Air pollution problem especially in kraft mills
• High energy consumption
• Competition from import.

16.4 RAW MATERIAL

Paper industry consumes a wide variety of raw materials—cellulosic derived from
forest, agricultural residues and waste paper; non-cellulosic coal, chlorine, lime, sodium
hydroxide, sodium sulfide, fuel oil, talcum powder, etc.
Major raw materials used by paper industry is bamboo, wood, bagasse, waste paper
and agricultural residue like wheat straw, rice straw, jute sticks, hemp, kenaf, grasses,
sea weed, etc. Apart from this, paper industry consumes large amount of chemicals like
caustic soda, sodium sulfide, sodium carbonate, chlorine, hypochlorite, mineral acid;
coal, talcum powder, etc.
Pulp and Paper Industry 235

India has a landmass of 3.29 million [Link] and 0.629 million [Link] of forest, i.e.
nearly 2.5% of world’s geographical area, only 1% of the forest area supporting 16% of
world populations. Indian forestry is at a cross road, and actually only 12% land area
has good forest cover against the official figure of 19% (Jameel, 1995). With fast depletion
of forest raw material, large integrated mill which accounts for about 38% of the total
production are facing serious challenges, and hardly there is any scope for substantial
capacity expansion unless and until they go for secondary fiber utilization. Small and
medium mills based on agro-based accounts for nearly 31% of India’s production. With
depleting forest raw material, waste paper, agricultural residues like bagasse, wheat
straw, rice straw, jute, grass, etc. are likely to play important role in meeting the future
demand of raw material for paper industry. Table 16.3 gives the detail of raw materials
used by small and large integrated pulp and paper mills.

Table 16.3: Raw material consumption in small and large integrated pulp and paper mills
Requirement per ton of paper
S. no. Raw materials
Small paper mills Integrated pulp and paper mills
1 Cellulosic raw material, kg (hard­ 2500–3000 2200–2500
wood, soft wood, agricul­tural
residues, etc.)
2 Cooking chemicals, kg as Na2O 70–90 310–360
3 Caustic for bleaching 20–35 20–35
4 Chlorine, kg 100–160 130–160
5 Salt cake, kg – 60–70
6 Lime (available CaO (60%) kg for 70–100 70–100
bleaching
7 Lime (available CaO 60%) for – 350–450
causticizing section, kg
8 Coal, ton 1.0 – 1.35 1.5 – 3.0
9 Sulfuric acid, kg – 6–7
10 Alum, kg 50–60 50–60
11 Rosin and wax emulsion, kg 10–12 10–12
12 Starch, kg – 11
13 Hydrochloric acid, kg – 2
14 Furnace oil, kg – 75
15 Water, m 3 150–300 150–300
16 Power, kWh 1200–1300 1300–1800
17 Steam, ton 6.0–7.0 11–16
18 Soda ash as % of rosin 7–8 7–8
19 Talcum, kg 120–150 150–180

Problems in utilization of hard wood: Although hardwood is being used extensively as raw
material because of their availability, various problems are there in utilization which
include debarking, chipping problem due to high density chips difficult to chip, higher
236 Chemical Process Technology

reject, problem in washing due to more fines and foam, bleaching of mixed hard wood
and bamboo pulp creates problems due to varying bleach requirement, shade variation
as various species have different shade, problem in evaporator, higher percentage of
hard wood affects readability of machine lower strength.

16.4.1 Secondary Fiber in Paper Making

Increased use of recycled fiber/paper is the current trend in the paper industry globally
as it is one of survival routes for the paper industry against dwindling fiber resources
and environment- related issues. Collection of domestic secondary fiber is an initiative
of corporate social responsibility; shift in the raw material consumption pattern in
India and global paper recycling pattern is given in Tables 16.4 and 16.5, respectively
(Raghuveer, 2012, Goyal 2018). Potential sources of waste paper are domestic refuse,
industrial refuse, office refuse, trade refuse, etc. In India around 65% of paper industry
requirement of waste paper is met through imports which is on increase year by year
(Mukundan, 2011).

Table 16.4: Raw material consumption pattern in India Table 16.5: Paper recycling in
% share different countries
Year
Wood Agro residue Waste paper USA 65%
1970 8.4 9 7 Europe 70%
2000 39 31 30 UK 40%
2011 31 22 47 China 30%
2017 30–35 20–22 45–50 India 20%

16.5 INNOVATING TECHNOLOGIES IN PAPER INDUSTRY

Innovative new products and technology are essential for growth of any industry. Paper
industry is no exception to this. In recent times, various approaches have emerged
like innovative process technological solutions for paper mill processes application
of nanomaterials for enhancing product quality, adoption of biorefinery concept for
effective utilization of all constituents of fibrous material, production of bio-fuels, bio-
chemicals, biocomposite, intelligent packaging, etc. from wood and other raw material
(Thapliyal, 2018).

16.6 PROCESS STEPS IN THE MANUFACTURE OF PULP AND PAPER

16.6.1 Pulping and bleaching

Paper industry uses wide variety of raw materials employing different type of pulping
and bleaching processes depending on the type of raw materials and requirement of
pulp furnish for final paper making. Both unbleached and bleached pulp is produced
to meet the requirement of paper. Requirement of bleaching chemicals are also varying
depending on the quality of paper and brightness and environmental considerations for
cleaner and greener paper. Various steps in pulping and bleaching process are given in
Table 16.6. Pulping and bleaching play important role in providing strength to paper
depending on fiber length, cellulose content.
Pulp and Paper Industry 237

Table 16.6: Pulping and bleaching process

Acquisition of raw material Hard wood, soft wood, bagasse, wheat and rice straw, sabai
grass, etc.
Raw material preparation Debarking, depithing, chipping, cutting, screening
Pulping
• Chemical • Sulfate (Kraft), soda pulping, sulfite pulping
• Semi-chemical • Neutral sulfite semi-chemical (NSSC)
Mechanical pulping • Stone ground wood (SGW)
• Thermomechanical pulp (TMP)
• Refiner mechanical pulp (RMP)
• Cold soda refiner mechanical pulp (CRMP)
Sulfite • Acid sulfite higher percent of free SO2
(Ca, Mg, Na, ammonia base)
• Bisulfite: (little or no free SO2
(Ca, Mg, Na, ammonia base)
Washing and screening 3–4 stage washing, screening and enrichening
Bleaching • Bleaching chemicals: Oxygen, ozone, chlorine, caustic soda,
chlorine dioxide, calcium hypochlorite
• Conventional bleaching sequence CEHH, CEH, CEHD, for
chemical pulp
• Advance bleaching sequence
• Hydrogen peroxide, sodium peroxide, hydrosulfite for mechanical

Chipping: Chipping is a important step in pulping, and chipping quality plays important
role in the overall quality of pulp. Efficiency of debarking process, chip size—length,
thickness, uniformity of size, removal of dust and fines are important factors affecting
pulping efficiency and quality of pulp. In case of bagasse depithing is very important
in overall quality of pulp and paper. In case of agricultural residue size of the straw
sand removal of dust also is important. In chipping of bamboo and wood drum chipper
and disk chipper are used.

16.6.2 Kraft Pulping Process

Kraft pulp is having higher strength and important in pulping of wood and bamboo.
Kraft pulping involves pulping, washing, screening and centri cleaning, and bleaching.
Pulping involves separation of fiber for chemical or mechanical pulping, removal of
knots, washing of pulp for recovery of chemical, rejects uncooked material, sand and
other foreign material. Bleaching of pulp involves bleaching of washed and screened
pulp with bleaching chemicals—chlorine, caustic, hypochlorite, chlorine dioxide, ozone,
hydrogen peroxide, and sodium hydrosulfite (Fig. 16.3). Conventional uses of bleaching
sequences were (CEHH, CEH, CEHDED, CEDED). Many of the mills in India have also
gone for oxygen delignification and newer bleaching sequences.
Cooking of raw material is done by batch digester, continuous digester. Spherical
batch digester is commonly used for cooking agricultural residues. Cooking liquor used
in kraft pulping process is sodium sulfide and sodium carbonate. Cooking cycle may be
around 3–5 hours depending of raw material and extent of cooking in batch digester.
Typical continuous digester consists of upper heating zone, upper cooking zone, lower
cooking zone, and washing zone. Sequence of operation in coking in digester is chip
238 Chemical Process Technology

filling, presetting, liquor charging, heating-up and pressure-up period, cooking and
blowing.
Bulk density : 130–150 kg/m3
Bath ratio : 1 : 3, sulfidity about 15%
Cooking temp. : 170–175ºC
Pressure : 7–7.5 kg/cm2

Fig. 16.3: Kraft pulping and bleaching process

16.6.3 Pulping of Agricultural Residue

Pulping of agricultural residues—rice straw, wheat straw, grasses, jute sticks, etc. require
mild cooking condition as compared to hard wood and soft wood pulping. Figure 16.4
illustrates the agro residue pulping and bleaching process. Various steps involved are:
• Cutting and dusting
• Cooking batch or rotary spherical or tumbler digester
Bulk density : 130–150 kg/m3
Bath ratio : 1:6, Alkali: 8–10%
Cooking temp. : 135–140ºC
Temp to rise : 135ºC 1 hour
Time at : 135–140ºC 2 hours
• Blowing
• Washing and screening, centri-cleaning,
• Bleaching
• Recovery of chemicals.
Pulp and Paper Industry 239

Fig. 16.4: Agro residue pulping and bleaching

Problems in Utilization of Agricultural Residues

Some of the major problem in utilization of agricultural are low bulk density, seasonal
availability, higher pollution load, higher percentage of silica, poor washing due to
slow drainage, high dilution, problem in evaporator due to higher percentage of silica,
longer wire parts due to poor drainage, lower strength of pulp and paper.

16.6.4 Bagasse Pulping

Due to availability of bagasse from sugar mills, a number of agro-based paper mills are
using bagasse. About 10% of the bagasse is available from sugar mills.
Bagasse 60% fiber and 30% pith, 60% good quality fiber 30% pith, and 10% water.
• 0.25 ton of bagasse (dry) per ton of sugarcane.
• 3 tons of bagasse per ton of unbleached pulp.
Bagasse with 50% moisture and about 2–2.5% sucrose and water-soluble material.
Process: Process of bagasse pulping involves depithing and pulping of depithed bagasse.

Depithing: Removal of pith is necessary before pulping as pith has high ash, difficult
to bleach and has little value in paper making. Various depithing processes are dry
depithing, wet depithing, and combined depithing.
Pulping, washing and screening: Cooking of bagasse can be done in batch or continuous
digester. Typical cooking conditions for bagasse pulping are: Batch cooking 10–12%
NaOH, 160ºC, 6–7 kg/ash, 2 hours, bleaching requirement 5–6%, 3-stage brown stock
washing is done which is followed by screening and centri-cleaning. Details of various
digesters used in pulping are illustrated in Figure 16.5.
Bagasse newsprint: Bagasse newsprint is made for 50% bagasse having good printing
quality, run-ability, opacity, and rapid absorption

Bagasse pulpling process

Depithing: Dry depithing, wet depithing, combined depithing. Pith has high ash, difficult
to bleach and has little value in paper making.
Pulping: Batch cooking 10–12% NaOH, 160ºC, 6–7 kg/cm2, 2 hours, bleaching requirement
5–6%.
240 Chemical Process Technology

Fig. 16.5: Various types of digester

16.7 MECHANICAL PULPING

Mechanical pulping has significant importance in paper making because of the high
yield and its requirement in newsprint. Conventional method of mechanical pulping
was groundwood stone pulping which is being still used by many mills. However, many
new generation mills have gone for refiner mechanical pulping or thermomechanical
pulping. Process flow diagram for mechanical pulping is shown in Figure 16.6.
Stone groundwood (SGW): Primary action in grinding zone involves compression
and release of wood as the grit projecting from the pulp stone surface passes of the
underneath of the wood. The function of wood as wood, as it is deformed, friction of
Pulp and Paper Industry 241

Fig. 16.6: Mechanical pulping

wood and pulp stone and friction of fluid generate heat which causes softening of the
lignins, and resins binding the fiber and also generate vapor pressure which assists in
separating the fiber from the wood wall. The act of compression and release of wood
fiber flushes fluid in and out of the wood wall thus dividing some of the binding agents
and assisting in the release of the fiber from wood. Pulp stone manufacture supply
their basic abrasives, silicon carbide, aluminum oxide and modified aluminum oxide.
The grinding surface of the pulp stone will be maintained as near constants possible to
ensure uniform quality of the pulp.
Motor 5000 h/s – 10000 h/s, speed of the pulp stone is 35-40 m/sec, 360 rpm.
Purpose of grinding is to fiber the wood with a minimum damage to fibers and to
develop quality required for the end wood, thereby lowest consumption of energy
and grinding material and higher production for grinding and desired to minimize the
products as the cost of the following variables are important: Wood—species, shape
of bolts manufacture of wood; Stone—type of abrasives, size of grit, type of pattern,
depth of grooves, extent of wear.
Grinder—type of grinder, specific grinding pressure which is interrelated to the load
and the rate of wood advance, length of grinding zone, width of stone-grinding area,
tangential speed of stone, pulp temp, pulp consistency, shower temperature, depth of
emersion of stone in pil.
5–10 ton/day
50–1000 h/sec
20 ton/day 5000 h/sec
Silicon carbide, aluminum oxide sintered together.
242 Chemical Process Technology

Refinery Mechanical Pulping

This involves mechanical reduction of chips in a double rotating disk refiner with the
use of two refiners in series and gave pulp much stronger than SGW in tensile burst
and tear strength. Although soft wood does need any treatment but hardwood needs
light chemical soak with about 1–1.5% NaOH + 0.7–1.0 Na2SO3 at a temp of 75–80ºC.
Refining: Fiberizing of chips was earlier done by rod mill. The chips were fed in a rotating
drum at one end; the defilation was achieved by the crushing action of a number of
steel rods, and the fibers were collected at the opposite end of the drum. The variables
in refining are speed of rotation, disk interdistance, load, temperature, and consistency.
Refiner mechanical pulp (RMP): RMP involves mechanical reduction of chips in a precision
double-rotating disk refiner with use of two refiners in series. Stronger pulp than SWD
in tensile, burst and tear strength and permitted reduction of chemical pulp.
Thermomechanical pulping (TMP): Thermomechanical pulping consists of refining of
chips in pressurized environment with steam and chemicals in gas phase, following
by washing, screening, refining, bleaching, short steaming period with a duration
2–3 min at about 110–120ºC at refining pressure of 10–25 psi in the first stage with
second stage refining under atmospheric conditions. Refining is done at temperature
of 100–13ºC improved pulp quality long fiber fraction is increased because of softening
of the lignin at elevated temperature which losses the bond between the fibers in the
wood structure. The usage of small amount of chemical either swelling (NaOH) and
or brighter NaHSO3 increase giving high strength and brighter pulp, during TMP less
damage to pulp. Various variables are chip quality, chip washing, presteaming, solute
pattern, plate size, speed, and consistency.
• Power 100–200 HPD/T
• SWPG 65–85 HPD/T
Some of the advantages of thermomechanical pulping are:
• Complete utilization of the trees
• Greater flexibility of raw material utilization enabling utilization of cheaper raw
materials, as wood stacks, edgings, sawdust, shaving, and other refuse
• No or very little consumption of chemicals
• Pulp with good bonding properties and high content of long fibers, improved
strength characteristics, improved paper machine runnability, higher production,
and lower costs
• Lower shive content and simplified cleaning
• Good bulk, improved quality and printability
• Minimum labor cost
• High yield and high strength resulting in either reduced or eliminated costly chemical
pulp, improved quality and lower cost/ton
• More and better utilization of the available raw material
• No air-atmospheric pollution, little water pollution and reduced environmental
damage.
• Adaptability to easier control automatic and computer control
• Good bulk, improved quality and printability.
ƒ 1300 kWh/ton: stone ground
ƒ 1475 kWh/ton: RMP
ƒ 1475 kWh/ton: TMP
Pulp and Paper Industry 243

In chemical pulping substances if the middle lamellas chemically dissolved to an

extent that makes fiberizing possible as that mechanical treatment is more elaborate
machinery.
Mechanical pulping gives nearly quantitative yield but causes rupture of the fiber
walls on fiberizing and gives pulp which contains pulping by pressing wood against a
revolving grindstone in the presence of water to cool the stone, which become heated
by friction.
Stone surface is burred to a certain pattern of grooves before the stone is engaged in
production.
Production refiner mechanical pulp involves two basic steps.
• Fiberization (defibration)—centers around original wood structure to single structure.
• Fibrillation—reduces the portion
Chemi-thermomechanical Pulping: This involves short cooking with 1–2% caustic
and sodium sulfate which facilitate the separation maintaining maximum strength
characteristic. It gives better strength and bright pulp.
Advantage: Power shaving, superior quality of pulp and finished product, permits
utilization of higher percent of mechanical pulp, power shires, minimum labor, high
yield, and less pollution.
Power Consumptions
1300–1400 kWh/ton SWW
1475 kWh/ton RMP
1475 kWh/ton TMP
Bleaching of Mechanical Pulp
Hydrosulfite: Zinc hydrosulfite and sodium hydrosulfite are commonly used for
groundwood pulp and refiner pulp. Zinc hydrosulfite is prepared by reacting zinc
dust with sulfuric acid. Sodium hydrosulfite can be generated by reacting sodium
borohydride and bisulfite.
Peroxide: Hydrogen peroxide and sodium peroxide are recognized as effective economical
bleaching agents. They do not form chlorinated organic derivatives. They are particularly
used in the bleaching of high lignin wood pulp and as a final stage in chemical pulp
bleaching.

16.8 NEWSPRINT
Newsprint is one of the major portions of paper produced and plays important role in
information, cultural, and economic growth. Newsprint typical contains 70% chemi-
mechanical pulp from eucalyptus and 30% chemical pulp from reed and bamboo.
Eucalyptus wood is chipped screened and the chips are washed. The washed chips
are treated with steam and caustic soda solution. The impregnated chips are pressed
to remove spent liquor and is refined in two stages. Then pulp is washed on brown
pulp washer and bleached by two-step hypochlorite treatment. The bleached pulp is
again refined in a third step refiner, screened, center cleared and dewatered in a
thickener drum and stored. Process flow diagram of newsprint manufacture is given in
Figure 16.7. Newsprint is a paper of printing category embossing in itself the qualities
like runnability, opacity and low cost.
244 Chemical Process Technology

Advantage of groundwood pulp in newsprint: Advantage of ground wood pulp in news-

print furnish are:
• Higher bulk-improves calendar action, improves formation because of time fraction,
decreased far-sightedness, better and improved opacity inhibits show through better
ink absorptivity, absence of print through, improved surface.

Fig. 16.7: Process of newsprint manufacture

Quality of good newsprint: Runnability, good printability, minimum two-side uniformity.

Pulp formation should need the following requirements:
• Low freeness 50 csf
• Specially good screening
• Good pulp strength property
• Uniform pulp quality
• Controlled bleaching system to maintain required brightness
Mechanical pulp has to have good wet end strength, good bonding
Chemical pulp used in newsprint hard wood pulp, bagasse pulp chemical
Bagasse TMP, CTMP
Problems in Utilization of Hardwood
• Debarking
• Chipping problem—high density chips difficult to chip
• Higher reject
• Problem in washing due to more fines and foam
• Bleaching of mixed hardwood and bamboo pulp creates problem due to varying
bleach Requirement
• Shade variation, darker shade
• Problem in evaporator
• Higher percentage of hardwood affects runnability of machine lower strength.
Newsprints pulp
Newsprint pulp furnish consists of kraft pulp and mechanical pulp.
Pulp and Paper Industry 245

Furnish
25–30% Kraft pulp
70-75% Mechanical pulp
Raw material: Bamboo, hardwood, bagasse,
Advantage of groundwood pulp:
• Higher bulk—improves calendaring action
• Improve formation because fine fraction
• Better and improved capacity, inhibits show through better ink absorbency
• Absence of print through good bonding.
In bleaching of mechanical pulp, zinc hydrosulfide 1%, hydrogen peroxide.

16.9 SULFITE PROCESS

Sulfite process was earlier use for pulping; however, it has been replaced with kraft
pulping. Table 16.7 gives details of important terms being used in sulfite process.

Table 16.7: Important terms being in sulfite process

Terms Description
Total sulfur dioxide Total SO2 as determined by an iodometric titration and expressed as %
total SO2
Free sulfur dioxide Free SO2 is the actual free SO2 plus half of the SO2 in the bisulfite of the
base. It is also called available SO2.

Combined SO2 Difference between total SO2 and free SO2

Acid sulfite: The process in which the cooking acid contains a high percent of free SO2
pH 1.2–1.5. Not suitable for resinous wood.
NaHSO3 + SO2

Bisulfate: The process in which the cooking liquor contains a predominance of bisulfate
ion in the 3.6 pH ranges with no free SO2.
NaHSO3

Neutral Sulfite:
Na2SO3 + Na2SO3 pH = 7–9
SO2 + H2O H2SO3
CaCO3 + 2H2SO3 Ca(HSO3) + CO2 + H2O
CaO + H2O Ca (OH)2
Ca(OH)2 + H2SO3 Ca(HSO3)2 + 2H2O
Mg(OH)2 + H2SO3 Mg(HSO3) + 2H2O
Na2CO3 + 2H2SO3 NaHSO3 + H2O
NH3 + H2O NH4OH
NH4OH + H2SO3 NH4HSO3 + H2O
246 Chemical Process Technology

Rate of pulping: NH3 > Mg > Na

Pressure: 620–755 kPa. Temperature: 125–160ºC

Total cooking time 6–12 hours.

Cooking acid: 7–8% of total SO2.
1 ton of pulp: 175–220 kg of SO2 55–68 kg MgO

16.10 COMMONLY USED TERMS IN PULPING

Commonly used term in pulping is given in Table 16.8.

Table 16.8: Commonly used terms in pulping

Terms Description
White liquor Cooking liquor obtained after causticizing green liquor
containing NaOH, Na2S, and small quantity of Na2CO3
Black liquor Liquor obtained after washing of pulp after cooking which
is further concentrated for burning in furnace to recovered
chemicals.
Green liquor Liquor obtained after dissolving smelt from furnace in weak
liquor from causticizing section
Active alkali NaOH + Na2S
Effective alkali NaOH + ½Na2S
Total titratable alkali NaOH + Na2S + Na2CO3
Sulfidity Na2S/titratable alkali
Causticity NaOH/NaOH + Na2S
Causticizing efficiency NaOH/(NaOH + Na2S) × 100
Reduction Na2S/(Na2SO4 + Na2S)
Over all recovery Recovery ± black liquor stock/froth liquor consumed
K no. (Permangnate number) No. of 0.1 N KMnO4 consumed by 1 g of moisture free pulp.
Dilution factor (DF) DF = W – E
W = Water added per ton of mass
E = Water going in pulp per ton of pulp
Bath ratio Wood to liquor ratio
Consistency BD pulp/ total pulp weight (100 g ), i.e. wt of BD pulp in 100 g
of pulp + water mixture
Copper no. No of milligrams of metallic copper which is reduced from
cupric hydroxide to cuprous oxide in alkaline medium by 100
g of pulp
Kappa no. 837+ 0.0323*40 mL KMnO4 no.
Pulp and Paper Industry 247

16.11 RECOVERY OF CHEMICALS

Chemical recovery system is an integral part of pulp and paper units and the efficiency of
chemical recovery plays an important role in economics. Efficiency of chemical recovery
units in terms of thermal efficiency, energy recovery and conversion of thermal energy
to electrical energy has tremendous impact on overall economy of pulp production
(Kulakarni, 2010). Although earlier agro-based mills were not having recovery furnace
due to high silica content of black liquor and smaller capacity, now chemical recovery in
agro-based mills have been made mandatory. Important terms in recovery of chemicals
are given in Table 16.9.

Table 16.9: Important terms in recovery of chemicals

Active alkali NaOH + Na2S

Effective alkali NaOH + ½Na2S

Total titratable alkal NaOH + Na2S + Na2CO3
Sulfidity Na2S/titratable alkali
Causticity NaOH/NaOH + Na2S
Causticity efficiency (NaOH/NaOH + Na2S) × 100
Reduction Na2S/(Na2SO4 + Na2S)

Over all recovery Recovery = black liquor stock/fresh liquor consumed

16.11.1 Kraft Recovery

Recovery of chemicals from black liquor is very important for overall economy of paper
industry. Kraft recovery process flow diagram is shown in Figure 16.8. Various sections
in kraft recovery plant are:
• Evaporation section and further concentration: Multiple effect evaporator, direct
contact, cascade evaporator, cyclone evaporator, venture scrubber
• Recovery furnace: Furnace, ESP (Fig. 16.9)
• Dissolving tank and green liquor generation
• Causticizing and clarification
• Lime sludge reburning

Fig. 16.8: Kraft recovery process

248 Chemical Process Technology

Fig.16.9: Kraft recovery furnace

Black Liquor Oxidation: Black liquor oxidation has become integral part of recovery section
for reducing the emission of volatile sulfur compounds. Oxidation of black liquor by
air reduces the emission of odorous sulfur compounds. Mercaptans and other sulfur
compounds are oxidized into less volatile chemicals. Both weak black liquor and
concentrated black liquor oxidation have been reported. Typical composition of black
liquor from wheat straw pulping is given in Table 16.10.
Various steps involved in kraft recovery section are:
• Concentration of black liquor with inlet 12–18% and outlet 40–50% long tube
evaporator. Normally five to six effect evaporator is used. As the black liquor becomes
highly viscous, further concentration is done by direct contact evaporator and falling
film evaporator
• Further concentration in direct contact evaporator to 60%: Using cyclone evaporator,
cascade evaporator and venturi scrubber. In some of the mill falling film evaporator
is being used to achieve higher concentration of black liquor which is not possible
with conventional evaporator.
• The concentrated black liquor is sprayed in the furnace where black liquor is
incinerated to yield smelt and flue gases. A typical recovery furnace consists of air
preheater, economizer, furnace and boiler, cyclone, venturi scrubber, and electrostatic
precipitator.
• Addition of makeup chemicals Na2SO4 (salt cake) in thick concentrated black liquor
which is reduced to Na2S in the furnace in presence of carbon
• Incineration of black liquor in recovery furnace
• Reducing zone in bottom to burn organic
• Dying zone
• Oxidation zone.
Reactions in recovery of chemicals from black liquor
The main reactions are (1–3 predominantly)
Na2O + CO2 Na2CO3

Na+ + H+ + S2– NaHS

Pulp and Paper Industry 249

Table 16.10: Typical composition of black liquor from wheat straw pulping
Parameters Wheat straw black liquor
Total solids 10.8
Swelling volume ratio, mL/g 10
Gross calorific value 2890
Silica as SiO2% , w/w 2.87

Acid insoluble as SiO2%, w/w 3.0

Chloride as Cl%, w/w 4.3

Potassium as K%, w/w 6.0
Sodium as Na%, w/w 15.0
Calcium as Ca%, w/w 0.08
Inorganic as NaOH%, w/w 35.01
Organics %, w/w 64.99

Na + OH– NaOH
1
Na2O + SO2 + O22 Na2SO4
Na2S + 2O2 Na2SO4
Na2SO4 + Na2S + O2 2Na2S2O3

Other reactions:
Na2SO4 + 2C Na2S + CO2
Na2SO4 + 4CO Na2S + 4CO2

• Dissolving smelt in dilute wash liquor or water to produce green liquor, containing
sodium carbonate and sodium sulfide.
• Causticizing of green liquor with lime to produce white liquor, lime sludge. A
typical causticizing section consists of lime slaking with green liquor, dreg clarifier,
causticizing tank, clarifiers, rotary filter, lime kiln.
Na2CO3 + CaO + H2O 2NaOH + CaCO3
• Burning of lime sludge to produce lime.
CaCO3 CaO + CO2

Typical Characteristics of Black liquor

1 ton of black liquor—2.2 tons of steam
Black liquor solid—1.30 ton/ton of pulp
Weak black liquor per ton of pulp—10–12 m3
Calorific value of black liquor—3080 cal/g
Black liquor—organic 70%, inorganic 30%
Weak black liquor—Na 28 g/L
RAA—10.85 g/L
250 Chemical Process Technology

16.11.2 Recovery of Chemicals in Agro-based Mill

With the shortage of forest based raw material and to preserve the forest, the paper
industry in Asia and other parts of the world is forced to use non-woody fibrous raw
materials. India is one of the leading countries using substantial proportion of non-wood
materials which constitute about 50% of total raw material furnish (Dixit et al., 2012).
Non-wood raw materials are characterized by high silica content which varies from
1.5 to 20%. Most of the silica present in raw material passes into black liquor. Presence of
silica in relatively high concentration creates numerous problems in chemical recovery
plants. (Dixit et al. 2010). Evaporator, recovery furnace, and lime kiln operation are
adversely affected by presence of silica in black liquor (Ibrahim, 1988). The process of
distillation of bamboo and straw black liquors by carbonation has been developed by
Central Pulp and Paper Research Institute, Saharanpur.
Due to high silica content of the agricultural residues recovery of chemical from
agro-based mills have caused major concern in Indian paper mills. Table 16.11 gives the
details of processes for recovery of chemicals from agricultural residues black liquor.
Black liquor from cooking agricultural residues has high silica content and cannot
be concentrated to high solid contents to enable its burning in conventional recovery
systems. Although technologies are available and being practiced in many mills in other
parts of world; however, due to poor infrastructure still recovery of chemicals is not
being practiced by majority of mills in India, posing serious environmental pollution
problems. Pollution load in agro-based small mills having no chemical recovery is
almost three times to that of pollution load in large integrated mills.
Some of the currently accepted technologies for recovery of chemicals for agro-based
black liquor are: Rotary roaster, roaster cum smelter, Broby smelter, dry pyrolysis
process, wet air oxidation process, and Copeland reactor. Some of the emerging
technologies are wet cracking process, Chemsec process, thermochemical conversion
reactor system, super critical wet oxidation process, direct cauterization process, ABC
process, direct alkali recovery system (DARS) or ferrite process. In the fluidized bed
soda recovery system where the weak black liquor containing high silica content is
concentrated to about 45% concentration in multiple effect evaporator, venturi scrubber
and cyclone system and is sprayed in the fluidized bed combustion system.

Table 16.11: Processes for recovery of chemicals from agricultural residues black liquor
Process Description
Ferrite process (DARS process) 30% conc. black liquor burnt with ferric oxide at temp.
850ºC.
Na2CO3 + Fe2O3 2NaFeO3 + CO2

2NaFeO3 + H2O 2NaOH + Fe2O3

Wet air oxidation process Oxidation of organic matter at high temp. 320–320ºC
pressure 175–250 kg/cm2
Ultrafiltration and reverse osmosis Sodium compound is removed as permeate. High molecules
weight lignin fraction is rejected in interface.
Copeland process 34–35% solid liquor is burnt in fluidized bed reactor,
650–700ºC.
Contd...
Pulp and Paper Industry 251

Table 16.11: Processes for recovery of chemicals from agricultural residues black liquor (Contd...)
Process Description
BKMI process Evaporation 35–37% in evaporator. Last two effect
falling film. Up to 50% in direct contact evaporator, then
concentrated black liquor is burnt.
Smelter cyclone evaporator 18–20% evaporation in multiple effect evaporator up to
50% in cyclone evaporators. Concentrated black liquor is
fired in furnace.
Destomax recovery system Similar to smelter cyclone process
Burning of black liquor after desali­ Removal of silica by carbonation followed by concentration
nation and burning

16.12 STOCK PREPARATION AND PAPER MAKING

Paper consists of a matted or felted sheet of fibers formed from water suspension of fiber.
The pulps obtained from pulp mill after washing, screening and bleaching are not yet
satisfactory for making and require further processing to develop good fiber bonding
and impart several characteristics like surface smoothness, sizing, color addition of
sizing chemicals, color and additives and other chemicals like foam and pitch control,
retention aids, etc.
Stock preparation: Cellulose fibers must be subjected to mechanical treatment before
they can be made into paper and board. Beating and refining is done to develop good
fiber bonding and high paper strength. Typical flow diagram of stock preparation and
paper making process is given in Figure 16.10.

Fig. 16.10: Process of stock preparation and paper making

Paper making: Conversion of pulp from stock preparation into a sheet of paper/board
using Fourdrinier machine or mold machine. Figure 16.11 gives the details of typical
paper making process in Fourdrinier machine. A typical mold machine contains mold
and felt for support of the initial paper mat.
252 Chemical Process Technology

Fig. 16.11 Paper making process

16.12.1 Beating and Refining Process in Stock Preparation

“Beating” and “Refining” are the operation of mechanically treating the pulp fibers.
Refining usually refers to fiber separation and cutting; whereas beating action may
include the above two effects and also fibrillation or bruising effect of the fiber. There
are three main types of beating/refining equipment:
i. Beaters
ii. Conical refiners
iii. Disk refiners
Beating/refining of pulp is measured by “Freeness”. A “free pulp” drains readily,
whereas “slow pulp” drains its water slowly. Freeness can also be defined as the water
holding capacity of fiber.
The various process steps involve in stock preparation section are:
• Refining/beating of pulp stock through beaters/refiners
• Blending the refined stock in case more than one pulp furnish
• Addition of chemicals to make suitable for the desired product of papers and board
• Transferring prepared stock of pulp to machine chest.
Beaters: Beating includes fiber separation, cutting and fibrillation or brushing effect.
However, the action of the beater is primarily of rubbing or crushing nature. The
operation of beater is carried out at 5–6% consistency. The circulating power requirement
is high. It can be used for mixing and blending the chemicals. Beaters are important
even for making special grade of papers.
Conical Refiners: Beaters have been replaced with refiner which has advantage of low
space requirement and less energy consumption over the conventional old beaters.
Refiners can be used on continuous basis where fibers flow parallel to the bars of the
rotor and stator. Refining refers to fiber separation and cutting, conical refiners and disk
refiner. Increase of beating and refining improves bursting strength, folding endurance,
smoothness, formation and other strength properties.
The process involves cutting of fibers; however, it can also be made to do considerable
fibrillation in case of bars on the rotor and casing are wide, i.e. wide angle refiner.
Disk refiners: Disk refiner has received considerable interest during recent year. Disk
refiner consists of rotating disks with grooves/bars on either side positioned between
two stationary discs with grooves on the inner side. The stock is admitted through two
inlets, and it passes outward through a pipe. Disk refiner has higher power economy and
requires 20–25% less power with very less space requirement than the conical refiners.
Disk are available with variety of patterns of configuration resulting in different actions
Pulp and Paper Industry 253

like fibrillation. Short fibers pulp can be used to achieve better strength properties. These
refiners can operated at 3–5% consistency and also at 30–40% consistency. Changing of
disk is easier with simple maintenance.
Blending and mixing of chemicals: Stock preparation section involves blending and mixing
of rosin, alum, loading material (talcum powder, calcium carbonate, titanium dioxide),
dyes, whitening agent, starch, gum, sodium silicate, wax emulsion mixing chest. Refined
pulp stock of required quantity is taken and chemicals are added according to grade
of paper and board.
Sizing: Paper making fibers have strong tendency to interact with water due to hydrophilic
nature of cellulosic fiber. The process which imparts resistance to water penetration is
called sizing process. Sizing makes the fiber surface water repellent by using chemical
additive. In unsized paper liquid tends to spread out on the surface of paper, and
the process is called “feathering”. Various sizing agents like rosin, paraffin waxes,
wax derivatives, wax emulsions and synthetic sizing agents like alkyl ketene dimer
(AKD) and alkenyl succinic anhydride (ASA) are being used to make paper reasonably
hydrophobic. Requirement of good internal size (Jenkins, 2007):
• The size must be readily available and chemically stable.
• It must be possible to add in a form that ensures good and even distribution across
the papermaking fibers.
• The size must be retained in the wet end.
• The molecules must orientate themselves so that the hydrophobic end is away from
the fiber.
• The size must be sufficiently hydrophobic so that sizing is achieved in cost effective
manner.
• The size must not cause unacceptable problem in paper and board manufacture.
Sizing may be internal sizing or surface sizing or external sizing. Mainly three type
of external sizing is used (i.e. acid sizing (using alum-rosin), neutral sizing/alkaline
sizing). In internal sizing the sizing chemicals are added and mixed in pulp whereas
in external sizing the sizing chemical applied on the surface of paper.
Acid sizing (alum-rosin) is most adopted sizing process in the paper industry since
long because it is cheap, reliable and reasonably effective. From the conventional acidic
system with alum-rosin sizing, the paper industry has changed to neutral sizing using
(dispersed rosin sizes) and alkaline sizing with synthetic sizing chemicals like AKD and
ASA. The driving force for this change is process advantage, product improvement and
environmental considerations. Some of the weaknesses of acid sizing are: aging effect
in paper, restriction of calcium carbonate use, corrosion in machines, reduce brightness
of paper, high sizing cost (Patra, et al. 2007; Panwar, 2007; Sood, 2007).
Some of the advantages of AKD sizing are (Panwar, et al. 2007):
• Increase equipment life due to less corrosion at higher pH
• Increase in brightness and optical properties
• Increase in permanency of paper
• Increase in machine clothing life due to less choking
• Gain in machine runnability due to better drainage
• Good smooth feeling on paper surface
• Reduction in fluff.
254 Chemical Process Technology

Alum rosin sizing: When rosin is treated with alkali (sodium carbonate/sodium hydroxide),
it is saponified and forms a water-soluble soap called “rosin size”. The principal chemical
reaction which takes place may be represented as follows:
2C19H29COOH + Na2CO3  2C19H29COONa + H2O + CO2

C19H29COONa is the sodium salt of acetic acid. The reaction is reversed when the rosin
soap is treated with acid; but it is believed that the addition of alum forms aluminum
absetate as follows: ¬
6C19H29 COONa + Al2(SO4)3 3Na2SO4 + 2Al + (C19H29COO)3

Aluminum absetate works as the cement for the pores and capillary of the fibers and
prevents water and ink to pass through it. The paper makers’ alum is aluminum sulfate
and represented as Al2(SO4)3 14H2O and approximate analysis should be as follows: ¬
Total Al2O3 = 17.2 %
Combined Al2O3 = 16.5%
Insoluble = 0.07%
Fe2O3 = 0.02%
The iron content of alum should be less than 0.3% as Fe2O3 for writing and printing
papers. More iron content in alum will mainly cause color reversion, fall in rosin contain
acetic acid (C19H29COOH),
Rosin soap Sodium salt of acetic acid
Alum forms aluminum absetate.
C19H29COOH + Na2CO3 C19H29COONa + H2O + CO2
C19H29COONa + Al2(SOO)3 Na2SO4 + Al2(C19H29COO)3
Loading: Means the incorporating of inorganic materials into fibrous web to improve the
quality. The principal fillers used are clay, talcum powder, calcium carbonate, titanium
dioxide, zinc sulfide, calcium sulfate. The above fillers are chosen due to the followings:
i. High degree of whiteness/brightness (80–98ºpv)
ii. High index of refraction (1.5–2.7)
iii. Small particle size (0.3–10 microns)
iv. Low solubility in water
v. High specific gravity than cellulose (2.60–4.50).

Fillers are also added to paper to improve their brightness or whiteness. Bleached pulp
with a brightness of about 70ºpv and chemical pulps of 80–90ºpv are most frequently
used. Fillers vary in brightness from 80–98ºpv and may increase the paper brightness.
It can be more economical to meet a brightness specification by using less severely
bleached pulps and adding fillers for the required increment in reflectance.
Coloring: Dyes and colors are added to manufacture colored paper. There are three types
of dyes normally used: acid dyes, basic dyes and direct dyes. Some of the commonly
used dyes in coloring paper are:

Other Chemicals and Additives

i. Whitening agent: This compound also called optical whitener, optical bleaching
agents. The compound when added to paper and board, it absorbs light in the
Pulp and Paper Industry 255

ultraviolet range and reemits it in the visible range, thus making the paper appear
whiter.
ii. Starch and gums: Starch and gums are used for improving physical strength
properties of paper and board due to better bonding of fibers. Refining energy is
also reduced with this use.
iii. Sodium silicate: Addition of sodium silicate improves stiffness and rattle, improve
finish, reduced fluff, increases retention of filler. It also helps in improving ash%
and bursting strength.
iv. Wax emulsion: Wax emulsion is used with rosin size for reducing rosin consumption
per ton of paper, and it is cheaper than rosin. It is used as partial substitute of rosin.

16.12.2 Paper Machine

The pulp from stock preparation section after beating/refing and centri-cleaning enters
to the manifold and then to head box which is connected to paper machine. Head
box may be of two types, i.e. open head box and pressurized head box. From
head box pulp flows to paper machine. The function of the head box is to receive cleaned
pulp stock at the consistency of 0.2–0.8% and distribute it uniformly across the width
of wire at constant head. Rollers are the one of the main parts of paper machine. There
are different types of rollers. The rollers may vary from small diameter paper lead rolls,
felt rollers, wire rollers to big diameter rollers like press rollers and drying cylinders.
There are different types and numbers of rollers in paper machine according to type,
size and speed of paper machines which is regularly increasing (Gupta , 2017). In paper
making, two types of paper machine are commonly used. This may be MF machine or
MG machine (Yankee or combined machine) and mold machine. Rectifier roll/Evener
on rolls is used to provide necessary agitation and even out distribution of fibers.
Fourdrinier Machine
Fourdrinier machines are two types. It may be MF machine or MG machine (Yankee
or combined machine). Fourdrinier machine is characterized at the wet end by a head
box which delivers stock to a moving woven-wire part belt supported by table rolls
suction boxes (Holt, 1964). Figure 16.12 gives details of combined mold and Fourdrinier
machines.
Fourdrinier wire part: The wire part consists of endless wire to support the weak web
and drain out water. When stock enters on the wire, the consistency of stock remains
0.5–0.6%, i.e. 99.5 g water and 0.5 g pulp in 100 g of pulp stock. Such a huge amount of
water is removed on the wire part, press section and dryer section. About 97% water is
removed on the wire part, 1.5% on the press section and about 1.0% by the dryer part.
Out of 97% water removal on wire part, 83–85% is drained in forming zone mainly due
to table rolls, 10–125 is removed by wet and dry suction boxes and 2–3% by suction
couch roll. Dandy roll and shake are used to improve the sheet formation. Shake helps
in improving evenness of fiber orientation which improves physical properties, drainage
of free stock (less beater stock) is retarded by shake, particularly in forming zone which
improves formation. Dandy roll is also used for water marking. It also smoothens the
top surface of paper. It helps in breaking froth bubbles. It also makes a sheet more
dense and compact.
Web leaving the press section, contains 35–40% solids. The remaining water from the
web is removed by steam dryer. In drying, the sheet is passed round the cylinders and
256 Chemical Process Technology

Fig. 16.12: Combined mold and Fourdriniers machine

held in intimate contact with the heated surface by means of dryer felts. The number of
cylinders and its arrangement in various sections is determined by the following factors:
basis weight of sheet, weight of the water to be evaporated, speed of the machine, and
pressure of steam in various sections. The dryer sections are divided in 4–5 groups,
depending on size of machine.
Table rolls: Table rolls serve two purposes: To support wire and to create vacuum at
outgoing nip, this tends to pull water from the web. Water is also removed by surface
tension. Water is removed by gravity flow and micro-vacuum.
Suction boxes: Water which cannot be removed by table rolls is removed by mild vacuum
through series of suction boxes (3–7 nos.). These boxes are connected with a vacuum
pump. The suction boxes remove a good part of the remaining water, at the same time,
compact the sheet.
Suction couch roll: About 2–3% water is removed by suction couch, where high vacuum
is applied (12–15 mm Hg). A lump breaker roll is normally used to make the sheet more
compact. When web leaves the couch roll, it carries about 18–2 dryness.
Press part: The next step is to remove moisture from the web by mechanical means, i.e.
by process of pressing the web, without affecting the quality of paper and board. Three
types of presses are normally used: Plain press, suction press and reverse press In plain
press, water is removed by mechanical pressing and suction vacuum. Other modern
presses are grooved press, unipress, trinip press, etc. The felts are used for carrier of
water between stonite and rubber rolls. As the paper web leaves the press section, it
carries about 35–40% solids.
Dryer part: When web leaves the press section, it contains 35–40% solids. The remaining
water from the web is removed by thermal method, which is very expensive.
Pulp and Paper Industry 257

In the conventional method of drying, the sheet is passed round the cylinders and
held in intimate contact with the heated surface by means of dryer felts. The number
of cylinders and its arrangement in various sections is determined by the following
factors
a. Basis weight of sheet
b. Weight of the water to be evaporated
c. Speed of the machine
d. Pressure of steam in various sections.
The dryer section is divided in 4–5 groups, depending on size of machine. This is
adopted due to the followings:
a. In order to allow a degree of shrinkage control.
b. To reduce the possibility of sheet creasing and breaking.
The Yankee cylinder: The Yankee cylinder is a large drying cylinder generally of 12–18 ft
diameter. It has a very high polished surface, against which the sheet is pressed by one
or more press rolls. The drying cylinder is generally unclothed. The Yankee cylinder
was developed to impart a high smooth finish to one side of sheet. Hence, the term
“machine glazed” or MG paper applied to paper.
Calendaring: After the sheet is dried, it is passed through a stack of heavy metal rolls,
where it is calendarized under high pressure. The purpose of calendaring is to smooth
down the felt and wire marks, to remove cockle and to level off lumpy formation and
to make sheet of uniform caliper.
Reeling: The final paper and board having moisture of 4–6% is reeled on pope realer.
The empty shell on which paper and board of reeled rests on the drum and driven
round by virtue of the surface friction between them. The full roll of paper or board is
removed by crane for rewinder/cutter.
Cylinder mold machine: Cylinder mold machine differs from Fourdrinier machine by
replacing Fourdrinier wire part by cylinder mold part. Cylinder machine makes use
of cylinder structure which supports the forming wire mesh. Stock is supplied to the
outside of the rolls. This is used for making paper board.
There are two types of mold operation: ¬
a. Uniflow cylinder vat: In uniflow cylinder vat movement of stock in direction of
mold. When the movement of stock is in the same direction as the mold rotation; a
stronger sheet results and good formation can be achieved.
b. Counter flow cylinder vat: In counter flow cylinder mold, the movement of stock is
in the opposite direction as the mould rotation. This design is mainly used in heavy
board machines.
In the mould machine, the stock is picked up on a wire covered cylinder mold and
then transferred to a felt which carries it to the next cylinder mold. This process is
repeated until a multiply board of several plys is obtained. From cylinder mold, the
board passes to the same stages as that of Fourdrinier machine, i.e. press section, dryer
section, calendar and reeler, etc.
Slitter rewinder and cutters: On slitter rewinder, the parent paper rolls are rewound and
cut as per the market size. Similarly on duplex cutters numbers of paper parent rolls
are cut at the same time as per the market size of the sheets. The reels are packed and
sheets are sorted for defective portion and then counted and packed.
258 Chemical Process Technology

16.13 ADVANCES IN PULP AND PAPER INDUSTRY

Summary of some of the developments in pulp and paper industry are given below:
Forest Management: Sustainable forest productivity with fast growing species with
high yield, clonal propagation of soft wood, good harvest management.
Main focus areas in forest management are: (1) Biotechnology application, (2) Basic
physiology of forest productivity, (3) Sustainable soil productivity, and (4) Remote
sensing technologies to improve forest inventory and management.
• Mechanical: In order to improve yield and quality of mechanical pulp, some of the
developments are thermomechanical pulping, refiner mechanical pulping
• Biotechnology application: Bio-pulping, bio-bleaching, enzymatic deinking, enzymatic
refining
• Pulping: Technological development in the area of pulping are: extended delignification
using polysulfide, anthraquinone, oxygen, super batch, rapid displacement heating,
enerbatch, modified continuous cooking, extended modified continuous cooking,
isothermal cooking, black liquor impregnation isothermal cooking, pulping, steam
explosion pulping, bio-pulping, explosion pulping, etc. (Pulliam, 1997). Some of
the options for reducing kappa number of pulp before bleaching are extended
delignification using polysulfide, oxygen, and anthraquinone. Another option for
extended delignification is by using chemical additives, oxygen delignification, bio-
pulping, and explosion pulping.
• Bleaching: Pulp are classified as chlorine gas free (CGF), chlorine chemical free
(CCF), molecular chlorine gas free (MCGF), non-chlorine compound (NCC), active
chlorine free (ACF), absolutely chlorine free (ACF), almost chlorine free (ACF),
elemental chlorine free modified (ECFM), and totally chlorine free (TCF). Sequence
of development in bleaching is given in Table 16.12.

Table 16.12: Sequence of development in bleaching (1950–1990 onward)

Year Bleaching sequences
1950–1975 CEH, CEHH
1975–1990 CE (DC), O (ED) (EOP) (EP), DEDED
1990 onward (DZ) DED
(ZD) EDED
APDED
QPDED
D (DC) CO (EO) (EOP)
P (PO) OZPAAPXX
C: chlorination, E: alkaline extraction, H: hypochlorite, D: chlorine dioxide, DC; Combination
of chlorine dioxide and chlorine, O: oxygen, EO: alkaline extraction under mild condition,
EOP: alkaline extraction under both under hydrogen peroxide a, P: peroxide, PO: peroxide
under oxygen pressure, Q: chelating, Z: ozone, PAA: peroxy acetic acid, Px: peroxymonosulfonic
acid, X: enzymes, AQ; anthraquinone pulping, PS: polysulfide
Source: Chirat and Lachenal,1997.
Pulp and Paper Industry 259

  Oxygen bleaching is getting importance because of lower pollution load and low
AOX generation (Satish Kumar et. al. 2017). Ozone bleaching has been also found
beneficial in reducing effluent load and reducing effluent volume, COD load, color
and AOX discharge.
• Washing and screening: There has been continuous up-gradation of washing and
screening. Drum displacer, pressure diffuser, displacement presses, combined
deknotting and fine screening, high temperature screening before washing, reverse
cleaners, etc. are some recent developments.
• Evaporation and recovery: Direct contact evaporation causes more H2S emission. Agro-
based paper mills require more energy to recovery of chemicals since it has high silica
contents. Black liquor losses from mills without recovery pose a serious environmental
problem and result in energy inefficiencies. Use of falling film evaporator and
replacement of direct contact recovery are some of the developments.
• Fiber modification: Enhancing the opacity of fiber through pigment particles, better
fiber loading, pressurized sensitive adhesives (PSAS)
• Paper machine: High speed machine with sophisticated instrumentation and control;
closed hood and insulation of dry cylinder end; installation of trinip press.
• Recycling of fiber: Improved recycling reduces pressure on wood and often results
in lower energy consumption, less chemical usage and lower pollutant production.
• Deinking: Enzymatic deinking using celluloses.
• Effluent treatment system: Vibrating shear enhanced processing (vseptm) using
ultrafiltration and nano-filtration avoiding fouling problem exhibited by conventional
membrane system, pressurized ozone/ultrafiltration membrane systems for removing
total solids from paper mill process.
• Biotechnology application in paper industry (Mall 2017–18)
ƒ Aerobic treatment of waste-water: Land application and irrigation, activated sludge,
trickling filter and rotating biological disk system
ƒ Aqua culture treatment of waste-water
ƒ Anaerobic digestion of sludge for energy recovery
ƒ Bio-refinery concept for biomass: sustainable bio-processing of biomass and waste
for production of alcohol and alcohol-based chemical
ƒ Corrosion control
  Now paper mills are looking for:
♦ Improved product appeal (higher brightness)
♦ Odorless mill
♦ Better fiber properties.
♦ Improved runnability.

It is believed that high capacity utilization, strong demand outlook, moving into
environmental friendly and value added products and capacity expansions are key
signs of attractiveness of paper industry ([Link] [Link]/grwth-
paper-industry-india March 9, 2018).

16.14 VARIOUS GRADES OF PAPER

Various grades of paper are being manufactured and available in the market having
varying basic weight and color, brightness and strength: abrasive kraft, absorbent kraft,
260 Chemical Process Technology

antirust paper, antique and art paper, wrap paper for beedi, bond paper, carbon paper,
carbonless paper, card board of different, cigarette tissue paper, coated paper, cream
wove paper, electrical insulating paper, general writing paper, grease proof paper,
gypsum board, fax paper, duplex and triplex board, poster paper having different
colors, cheque paper, news paper, sanitary tissue paper, soap wrapper, poster, tea bag
paper, file board paper, corrugated paper, etc.

BIBLIOGRAPHY
1. “Handbook of pulp & paper Technology” Edited by Britt KW. Reinhold Publishing Corporation,
1964.
2. Brendan van W, Metais Alexis, Madhavan N. IPPTA Vol 29 No.1, Jan–March 2017 p.206.
3. Chirat C, Lachenal D. “Pulp brightness race to keep up with technology”. In Advances in Bleaching
technology P 1 Edited by Patrick KN. Miller freeman Inc US, 1997.
4. Dixit AK, Jain RK, Mathur RM. “Incineration of black liquor mixed with waste biomass—An
option to achieve zero black liquor discharge in small agro based paper mills” IPPTA Vol 24,
No. 3, 2012, p.161.
5. Dixit AK, Thapliyal BP, Jain RK, Mathur RM. “Desilication of Bamboo and Straw Black Liquor”
IPPTA, Vol 22, No. 3, 2010, p.121.
6. Eloranta J. “Indian pulp & paper industry—challenges and opportunities”. In paper International,
January–March 2010, p.12.
7. Goyal MK. IPPTA Volume 30 No. 1 January–March 2018.
8. Gupta Shalabh. “Maintenance of Rollers for paper industry” IPPTA Vol 29 No. 4, 2017.
9. Holt SG. “The paper machine” Chapter 12 in hand book of pulp and paper technology” Edited
by Britt KW. Eeinhold Publishing Corporation, 1964.
10. [Link] [Link]/grwth-paper-industry-india March 9, 2018.
11. Ibrahim H. “Proceedings of the International non-wood pulping and paper making” Beijing,
Vol II, 1988, p.877.
12. Jameel H, Gratzl J, Prasad DY, Chivukula S. “Extended delignification with AQ/Polysulfide.”
Tappi, 78(9) 1995, p.151.
13. Jenkind S. Key note address in IPPTA workshop on “Wet end chemistry with special emphasis
on alkaline sizing” IPPTA J Vol 19, No. 4, 2007, p.57.
14. Kulkarni, A.. “Removal of non-process elements in chemical recovery-A review technologies”
IPPTA, Vol. 22, No. 3.3, 2010, p.113.
15. Mall ID. “Environmental Management Strategies in Pulp and Paper Industry”. Faculty
Development Programme on “Industrial Pollution Abatement and Waste Management held
at Department of Chemical Engg, Bundelkhand Institute of Engg and Technology, Jhansi Feb
19–23, 2018.
16. Mall RC, Narayan Moorthy R. “A overview of Indian pulp and paper Industry,” Green Solution
Week, Sweden, 2010.
17. Mall ID. NPTEL Web and Video Course Organic on Chemical Technology 2013.
18. Mall ID. “Petrochemical Process Technology” First Edition Macmillan 2006, Reprint 2016, Second
edition 2017 Laxmi Publication.
19. Mukundan PG. In paper vol. 14, Issues 2, 2011, p.3.
20. Nair MBBD, IPPTA, Vol 24, No. 3 2012, p.3.
21. Panwar MP, Upadhya AK, Sharma PN. “Case study on alkaline sizing in agro based paper
manufacturing” IPPTA J, Vol 19, No. 4, 2007, p.9.
22. Patra MK, Chandra MK, Bhuyan BK. “Alkaline sizing and our mill experience” IPPTA J, Vol.
19, No. 4, 2007, p.97.
23. Pryke DC. “Environmental solution for the pulp and paper industry” (1991) Edited by Kelly,
Ferguson, Miller Freeman Inc. US.
Pulp and Paper Industry 261

24. Pulliam, T. Advances in bleaching technology P 1 Edited by Patrick KN. Miller freeman Inc US,
1997.
25. Raghuveer S. “Collection of domestic secondary fiber an initiative as corporate social
responsibility” IPPTA, Vol. 24, No.3, 2012, p.51.
26. Ray AK. Proceeding of meeting on clearer production in pulp and paper mills organized by
United Nations Environmental Programme (UNEP), Bangkok and Central Pollution Control
Board, Delhi, India, April 25–26, 1997.
27. Sankaralingam P, Chinnaraj P, Subramaniam S. “Pulping and bleaching of MeliaDbai clone K
10: A short Rotating pulpwood clone to improve Environmental and Economical performance”
IPPTA Vol 29, No.1 January–March 2017, p.167.
28. Satish Kumar, Bhardwaj NK, Kumar P. “Pollution reduction from pulp bleaching effluents by
process change” IPPTA Volume 29 No. 2, June 2017.
29. Singhania HP. IPPTA Volume 30 No. 1 January–March, 2018.
30. Sood YV, Tyagi S, Pandey PC, Roy TK. “Paper quality improvement options and effective ways
of neutral/alkaline sizing of indigenous pulps” IPPTA J, Vol. 19, No. 4, 2007, p.69.
31. Sundra Kumar D, Marimuthu P. “Sweet sorghum stalks-An alternative agro based raw material
“for paper making”. IPPTA, Vol 24, no. 3, 2012, p.47.
32. Thapliyal BP. IPPTA Vol 30 No. 1 January–March 2018.
17
Sugar and Alcohol Industry

17.1 INTRODUCTION
Sugar industry is one of the most important agro-based industries in India and has
an important impact on rural economy. India is the second largest sugar producing
country in the world. Sugar production during 2007–08 was of ` 263 lakh. There are
624 sugar factories in the country as on 31-03-2009. Sector wise breakup is as given in
Tables 17.1 and 17.2.

Table 17.1: Profile of sugar mills in India

Particulars 2010–11 2011–12 2012–13 2013–14 2014–15 2015–16 2016–17
No. of factories in 507 529 526 509 538 526 493
operation
Cane acreage (000 4885 5100 5279 5341 5307 5284 4945
hectares)
Sugarcane production 3424 3538 3544 3456 3668 3369 3036
(lakh tons)
Molasses production 10970 11824 11744 10882 12482 10837 9026
(000 tons)
Source: Sugar Manufacture Association 2016–17 [Link]

Table 17.2: Profile of sugar industry

Sector No. of sugar factories
Private 245
Public 62
Cooperatives 317
Total 624
As per 2010–11
Area 4.98 million hectares
Cane production 346.00 million tons
Sugar production 24.20–24.50 million tons
Source: Business Standard, April 24, 2012.

262
Sugar and Alcohol Industry 263

Uttar Pradesh and Maharashtra are the two largest sugarcane producing states in
the country, accounting for more than 80% of the annual crop production. India is one
of the largest producers of alcohol in the world and there has been a steady increase in
its production over the last 15 years, according to fresh statistics.
India is a dominant producer of alcohol in the South-East Asian region with 65% of
the total shares and contributes to around 7% of the total alcohol beverage imports into
the region. More than two-thirds of the total beverage alcohol consumption within the
region is in India, according to figures in the newly compiled Alcohol Atlas of India.
There has been a steady increase in the production of alcohol in the country, with
the production doubling from 887.2 million liters in 1992–93 to 1,654 million liters in
1999–2000 and 2277600 KLPA in 2016–17 with total number of units 166. Sugar industry
is highly seasonal industry, with season lengths varying widely (Gupta RC. “Pulp &
paper Indistry Vision 2025 and Beyond”IPPTA Volume 26, No. 1, Jan–March, 2014).
Various advances in sugar and alcohol industry are:
• Gur to Khandsari to sugar
• Higher crushing capacity from <1250 to 1250–2500 to 2500–5000 to 10,000
• Wingler (Mangle) crusher, roll crusher to screw explorers
• Higher sugar recovery from 6–7.8 to 10.0
• More refined sugar in cube and small packet for hotels
• Higher yield of cane: Average yield 69.80 ton per hectare
• More and more Integration of sugar with paper, alcohol and chemicals
• Higher blending of alcohol in fuel. Present 5% (Target 10%)
• Direct production of alcohol from juice
• Improvement in environmental management in alcohol plant to improve color and
reduce COD.

17.2 PROCESS STEPS IN SUGAR MANUFACTURE

Sugar contains 70% water, 14% fiber, 13.3% saccharose (about 10–15% sucrose) and 2.7%
impurities. The yield of sugar depends mostly on the quality of cane and the efficiency
of the extraction of juice crushing, milling and squeezing of juice through a series of
pressure mills containing grooved walls. Weak juice and make up water is added as
extractant before squeezing to maximize juice yield. After crushing and extraction of
juice, bagasse is left as residue which is about 33.3% of the total cane crushed. Bagasse
is used as fuel for boilers. However, about 10% of bagasse is available surplus which is
used for paper making; it can be also used for manufacture of alcohol.
Purification of juice for removal of impurities by addition of calcium phosphate is
followed by addition of lime to precipitate the impurities in the form of colloid. This is
followed by bubbling of SO2 for maximum flocculation of impurities. SO2 also acts as a
bleaching agent. Further the flocculation of the impurities is achieved in the continuous
settler. Double carbonation using CO2 and double sulfitation using SO2 is used. The
clarified solution goes to evaporator and the underflow of clarifier goes to rotary filter
for removal of the impurities as cake. The filtrate containing sugar from the rotary filter
is recycled. Clarified juice is concentrated in the multiple effect evaporator to about
40%. The concentrated syrup is again bleached by passing SO2 through it. Concentrated
sugar solution is then sent to vacuum pan where thickened syrup is boiled three to
four times and then sent to crystallizer where separation of sugar crystal takes place.
264 Chemical Process Technology

It is sent to high speed basket centrifuges for separation of sugar crystal. The syrup
is re-concentrated and cooled successively to obtain one or two crops of crystal. The
final mother liquor called molasses is sent to distilleries for production of alcohol by
fermentation process. Schematics diagram of sugar production process is shown in
Figure 17.1.

Fig. 17.1: Schematics of sugar production process (Source: Kaul, et al. 1990)

Processing sugar beet: Sugar beet contains 75% water and about 17% sugar. In
processing of beet, first it is washed and sliced. The slices are then sent to rotary diffuser
where a counter current flow of water is used to remove sugar from beet slices. Various
stages in manufacture of sugar from sugar beets are:
Extraction of juice: This involves washing, shredding and extraction of juice.
Juice purification: The extracted juice is purified using lime and CO2 for removing non-
sugar substance from the juice.
Evaporation of juice: Evaporation of the purified juice from 15% sugar content to 65–70%
sugar content.
Crystallization: Crystallization of concentrated sugar solution to sugar crystal. Molasses
are left behind after crystallization which is used for production of alcohol.
Refining of the raw sugar: The raw sugar is dissolved, filtered and crystallized again to
get high grade refined sugar.

17.3 ETHANOL
India is amongst two largest sugar-producing countries in the world and converts the
molasses from sugar plant to alcohol. India is fourth largest producer of ethanol in the
world and second largest in Asia. India produced about 111 crore liters alcohol annually
which is expected to be 139.5 crore liters in 2017–18 (https;//. [Link]). The
Sugar and Alcohol Industry 265

demand for potable alcohol has been ever increasing (Chauhan, et al. 2012). Today
95% of ethanol is produced by fermentation and only 5% is produced from petroleum
feedstock by ethylene route.
Ethanol has become one of the important products as alternative feedstock for large
number of organic chemicals and fuel. Ethanol is an oxygenated fuel that contains 35%
oxygen, which reduces particulate and NOx emissions from combustion (Badger, 2002).
Alcohol is now being used for potable liquor, as chemical feedstock, as solvent, and as
oxygenates. Process manufacturing of alcohol is shown in Figure 17.2.
Various routes for manufacture of ethanol are:
• Alcohol from fermentation of molasses
• Alcohol from lignocelluloses biomass
• Alcohol from starchy feedstock

Fig. 17.2: Process of manufacturing of alcohol

17.3.1 Fermentation of Molasses

Molasses are the residues left after extraction of crystallized sugar and are one of the
major by-products of the sugar industry. Ethyl alcohol is made from molasses by
fermentation process utilizing yeast enzymes.
A typical distillery consists of:
• Molasses handling
• Fermentation feeding system
• Preparation of yeast inoculum, propagation of yeast
• Fermentation
266 Chemical Process Technology

• Distillation of dilute alcohol for removal of impurities

• Concentration of the dilute alcohol to rectified spirit and absolute alcohol
• Petrochemical route via catalytic hydration of ethylene and ethylene esterification
and hydrolysis
1. Molasses handling: It involves weighing of the molasses and pumping of molasses to
the molasses tank from which the measured quantity of molasses is transferred to
the fermenter.
  Preparation of yeast inoculum, propagation of yeast: Yeast material is prepared in
water cooled yeast vessels by inoculating molasses with yeast and then transferred
to aerated yeast activation vessel to allow time for yeast cell multiplication.
2. Fermentation: It involves fermentation of fermentable sugars by microorganism
and formation of alcohol and other by-products. Yeast (Saccharomyces cerevisiae) is
commonly used for the fermentation of glucose to ethanol. After the fermentation
alcohol of 7–8% strength is obtained. Fermentation is exothermic process and heat
is generated. Removal of heat is necessary to maintain the temperature in fermenter.
High temperature lowers the alcohol productivity. Nutrients are added to the
fermenter intermittently depending upon the requirement. Sulfuric acid is added to
adjust the pH of fermenter liquid. Excess foaming in the fermenter is controlled by
antifoam solution. During the normal operation treated yeast cells recovered from
the fermented wash are recycled from the yeast treatment system to activation vessel
and after that transfer to the fermenter.
  After fermentation is completed, the dil. liquor (8–10% alcohol) is preheated and
pumped to the beer still where the alcohol 50–60%) and other volatiles like aldehydes
are distilled off from the top and send to the aldehyde column for separation of
aldehydes and other low boiling impurities. The residue from the bottom of the
beer column is known as slopes or tillage are discharged and treated for recovery of
energy or concentrated and used. Alcohol drawn from side stream of the aldehyde
column is sent to rectifying column. The azeotrope alcohol containing alcohol about
95–96% alcohol is taken as top side stream from the rectifying column.
3. Alcohol recovery: This section involves the recovery of alcohol from the fermentation
section to minimize the possible losses of alcohol along with generated CO2 and
sludge from fermented.
Typical reactions involved are:
C12H22OH + H2O C6H12 O6 + C6H12 O6
Molasses Glucose + Fructose
C6H12 O6 C2H5OH + 2CO2

17.3.2 Alcohol from Biomass

In India, alcohol is mainly produced by the sugar and distillery industries as a by-product
of molasses fermentation. Technologies for producing ethanol from cellulosic biomass
through fermentation and chemical hydrolysis have been developed from laboratories
at commercial scale. Globally, if even 10% of biomass is used for fuel production there
may be substantial reduction in oil consumption.
Ethanol thus produced can be a promising chemical feedstock. US-based Primus
Green Energy has developed a high conversion efficiency biomass to gasoline
Sugar and Alcohol Industry 267

process based on innovative thermal–chemical conversion and the process can

generate 416 liters of gasoline per ton of biomass (Chemical Industry Digest, March
2012, p.56).
Lignocellulosic biomass is available abundantly and can be used as the alternative
feedstock for bioethanol production. Lignocellulosic biomass includes forest residues,
such as wood; agricultural residues such as sugarcane bagasse, corn cob, corn stover,
wheat and rice straw; industrial residues such as pulp and paper processing waste,
lignin from pulp and paper mills and municipal solid wastes, and energy corps, such
as switch grass. These have the potential for use as feedstock for the production of fuel
ethanol (Reshamwala, et al. 1995; Mielenz, 2001; Kim, et al. 2002; Kadam, et al. 2003;
Kumar, et al. 2010). The nature and availability of lignocellulosic feedstock in different
parts of the world depend on climate and other environmental factors, agricultural
practices, technological developments, and current usage/consumption (Claassen, et al.
1999; Van Maris, et al. 2006). Composition of various agricultural residues and wastes
is given in Table 17.3.

Table 17.3: Composition of common agricultural residues and wastes

Agricultural residue Cellulose (%) Hemicellulose (%) Lignin (%)
Hardwood stem 40–50 24–40 18–25
Softwood stem 45–50 25–35 25–35
Nut shells 25–30 25–30 30–40
Corn cobs 45 35 15
Grasses 25–40 35–50 10–30
Wheat straw 33–40 20–25 15–20
Rice straw 40 18 5.5
Leaves 15–20 80–85 0
Sorted refuse 60 20 20
Cotton seed hairs 80–90 5–20 0
Coastal Bermuda grass 25 35.7 6.4
Switch grass 30−–50 10–40 5–20
Solid cattle manure 1.6–4.7 1.4–3.3 2.7–5.7
Swine waste 6.0 28 –
Primary waste water solids 8–15 NA 24–29
Paper 85–99 0 0–15
Newspaper 40–55 25–40 18–30
Waste paper from chemical pulp 60–70 10–20 5–10
Source: Bhoopathy, 1998; Cheung and Anderson, 1997.

Process Technology
All conversion schemes involves following basic steps:
• Feedstock harvest, transport and storage
268 Chemical Process Technology

• Pretreatment of lignocellulosic biomass

• Enzyme hydrolysis of cellulose in the lignocellulosic materials to fermentable
reducing sugars
• Fermentation of sugar into ethanol
• Downstream processing of ethanol.
Pretreatment of biomass is a prerequisite to the biological conversion of lignocellosic
biomass to ethanol. Pretreatment is done either physically, chemically or biologically
to make pretreated biomass more amenable to subsequent cellulose hydrolysis.
Pretreatment alters the size and structure of the biomass as well as chemical composition
(Thakur, et al. 2011). Figure 17.3 shows process diagram of biochemical conversion
route of biomass to biofuels.

Fig. 17.3: Biochemical conversion route of biomass to biofuels

Ethanol from cellulosic material is produced either by acid hydrolysis using sulfuric
acid or enzymatic hydrolysis. Both dilute and concentrated sulfuric acids are used in
acid hydrolysis. Dilute sulfuric acid involves milder condition than concentrated sulfuric
acid hydrolysis. In acidic hydrolysis first converts cellulosic materials to sugar followed
by conversion of sugar to other chemicals.
Enzymatic hydrolysis of cellulose is an another route for alcohol. Enzymatic
processes required pretreatment of lignocellulosic to break the crystalline structure
of lignocellulosic and remove the lignin to expose the cellulose and hemicelluloses.
Depending on the biomass material physical or chemical pretreatment methods may
be used. Physical method may use high temperature and pressure, milling, radiation or
freezing. The chemical method uses a solvent to break apart and dissolve the crystalline
structure (Badger, 2002).
Technological Barriers: Some of the technological barrier which needs to be addressed
in efficient conversion of biomass to ethanol are (Thakur, et al. 2011): Pretreatment,
saccharification of cellulose and hemicelluloses matrix, simultaneous fermentation of
hexose and pentose sugars.

Pretreatment
The most commonly method used are steam explosion and dilute acid pre hydrolysis,
which are followed by enzymatic hydrolysis. Acid hydrolysis is only applied in the
two-stage acid processes; following acid pretreatment, both dilute and concentrated
versions occur. The enzymatic hydrolysis are accomplished by cellulose enzyme.
Advantage of lignocelluloses for ethanol production
• To a larger extent, locally/domestically and provide security of supply
• Generate low net greenhouse gas emission, reducing environmental impacts,
particularly climate change
• Also provide employment in rural areas
• Greater avoidance of conflict with land used for food and the feed production
Sugar and Alcohol Industry 269

• A much greater displacement of fossil energy per liter of fuel, due to nearly completely
biomass powered system
• Much lower net well to wheel greenhouse gas emissions than with grain to ethanol
processes powered primarily by fossil energy.
The process steps involved are:
• Gasification of biomass to hydrogen rich synthesis gas. The gasifier uses super­heated
steam at elevated pressure.
• Carbon dioxide separation and scrubbing of the syn gas
• Liquid fuel synthesis using four-stage catalytic system

17.3.3 Ethanol as Biofuel and Chemical Feedstock

Alcohol is a key feedstock for the manufacture of basic chemicals. Alcohol based
chemical industry occupies an important place in the Indian chemical industry and is a
key contributor to the growth of the sector. The current size of alcohol-based chemical
industry is $1.1 billion (` 4850 crore) (Indian chemical industry—Five Year plan 2012–17,
Indian Chemical Industry—XII Five Year plan, Government of India). According to
the OECD-FAO Agricultural outlook the demand for biofuel is shifting toward
developing countries which are increasingly putting in place that favor a domestic
biofuels market([Link]
equation-61170)

Indian Alcohol Industry

There are 340 distilleries in the country with a capacity of 3,500 million liters. However,
the capacity utilization is low mainly due to non-availability of sufficient molasses.
The past production of alcohol from the 10 major producing states viz. Andra Pradesh,
Gujarat, Karnataka, Maharashtra, Tamil Nadu, Uttar Pradesh, Uttaranchal, Bihar,
Haryana, and Punjab from year 2004–05 to 2009–10 is shown in Figure 17.4. Production
has been steadily decreasing from 2,500 million liters in FY07 to 1830 million liters in
FY10 registering a negative growth of 10% per year. Demand of alcohol in India is
shown in Figure 17.5.

Fig. 17.4: Alcohol production in India (million liters)

270 Chemical Process Technology

In India alcohol is mainly produced by the sugar and distillery industries as a

byproduct of molasses fermentation technologies for producing ethanol from cellulosic
biomass through fermentation and chemical hydrolysis have been developed from lab
to commercial scale. Ethanol thus produced can be a promising chemical feedstock as
well as biofuel. We will have to increase availability of molasses for this purpose.

Fig. 17.5: Alcohol demand in India (Source: Working group report on alcohol)

Ethanol as Biofuel
India is now going an unprecedented energy crisis due to dwindling energy resources.
The present import of crudes which is around 180 million tons per annum, is expected
to exceed 240 million tons per annum in the next 5 years, if the GDP growth of around
6–7% were to be sustained (Venkataraman, 2012). India is also importing 80 million
tons per annum of coal. Global crude oil prices are also surging unbated as global
crude oil is finite and depleting, there is continuously searching all over the world to
go for alternative energy sources. World demand for energy is expected to double by
2050 and this demand cannot be satisfied with conventional fuel resources like, crude
oil, natural gas and coal (Tuli and Gupta, 2010). In order to meet the rising demand of
energy and increasing population, alternate energy resources will play a important role
and biofuels based on ethanol are expected to grow rapidly. Biofuels developments
are primarily driven by three fundamental policy considerations: rural development,
energy independence, reduced carbon footprint.
Alcohol has been globally accepted as an alternative to gasoline and alcohol blend
gasoline are being used in many countries in varying proportion ranging from 5–20%
as ethanol. Brazil which is one of the major sugar producing industry introduced
commercial gasoline with ethanol content of about 25%. Even ethanol is being sold in
Brazil pure ethanol as E-100 fuel. Ethanol accounts for about 40% of the fuel consumed
by passenger vehicles (Sehagal, 2006). Brazil and US together account for about 70% of
world’s ethanol production. Blending characteristics of fuel oxygenates are presented
in Table 17.4 (Brockwell, et al. 1991). US the largest user of gasoline introduced gasoline
with 10% ethanol content. In some of the sugar producing country like Brazil high of
higher percentage alcohol being used as biofuel Similar trend has been observed in
several countries (Tuli and Gupta, 2010).
India is currently has a mandate for 5% blending of ethanol in petrol and is
being implemented Through the nationwide Ethanol Blending Program (EBP). About
3.5 billion liters of ethanol are being produced in about 320 distilleries in India which
Sugar and Alcohol Industry 271

is enough to cater to the 800 million liters requirement for 5% blending. However, the
national average blending in 2008–09 was only about 2% (Sarangi, 2011).
Gashol is new ecofriendly fuel containing blend of gasoline with 5–10% ethanol
from molasses. Gashol can be also made by blending gasoline and methanol. Gashol
has higher octaneor antiknock properties than gasoline and burns more slowly, cooly
and completely resulting in reduced emission (Lawson, 2004). The octane number of
gasoline increases with blending of 5% ethanol by 1.3–3.4 times. Blending of ethanol
increases the reid vapor pressure and vapor lock index. Ethanol increases the oxygen
content of the blend and is shown in Table 17.4 (Raje, et al. 2002).

Table 17.4: Blending characteristics of fuel oxygenates

Boiling Blending Average Oxygen Blending limits
point (ºC) R V P ( k g / octane content
O2 (vol.%) O2 (wt.%)
cm2) (R+M)/2 (wt.%)
Ethers
MTBE 131 8 110 18 15 2.7
ETBE 161 4 111 16 16 2.0
TAME 187 1 106 16 17 2.0
Alcohols
Methanol 148 60 120 50 – –
Ethanol 173 18 1158 35 10 3.7
MeOH 145/180 31 108 35 9.5 3.7
Blend GTBA 181 12 100 21 16 3.7
Source: Brockwell HL, Sarathy PR, Trotta R. ‘Synthesize ethers’, Hydrocarbon Processing.
1991;70(7):133.

Ethanol as Chemical Feedstock

Chemical industry utilizes a wide variety of raw materials like petroleum product
derived from crude oil and natural gas, ethanol, coke oven by products like coal tar
and other inorganic constituent. However, ethanol and coal play important role during
developing stage of petrochemical industry by providing feedstock for manufacture of
large number of organic chemical which is now being produced by petroleum route.
India is amongst the top sugar-producing industry in the world and produces ethanol
from the by-product molasses. Between 1960s and 1980s, numerous alcohol-based
plants came in different part of country manufacturing organic chemicals like ethanol,
ethylene, ethylene oxide and MEG, acetaldehyde acetic acid, acetic anhydride, butanol,
ethoxylate, pyridine, picolin butadiene, synthetic rubber, polymers like polyethylene,
PVC, etc. Indian glycol, VAM organics (now Jubilant Organosys), Synthetic chemicals
and rubber barely, Somaiya chemicals, SD chemicals, Kanoria chemicals, and larger
number of plants based on ethanol were started in India. Selected downstream products
of molasses and alcohol is given in Table 17.5. India first stated ethylene through ethanol
route by ICI in Rishra, West Bengal. Product profile of ethanol is given in Figure 17.6
(Mall 1995, 2006, 2015, 2017). Bioetahnol-based plants has been also started in other
part of the world. In Brazil, ethanol is being used in the production of petrochemicals
and polymers.
272 Chemical Process Technology

Table 17.5: Selected downstream products of alco-chemicals

Sr. Major application of downstream
Alco-chemical Downstream product
No. product
A. Plastics, Resins, Elastomers
1 Styrene ABS resins ABS products
2 Styrene SAN resins SAN products
3 Styrene Ion-exchange resins Water treatment, effluent treatment
4 Ethylene LDPE LDPE products
5 MEG Polyester films Packaging
6 Vinyl acetate EVA/VAE polymer –
7 Styrene SBR Tyres, footwear, belts and rubber
goods
8 Acetic anhydride/acid Cellulose acetate Bangles, films, spectacle frames
9 Styrene Poly-styrene PS products
10 Styrene PS foam Packaging
11 Vinyl acetate Emulsions Adhesives
B. Chemicals
12 Styrene Styrenated phenol Rubber chemical
13 Acetic acid PTA Polyester feedstock
14 Acetic acid Di-methyl-acetamide Solvent for acrylic fiber industry
15 Acetic acid Acetoacetates Pharmaceutical and pesticide inter­
mediate
16 Acetic acid Acetoacetanilide Dyestuff intermediate
17 Acetic acid Acetoacetanides –
18 Acetic anhydride Paracetamol Pharmaceuticals
19 Acetic anhydride Aspirin – do –
20 Acetaldehyde Vinyl sulfone Dyestuff intermediate
21 Acetic anhydride Acetanilide Dyestuff intermediate
22 Pentaerithritol Emulsions/dispersions Paint industry
23 Pentaerithritol PETN Explosives industry
24 Glyoxal Pharma Drugs and pharmaceutical
25 Glyoxal – Textiles
26 Ethyl acrylate Emulsions/dispersions Paint industry
27 Ethyl vanillin Flavoring-formulations Food processing industry
28 DDT Formulations Pesticide
29 2,4-D Formulations Pesticide
30 Ethylene oxide Condensates Various industries
Contd...
Sugar and Alcohol Industry 273

Table 17.5: Selected downstream products of alco-chemicals (Contd...)

Sr. Major application of downstream
Alco-chemical Downstream product
No. product
C. Synthetic Fibers
31 MEG Polyester fibers Textiles, tyre cord/yarn, industrial
yarn
32 Chloroacetic acid CMC –
33 Acetic acid/anhydride Vinyl acetate Adhesives/polymers
34 Acetanilide Sulfa drugs Drugs and pharmaceuticals
35 Acetanilide Intermediate Dyestuffs
Sources: Alcohol based industry marching into the 21st century, Ashok Kadakia, Chemical Business,
January 2000, p.39; Chemical Industry News, March 2003, p.69.

Fig. 17.6: Product profile of ethanol (Source: Mall 1995, 2006, 2014, 2017.)

17.4 INTEGRATION OF SUGAR, PAPER, DISTILLERY AND CHEMICAL PLANT

Integration of paper-sugar-distillery-chemical industries with introduction of minor
process modification/intensification could revitalize these interdependent industries.
Integration of sugar, distillery and paper manufacturing, chemical manufacture and
waste utilization is given in Figure 17.7 (Mall, 2012).
274 Chemical Process Technology

Fig. 17.7: Integration of sugar, distillery and paper manufacturing and

waste utilization (Source: Mall 2012)

BIBLIOGRAPHY
1. Badger PC. “Ethanol from cellulose: A general review”. 2002. p.17–21. In: Janick J, Whipkey A
(eds): Trends in new crops and new uses. ASHS Press, Alexandria, VA.
2. Bhoopathy R. “Biological treatment of swine waste using anaerobic baffled reactors”. Bioreactor
Technol. 1998,64:1–6.
3. Chauhan MS, Dikshit AK. “Indian distillery Industry: problem and prospects of decolourisation
of spent wash”. 2012 International conference on future environment and energy IPCBEE vol
28920120,p.119.
4. Chemical Industry Digest. March 2012, p.56.
5. Cheung SW, Anderson BC. “Laboratory investigation of ethanol production from municipal
primary wastewater”. Bioresour Technol. 1997;59:81−96.
6. Claassen PAM, van Lier JB, Lopez-contreras AM, van Niel EWJ, Sijtsma L, Stams AJM, de Vries
SS, Weusthuis RA. “Utilization of biomass for the supply of energy carriers”, Appl. Microbiol.
Biotechnol. 1999;52:741–55.
7. Data NC. “Chemicals from renewable resources”. Chemical Industry Digest. August 2011, p.75
8. Kadam KL, McMillan JD. “Availability of corn stover as a sustainable feedstock for bioethanol
production”. Bioresour Technol. 2003;88:17–25.
9. Kaul SN, Pathe PP, Nandy T. “An Overview of Waste Management in Sugar Industry”. Journal
IAEM. 1990;17: 55–78.
10. Kaur PP, Arneja JS, Singh J. “Enzyme hydrolysis of raw rice straw by crude cellulose from
Trichodermareesei”. Bioresour Technol.1988;66: 267–9.
11. Kim KH, Tucker MP, Nguyen QA. “Effects of pressing lignocellulosic biomass on sugar yield
in two-stage dilute acid hydrolysis process”. Biotechnol Prog. 2002;18:489–94.
Sugar and Alcohol Industry 275

12. Kumar Sachin, Singh Surendra P, Mishra IM, Adhikari DK. “Bioethanol Production from
Lignoellulosic biomasss”. IPPTAJ. 2010;22(3):143–50.
13. Mall ID. “Waste utilization and Management in sugar and distillery plants”. Chemical Engineering
World. 1995;30(1):51.
14. Mall ID. ”Waste Management in Sugar and Distillery plant for resource generation” SGAT
Bulletin. 2012;13(2).
15. McKendry P. “Energy production from biomass (part1): overview of biomass.” Bioresource
Technol. 2000;83:37–46.
16. Mielenz JR. “Ethanol production from biomass: technology and commercialization status”. Curr
Opin Microbiol. 2001;4(3):324–9.
17. Pollution Prevention hand book, World Bank group July 1998.
18. Reshamwala S, Shawky BT, Dale BE. “Ethanol production from enzymatic hydrolysis of AFEX-
treated coastal Bermuda grass and switch grass”. Appl Biochem Biotechnol. 1995;51/52:43−55.
19. Singh MP, Tuli DK, Malhotra RK, Kumar Anad. “Ethanol from Lignocellulosic biomass: prospects
and challenges”. Journal of the Petrotech Society. June 2008, p.39.
20. Sugar Manufacture Association 2016–17 [Link] Thakur
VV, Pandey D, Jain RK, Mathur RM. “Bioethanol from lignocellulosic materials”. In paper India
Vol 14, issue 2 March- April 2011, p.4.
21. Van Maris AJA, Abbott DA, Bellissimi E, van den Brink J, Kuyper M, Luttik MAH, Wisselink
HW, Scheffers WA, van Dijken JP, Pronk JT. “Alcoholic fermentation of carbon source in biomass
hydrolysates by saccharomyces cereviae: current status”. Antonie van leeuwenhoek. 2006;90:
391–418.
22. Varucha Misra, Shrivastava AK, Solomon S, Ansari MI, Shukla [Link]-Eurasian J. Agric.
& Environ. Sci. 2016;16(1):28–32. ISSN 1818-6769.
18
Soap and Detergent

18.1 INTRODUCTION
Soap is one of the oldest chemicals produced over two thousand years ago by
saponification of animal fats with the ashes from plants. Although soap is mainly used
as surfactant for washing, bathing cleaning, but it is also being used in textile spinning
and as important constituent of lubricating grease. Now soap and detergent have
become integral part of our society. There has been continuous development in soap
making technology starting with batch kettle making process in cottage industry and
to present continuous modern soap making process using either fat saponification or
by fatty acid neutralization utilizing a wide variety of natural and synthetic feed stock
(Zhu et al., 2004). Soaps are also key components of most lubricating grease which are
usually emulsion of calcium, sodium, lithium soaps and mineral oil.
Synthetic detergent is an effective substitute of washing soap and has become now
very popular replacing the soap. All soaps and detergents contain a surfactant as their
active ingredient. However, detergent has better cleaning properties than soap because
good detergency and has increasingly popular. Environmental issues during initial
stages because of non-biodegradable nature of the detergent caused major concern. With
the production of linear alkyl benzene there has been continuous increase in detergent
production because of the biodegradable nature of the detergent.
During 1940s and 1950s, the detergent market was primarily captured by the dodecyl
benzene (DDB), a product formed by alkylation of benzene with propylene tetramer in a
hard detergent alkylation unit. However, the branched structure of the alkyl group was
responsible for the poor biodegradability of the detergent, and the linear alkyl benzene
(LAB) was introduced in the early 1960s and substantially replaced its counterparts.
India is one of the largest producers of soap in the world. However, per capita
consumption of toilet bathing soap in India is 0.8 kg against 6.5 kg in USA, 4.0 kg in
China, 1.1 kg in Brazil and 2.5 kg in Indonesia. Soaps are the largest portion of the fast
moving consumer goods (FMG) markets with bathing soap and toilet soaps contributing
about 30% of the soap market. In India, soaps are available in five million retail stores out
of which 3.75 million are in the rural area. The major player in the personal wash soap
market are HUL, Nirma and P&G. In soap industry, the popular sector has witnessed
growth with toilet soaps ([Link]
industry-in-india).
Soap and detergent differ in their action with hard water. Soap forms insoluble
compounds with hard water containing calcium and magnesium ions which precipitates
276
Soap and Detergent 277

and reduces forming and cleaning while detergent may react with the ions responsible
for hardiness but the resulting product is either soluble or colloidally dispersed in water
(Austin 1984).

18.2 SOAP
Soap is the alkali salt of fatty acid. Some of the important fatty acids used in soap
manufacture are lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid, linoleic
acid, linolenic acid, reicinolenic acid. Fatty acids have varying chain length and may be
saturated or unsaturated. Fatty acid content of the oils varies. Unsaturated fatty acids
give softer soap with lower melting point and are less stable while soap from saturated
fatty acids are firm, slowly soluble, milder and have good detergency (Dixit, 2011). Total
fatty acid is considered beneficial ingredient of toilet soap. Property of soap depends
on the chain length of fatty acids in blend, amount of saturation and unsaturation,
formulation and soap structure. A judicious blend of oils and fats are necessary to
obtain soaps of ideal properties.

18.2.1 Categorization of Soap

Soap has been graded in terms of total fatty matter. Soap may be categorized as toilet
soaps or bathing soap or specialty soap like baby (comparatively of high purity),
transparent (soap with high glycerine content), herbal and antibacterial soap. Bureau of
Indian Standards (BIS) has categorized on the basis of total fatty matter (TFM): Grade I
(minimum 76%), Grade II (minimum 70%), Grade III (minimum 60%), and bathing bar
(minimum TFM 40%). Soft soaps are made by using potassium hydroxide instead of
sodium hydroxide. Bathing bars may be made from partial soap and partial detergent
or wholly synthetic detergent.

18.2.2 Raw Material

Soaps are commonly made from fats and oil and sodium hydroxide. Oils and fats can
be classified either lauric or nonlauric oils/fats. In soap making palm oil, coconut oil,
caster oil, neem oil, kernel oil, ground nut oil, ricebran oil and animal fat especially
tallow are used. Fatty acid present in tallow are mysteric acid, palmitic acid, stearic
acid, oleic acid, linoleic acid whereas the coconut oil contains lauric acid, mysteric
acid, palmitic acid, stearic acid. Different oils produce soaps of varying hardness, odor
and lathering properties. Normally 75–85% tallow and 15–25% coconut oil is used in
soap making. C12 and C14 soaps lather quickly but they produce an unstable, coarse
bubble foam while C16 and C18 lather slowly but lead to stable, fine bubble foamed.
For saponification, caustic lye (50% caustic soda) is used. Some of the other ingredients
in soap are talc as filler which also act as carrier for perfume, fragrance, sodium silicate
to give firmness to the soap, sodium carbonate, dyes to impart color

18.2.3 Soap Making Process

The soap making process consists of reaction of animal fats along with coconut oil with
sodium or potassium hydroxide. The traditional process consists of direct saponification
of oil and fats in batch process. The commercial process consists of saponification in
a kettle pan boiling batch process or a continuous process The production of soap
comprises saponification (soap making), removal of glycerol, soap purification, finishing
278 Chemical Process Technology

which consist of mixing and homogenization of the soap base with additive such as
perfumes, coloring matter, skin grooming substances and final extrusion, cutting
shaping and packaging.
Basic steps in soap manufacture are saponification, glycerine removal, soap
purification, finishing (Table 18.1). Figure 18.1 illustrates the process diagram for soap
manufacturing. Process for toilet soap bar making is shown in Figure 18.2.

Fig. 18.1: Soap manufacturing process: Direct saponification of

oils and fat and glycerine recovery

Table 18.1: Basic steps in soap manufacture

Saponification A mixture of tallow (animal fat), coconut oil, sodium hydroxide and
salt is mixed in fixed proportion and fed to a reactor (kettle or pan)
with and heated with steam. Effective mixing and proper blending of
raw material is very important to ensure a consistent reaction. The soap
batch is boiled using steam sparging. The soap produced is the salt of a
long chain carboxylic acid.
Contd...
Soap and Detergent 279

Table 18.1: Basic steps in soap manufacture (Contd...)

Opening of grain of Upon completion of saponification additional salt to the wet soap
soap and gly­cerin causing it to separate out into soap and glycerin in salt water as soap is
removal not very soluble in salt water. Glycerine is very valuable by-product of
soap, so effective removal is very important process. Upon addition of
salt the single phase soap is converted to two layers. The bottom layer
is high level of salt, glycerol and only small amount of soap while the
top layer is soap which is allowed to settle for several hours. Aqueous
solution called lye is drawn from the bottom which consists of most of
the glycerin which is sent to the glycerin recovery plant where glycerol
is recovered and purified.
Soap puri­fica­tion and The soap remaining in the kettle still contains some glycerin which is
drying removed by adding small amount of caustic soda in the wash column.
The soap and lye are separated. The lye removed is reused in the
process. The top neat soap layer still contains some caustic soda which
is neutralized with a weak acid such as citric acid. The separated soap
containing water are further dried by heating under vacuum.
Finishing Finally, additives such as preservatives, color and perfume are added
and mixed in with the soap and it is shaped into bars for sale.

Fig. 18.2: Process of toilet soap bar making

280 Chemical Process Technology

Reaction in Saponification Process

18.2.4 Continuous Saponification Process

Continuous saponification process has now replaced old batch process for making soap.
Although there are variety of commercial system available; however, all the process rely
on high speed saponification using intense mixing and continuous separation of soap,
lye and glycerol, drying and finishing of the soap. In the continuous process the blended
oils and fats along with appropriate amount of caustic lye and salt is continuously
fed to the pressurized, heated autoclave (temperature 120ºC and pressure 200 kPa).
The saponification process is very fast and proceeds very quickly requiring about
30 minutes or less. After saponification in autoclave with short residence time the
reaction products are fed to cooling mixer where further saponification is completed.
The soap stream from the cooling mixer is sent to the static separator where lye phase
containing, glycerol, caustic soda and salt are separated from the soap layer. The
soap layer still contains glycerine which is washed in a washing column with lye and
salt solution to remove impurities and allow further separation of glycerol. The soap
solution is added at the bottom column while the fresh caustic lye is added at the top
for washing. Final separation of lye with soap is achieved in centrifuge.
The soap from the crutcher is fed to feed tank where it is preheated in heat exchanger
and then sprayed into the spray dryer for drying. Removal of excess moisture from
vapor and entrained soap is achieved. Soap is separated by passing the vapor in a
cyclone. The dry soap is fed to noodles which is screw extruded. The extruded soap is
cut into small noodles. The measured base soap for the vortary air value blower is fed
to noodles. The soap from noodle silo is fed to noodles through sigma mixer and roll
mill. After milling it goes to preplodder, vacuum chamber and final plodder, bar cutter
and packing, wrapping and storage.

18.2.5 Glycerine Recovery

Glycerol is important by-product of soap manufacture. The process of soap manufacture
from fats and oils usually yield glycerol to about 10% of the value of the soap formed
and because of its application in many uses, its recovery is very important for better
economy of soap manufacture. Some of the major industrial application of glycerol
include manufacture of alkyl resins and flexible polyurethane for plastic industry. It
is also an important ingredient of in cosmetics and adhesive manufacture (Israel et
al. 2008). Sweet water from wash column and lye from the static separator containing
glycerol is processed for producing glycerine.
First step in glycerine recovery is the pretreatment of lye for removal of traces of
soluble soap in the lye. Ferric chloride is added to the lye to precipitate the soluble soap
Soap and Detergent 281

as ferric soap which is separated by filtration. The acidic filtrate after removal of soap
is acidic and contains excess ferric chloride. This is treated with caustic soda and ferric
chloride is separated as ferric hydroxide precipitate which separated by filtration. The
filtrate after removal of soap is sent to evaporation section. In multiple effect evaporator
dilute glycerine is concentrated to 52% glycerine. Some salt is separated at this stage.
The concentrated liquor after separation of salt is centrifuged and the concentrated
glycerine is sent to another single effect evaporator to achieve a concentration of about
84% glycerine. This is called crude glycerine which is further refined in special distillation
column at 140ºC and 755 mm Hg. The distillation column contains three condenser in
series from which different fractions of glycerine are recovered which is further treated
with activated carbon to achieve the finished product.

18.2.6 Soap Removal

The spent lye contains a small quantity of dissolved soap which must be removed before
the evaporation process. This is done by treating the spent lye with ferrous chloride.
However, if any hydroxide ions remain the ferrous ions react with them instead, so
these are first removed with hydrochloric acid:
HCl + NaOH NaCl + H2O
The ferrous chloride is then added. This reacts with the soap to form an insoluble
ferrous soap:
FeCl2 + 2RCOONa 2NaCl + (RCOO)2Fe
This precipitate is filtered out and then any excess ferrous chloride removed with
caustic:
2NaOH + FeCl2 Fe(OH)2 (s) + 2NaCl
This is filtered out, leaving a soap-free lye solution.

18.2.7 Salt Removal

Water is removed from the lye in a vacuum evaporator, causing the salt to crystallize
out as the solution becomes supersaturated. This is removed in a centrifuge, dissolved
in hot water and stored for use as fresh lye. When the glycerine content of the solution
reaches 80–85%, it is pumped to the crude settling tank where more salt separates out.

18.2.8 Glycerine Purification

A small amount of caustic soda is added to the crude glycerine and the solution then
distilled under vacuum in a heated still. Two fractions are taken off—one of pure
glycerine and one of glycerine and water. The glycerine thus extracted is bleached with
carbon black then transferred to drums for sale, while the water/glycerine fraction is
mixed with the incoming spent lye and repeats the treatment cycle.

18.3 SYNTHETIC DETERGENT AND LINEAR ALKYL BENZENE DETERGENT

A detergent is a surfactant or a mixture of surfactants having cleaning properties in
dilute solutions. Commonly, “detergent” refers to alkylbenzene sulfonates, a family of
compounds that are similar to soap but are less affected by hard water.
• High detergency in soft and hard water (they do not react with Ca and Mg solution.)
• Requirement of small quantity
282 Chemical Process Technology

• Detergency action at low temperature

• Do not hydrolyze.
During 1940s and 1950s the detergent market was primarily captured by the dodecyl
benzene (DDB), a product formed by alkylation of benzene with propylene tetramer
in a hard detergent alkylation unit. It was found, however, that the branched structure
of the alkyl group was responsible for the poor biodegradability of the detergent, and
the linear alkyl benzene (LAB) was introduced in the early 1960s have substantially
replaced its counterparts.
Although linear alkyl benzene is the major detergent being used due its low cost as
derived from petroleum feed, other surfactants used widely are fatty alcohol sulfates
(FAS), fatty alcohol ether sulfates (FES), fatty alcohol ethoxylates (AE).

18.3.1 Fatty Alcohols

There has been rapid growth in the use of fatty alcohols due its low toxilogical profile
and safe use, continued substitution of soap by alcohol based surfactants in the
personal care industry, strong sales of laundary liquids that use higher levels of alcohol
based surfactants, displacement of LAS surfactants by alcohol based surfactants, the
substitution of alkyl phenol eythoxylates by alcohol based surfactants( Brent, 2004). The
global market for fatty alcohol has shown significant growth. Oleochemical route to
alcohols starting from vegetable/animal oils and fats has dominant share (70%) of global
capacity of about 3.3 million tons synthetic alcohol produced from petrochemically
derived ethylene still continues to have a about 30% share (Chemical Weekly, November
29, 2011, p.197).

18.3.2 Classification of Detergent (Table 18.2)

Table 18.2: Types of specialty surfactants

Anionic Amphoteric Cationic Nonionic
Ether carboxylates Amphoteric acetates Amine oxide Alkyl polyglucosides
Acyl isethionates Betaines and siltaines
Phosphate esters
Sarcosinates
Sulfosuccinates
Taurates
Source: Chemical Weekly, November 29, p.200, 2011.
([Link]

Anionic Detergents
The detergency of the anionic detergent is vested in the anion. The anion is neutralized
with an alkaline or basic material, to produce full detergency (Kiwi Web). Typical anionic
detergents are alkylbenzene sulfonates. There are three kinds of anionic detergents: a
branched sodium dodecylbenzene sulfonate, linear sodium dodecylbenzene sulfonate,
and soap. The alkylbenzene portion of these anions is lipophilic and the sulfonate is
hydrophilic. Two varieties have been popularized, those with branched alkyl groups
and those with linear alkyl groups (Smulders et al., 2002).
Soap and Detergent 283

Cationic Detergents
The detergency is in the cation, which can be a substantially sized molecule. Strong
acids are used, such as hydrochloric acid to produce the CI anion as the neutralizing
agent although in essence, no neutralization takes place in the manufacturing process
(Kiwi Web). Cationic detergents are similar to the anionic ones, with a hydrophobic
component, but instead of the anionic sulfonate group, the cationic surfactants have
quaternary ammonium as the polar end. The ammonium center is positively charged.
(Smulders et al., 2002).

Ethoxylates
Ethoxylates are compounds that have long hydrocarbon chains, but terminate with
(OCH2CH2)nOH group. These groups are not charged, but they are highly hydrophilic
owing to the presence of many oxygen centers.

Nonionic or Zwitterionic Detergents

This detergent consists of nonionic constituents which are ionically inert. The vast
majority of all nonionic detergents are condensation products or ethylene oxide with
a hydrophobe. This group of detergents is enormous, and the permutation endless.
These are characterized by their (net) uncharged, hydrophilic head groups. They are
based on polyoxyethylene (i.e. Tween, Triton and Brij series), Chaps, glycosides (i.e.
octyl-thioglucoside, maltosides), bile acids, such as DOC, lipids (HEGAs), or phosphine
oxides. Zwitterionic detergents possess a net zero charge arising from the presence of
equal numbers of +1 and –1 charged chemical groups.

18.3.3 Basic Components of Detergent

• Detergent (Linear alkyl benzene sulfonate)
• Builders: Phosphate (Sodium tripolyphosphate boost detergent powder), citrates,
silicates, carbonates, zeolite
• Filters and processing aids: Sodium carbonate, sodium sulfonate
• Corrosion inhibitors: Sodium silicate
• Anti redeposition agent: Carboxy methyl cellulose
• Fabric brightners: Fluoroscent dyes
• Bluing: Improve whiteners by counteracting natural yellowing tendency
• Antimicrobial agents: Carbinilides, salicylanilides
• Enzymes: Decompose or alter the composition of soil and render the particles more
easily removable.
Some of the enzymes used in detergent are protease, amylase, lipase and cellulase.
The enzymes catalyze the breakdown of chemicals through addition of water and
helps in the removal of soils (Saini, 2001a). Polymers and enzymes play important role
in improving the detergency. Polymers help in soil removal, prevent insoluble salt
incrustation work as antisoil re-deposition, inhibit dye transfer. Use of optical brightener
enhances the brightness and whiteness. Processing aids when added to slurries of
detergent powder improve stability and homogeneity of slurries during mixing and
reduce viscosity (Saini, 2001b).
284 Chemical Process Technology

18.4 LINEAR ALKYL BENZENE

LAB basic raw material for detergent which was introduced in 1960s as substitute
for non-biodegradable branched. Other surfactants are alcohol sulfate (AS), alcohol
ethoxylates (AE), secondary alkane sulfonate, and alpha olefin sulfonates. LAB is a
clear colorless liquid with characteristic odor. It is most widely used as the basic raw
material for the manufacture of synthetic detergent. The linear alkyl benzene produced
from the C10 – C13 or C11 – C14 linear mono-olefins are useful detergent intermediate and
can be readily sulfonated to yield linear alkyl benzene sulfonates. These compounds
constitute the “active” ingredients of many house hold detergents. They are surface
active compounds (surfactants) which are combined with various builders (often
inorganic salts) to make up a detergent formula.
Linear alkyl benzene (LAB) is the basic raw material for production of most widely
used detergent. Linear alkyl benzene was introduced as substitute for nonbiodegrad­
able branched alkyl benzene. Process involved for LAB manufacturing is mentioned
in Table 18.3 and Figures 18.3 and 18.4.

Table 18.3: Process steps in LAB manufacture

Prefractionation To obtain C10–C14 range hydrocarbons from kerosene. (n-C10 to n-C13
for light and n-C11to n-C14 for heavy LAB)
The linear alkyl benzenes (LAB) unit requires a very specific feed in
terms of carbon number. The prefractionation unit is designed to process
a high purity C9 to C15 linear (normal) paraffin feed and to separate out
a heart cut with the desired carbon number which will range from n-C10
to n-C13 for light LAB and nC11–nC14 for heavy LAB.
Hydrotreator To remove sulfur compounds from feedstock
The purpose of this unit is to remove sulfur and nitrogen from the feed
without greatly changing its BP. If not removed, sulfur and nitrogen
would poison the sieve in the Molex Unit.
Paraffin separation To remove n-paraffins from kerosene by selective adsorption using
(Parex process) molecular sieve. The UOP MOLEX process is an effective method of
continuously separating normal paraffins from a stream of co-boiling
hydrocarbons by means of physically selective adsorption.
The feedstock is separated into a high purity normal paraffin fraction
at high recoveries and a non-normal paraffin.
Dehydrogenation Dehydrogenation of n-paraffins to olefins
of paraffins (Pacol This process dehydrogenates the high purity linear paraffin feedstock
process) from the prefractionation unit into the corresponding non-olefins, suitable
as feedstock for the downstream detergent alkylate unit.
Alkylation Alkylation of benzene with olefins to obtain LAB in presence of HF
or solid zeolite catalyst
This process alkylates benzene with linear olefins produced by the Pacol
unit in the presence of HF acid catalyst to yield LAB. The LAB thus
produced can be readily sulfonated to form a suitable ingredient for
many household detergents. This unit consists of three processing section:
i. Alkylation section
ii. Fractionation section
iii. Acid regeneration section
Soap and Detergent 285

Fig. 18.3: Prefractionation, pretreatment, and paraffin separation

Alkylation unit

LAB sulfonation
Fig. 18.4: Manufacture of linear alkyl benzene sulfonate
Although LAB demand grew by 14% per annum during 1984–90, future demand in
the country is projected to increase at a healthy growth rate of 7–8% as against 2–4%
worldwide (Table 18.4). India and China with huge population are the largest market
for LAB.
Table 18.4: LAB application in India
Application Share (%)
Consumer cleaning products 96.2
a. Synthetic detergents for fabric wash 90.1
• Popular 68.3
• Mid-price 13.3
• Premium 18.4
b. Scouring products 8.7
c. Liquid detergents 1.2
Contd...
286 Chemical Process Technology

Table 18.4: LAB application in India (Contd...)

Application Share (%)
Industrial and institutional cleaners 1.3
Other industrial application 2.5
Non-surfactant applications (varnish, cable fluid oil, lubricant) 0.1
Total 100
Source: Indian Oil Corporation (Chemical Weekly November 29, p.199, 2011).

Dehydrogenation of paraffin to olefin

Dehydrogenation of mono-olefin to diolefin

LAB manufacturing in India started in 1985 by IPCL in 1985 followed by Reliance

Industries, Tamil Nadu Petro Products, Nirma, and Indian Oil Corporation. Application
of LAB in India is mentioned in Table 18.4.
• IPCL, Vadodara : 50,000 TPA
• Reliance Industries, Patal Ganga : 1,00,000 TPA
• Tamil Nadu Petro Products : 1,20,000 TPA
• Nirma Limited : 75,000 TPA
• Indian Oil Corporation, Vadodara : 1,20,000 TPA
Total : 4,65,000

18.4.1 LAB by Solid Acid Catalyst

The conventional catalysts AlCl 3, H 2SO 4 and HF commercially used have the
disadvantage of causing corrosion of equipment as well as waste production. There
has been continuous search for development of noncorrosive solid catalyst with
similar catalytic properties. Some of the catalysts which have been developed are
SiO2–Al2O3, H–, ontmorillonite, amberlyst, H–Y, H-beta, HM (Almeida, 1994). World
LAB capacity was around 3 million tons with nearly 85% based on HF alkylation,
5% on the aluminum chloride process, and 10% on the newly developed fixed bed
alkylation. The fixed bed alkylation was first introduced on commercial scale in 1995 in
Canada by Petresa. Figure 18.5 gives details for LAB manufacture from fixed-bed technology.
Soap and Detergent 287

Fig. 18.5: LAB manufacture from fixed-bed technology

18.4.2 Manufacturing of Detergents

Detergents use a synthetic surfactant in place of the metal fatty acid salts used in soaps.
They are made both in powder and liquid form. Most detergents have soap in their
mixture of ingredients, but it usually functions more as a foam depressant than as a
surfactant.
A synthetic detergent, a sodium alkyl sulfate called sodium dodecyl sulfate, is
prepared by reacting dodecyl alcohol (dodecanol) with sulfuric acid:

The resulting dodecyl sulfate is converted to the sodium salt by a reaction with
sodium hydroxide:

18.4.3 Process of Making Powder and Liquid Detergent

Process steps involved in making powder and liquid detergent is given in Table 18.5.

Table 18.5: Various processes for making detergent

Powder detergent
Slurry making The solid and liquid raw ingredients are dropped into a large tank
known as a slurry mixer. As the ingredients are added the mixture heats
up as a result of two exothermic reactions: the hydration of sodium
tripolyphosphate and the reaction between caustic soda and linear
alkylbenzene sulfonic acid. The mixture is then further heated to 85ºC
and stirred until it forms a homogeneous slurry.
Spray drying The slurry is de-aerated in a vacuum chamber and then separated by an
atomizer into finely divided droplets. These are sprayed into a column
of air at 425ºC, where they dry instantaneously. The resultant powder
is known as ’base powder’, and its exact treatment from this point on
depends on the product being made.
Contd...
288 Chemical Process Technology

Table 18.5: Various processes for making detergent (Contd...)

Post dosing Other ingredients are now added, and the air blown through the
mixture in a fluidizer to mix them into a homogeneous powder. Typical
ingredients are soda ash (anhydrous Na2CO3), bleach (usually sodium
perborate NaBO3), bleach activator (e.g. tetraacetylethylenediamine),
enzymes (e.g. alkaline protease), color, and perfume
Liquid detergent
Soap premix manufacture Liquid detergent contains soap as well as synthetic surfactants. This is
usually made first as a premix, then other ingredients are blended into
it. This step simply consists of neutralizing fatty acids (rather than fats
themselves) with either caustic soda (NaOH) or potassium hydroxide.
Ingredient mixing All ingredients except enzymes are added and mixed at high temperature.
The ingredients used in the liquid detergent manufacture are typically
sodium tripolyphosphate, caustic soda, sulfonic acid, perfume and water.
The functions of these ingredients have been covered above.
Enzyme addition The mixture is cooled and milled, and the enzymes added in powder
form.

BIBLIOGRAPHY
1. Austin GT. “Soap and detergent”, Shreve’s Chemical Process Industries, 5th Edition, McGraw
Hill Publication 1975;p.529.
2. Brackmann B, Deutschland C, Claus-Dierk H. “Versatility of derived surfactants will propel
demand for fatty alcohols”. Chemical Weekly. August 24, 2004;p.155.
3. Chemical Weekly. November 29, 2011;p.197, 200.
4. Dixit S. “Toilet soaps and bathing bars”. Chemical Business. October, 2011;p.18
5. [Link]
6. [Link]
7. [Link]
8. Indian Oil Corporation. Chemical Weekly. November 29, 2011;p.199.
9. Israel AU, Obot IB, Asquo JE. “Recovery of glycerol from spent soap lye by-E-Journal of Chemistry
Vol.5, No.4, pp.940–5, October, 2008 [Link]
10. James AK. Reigel’s Handbook of Industrial Chemistry, 9th Edition, CBS Publication, 1997.
11. Mall ID. NPTEL lecture: Organic Chemical Technology, 2014.
12. New Zealand institute of [Link]/ChemProcess/detergents
13. Renaud P, Brackmann B. “Natural based fatty alcohols”. Chemical Weekly. August 24, 2004;p.155.
14. Saini SK. “Synthetic detergent powders: changing trends, part I”. Chemical Weekly. March 20,
2001a;p.149.
15. Saini SK. “Synthetic detergent powders: changing trends part II ”. Chemical Weekly. March 27,
2001b;p.141.
16. Smulders E, Rybinski W Sung E, Rähse W, Steber J, Wiebel F, Nordskog A. “Laundry Detergents”
in Ullmann’s Encyclopedia of Industrial Chemistry, 2002; Wiley-VCH, Weinheim.
17. Zhu S, Chambers JG, Naik V. Encyclopedia of Chemical Technology Kirk-othmer, 5th Edition,
Vol.22, 2004.
19
Petroleum Refining

19.1 INTRODUCTION
Petroleum and derivatives such as asphalt have been known and used for almost 6000
years and there is evidence of use of asphalt in building more than 600 years ago. Modern
petroleum refining began in 1859 with discovery of petroleum in Pennsylvania and
subsequent commercialization. The exploration of petroleum originated in the latter
part of the nineteenth century (Speight, 1999). Petroleum refining industry is going to
play important role in meeting the rising demand of fuel due to increase in population
and vehicle population. Today when globally 1.1 billion people lack electricity access
and 2.9 billion people still using firewood for cooking and heating, oil and gas industry
has an important role to play for eradicating energy poverty (Pathan, 2017). According
to IBFE the oil and gas sector is among the eight core industry and plays important role
in decision making and is expected to be one of the largest contributors to non OCED
petroleum consumption growth globally. Oil imports rose sharply to US$87.37 billion
in 2017–18. India was third largest consumer of oil in the world in 2017. India was
fourth largest LNG importer in 2017 after Japan, South Korea, and China. LNG import
increased to 26.11 bcm in 2017–18 from 24.48 bcm in 2016–17. Gas pipeline infrastructure
in country stood at 16,771 km at the bogging of September 2018. Crude oil consumption
is expected to grow at CGAR of 3.60% to 500 million tons in 2040 from 221.67 million
tons in 2017 ([Link] [Link]).

19.2 CRUDE OIL AND NATURAL GAS ORIGIN, OCCURRENCE, EXPLORATION AND
DRILLING
Oil and natural gas were formed hundred years ago from the prehistoric plant and
animals. It is believed that hydrocarbon formed by the thermal maturation of organic
matter buried deep in earth. Over the millions of years under extreme pressure and high
temperature, this organic matter converted to hydrocarbons consisting of oil and gas.
Hydrocarbons are present in the variety of forms: kerosene, asphalt, crude oil, natural
gas, condensates, and coal in solid form.
Oil and gas production includes exploration, drilling, extraction, stabilization. The
underground traps of oil and gas are called reservoir. Reservoir may be classified as
sandstone reservoir or carbonate reservoir. Some of the important reservoir parameters
are resevoir pH, temperature, porosity, permeability, initial oil saturation, oil gravity,
and in situ oil viscosity. Various types of traps are structural traps, stratigraphic traps and

289
290 Chemical Process Technology

combination traps. Most reservoirs contain water also along with oil and gas. Reserves
are classified as proven, probable and possible reserves. Earlier finding of oil and gas
was matter of luck and hit and miss process. To enhance the oil recovery (EOR) various
methods are being in use which include steam and CO2, hydrocarbon injection, polymer
flooding, nutrient microbial EOR. Tools used for oil and gas exploration are based
and dependent on gravity change, magnetic field change, time, change and electrical
resistance. However, it has become now more challenging and complex. With advent
of three-dimensional seismic technology which is based on the sound waves, identify
the subsurface formation by reflection of sound, there has been much improvement
in identification of oil and gas traps and reservoirs. Seismic technology significantly
improves the method of estimating the oil and gas deposits. Next step after exploration
is the drilling of exploratory well. Drilling may be vertical drilling or horizontal drilling.
Drilling may be performed on-shore or off-shore. Horizontal drilling and hydro-
fracturing has resulted in economical and more productive drilling of shale gas which
was not economical with conventional vertical drilling. Now various developments have
been made in horizontal drilling to improve clean and sweep efficiency and reduced heel
and tow effects by introducing nozzle-based inflow devices in sandstone and carbonate
reservoirs which improves the performance of wells (Sunbul et al., 2009). Some of the
commonly used words in oil and gas exploration, drilling, and processing are:
• Remote sensing for identifying geographic or geophysical properties
• Image processing for identifying the different attributes
• Geographic information system (GIS)
• Global positioning system (GPS) for identifying latitude and longitude of any location
• Seismic survey using sound waves
• Artificial neutral network (ANN) and artificial intelligence
• Supervisor control and data acquisition (SCDA)
• Sandstone and carbonate reservoirs. Sandstone reservoir is highly effective.
• Reserves: volume in place recovery rate
• Enhanced oil recovery (EOR): different methods using steam, CO 2 miscible
hydrocarbon, in situ combustion, polymer flooding, nutrient microbial EOR
• Various reservoir parameters: reservoir depth, temperature, permeability, initial oil
saturation, oil gravity, in situ oil viscosity
• Arctic oil
• Drlling mud and cuttings
• Weighting agent: lime and caustic soda to increase pH and control viscosity
• Conditioning constituents to achieve desired consistency, lubricity, density, pH
control, corrosion inhibition, weighting, and emulsification
• Porosity: porosity = Vpores/Vtotal
• Effective and total porosity, residual porosity. Porosity decreases with increasing
depth. Normally good and excellent porosity are in the range 20–30 and >30
• Permeability is expressed in m2. 1 darcy = 1 mm2
• Water and oil wettability index
• Formation value factor (FVF)
• Improved horizontal clean up sweep efficiency
Petroleum Refining 291

• Flares: Elevated or ground flares

• Mobility ratio
• Heel and toe effects
• Productivity index
• Production logging tools (PLT)

19.2.1 Opportunity Crude Tight Oil/Shale Gas and Shale Oil

Opportunity crudes are hard to process, poor quality, although less expensive.
Opportunity crude is Heavy sour crudes with high TAN containing higher oil sands/
bitumen. Opportunity crude is characterized by:
• Low API
• High TAN (Zuaata 2.4 BCF 2.5)
• High sulfur
• High viscosity
• High vacuum residue yield containing high TAN. CCR, sulfur, Ni, V
• High vacuum gas oil yields (high TAN. CCR, sulfur, Ni, V)
• Lower distillate.
Tight Oil/Shale Oil/Shale Gas
The oil and gas deposits are tightly held within geological formations and are not free
flowing, as the rick is very dense and not porous.
• Horizontal wells are used to greatly increase the well surface area exposed to
hydrocarbon rich deposits.
• Hydraulic fracturing is used to increase the porosity of the formation and allow the
hydrocarbons to flow.
• Production will not be via able without these techniques.
• Batch to batch variability
• Gravity ranges 20–25 API
• Low sulfur levels, but have high H2S levels.
• Low levels of nitrogen
• High paraffin content
• Heavy metals (Ni and V) are low.
• Level of alkaline metals may be high.
• Other contaminants Ba, Pb may be present.
• Filterable solid greater volume and smaller particle size
• Production chemicals or contaminants
• Tight oil can cause wax precipitation which degrade and lower desalter temperature
and plug cold train exchanger.
Rajasthan Crude
• The Mangala area, located in Block RJ-ON-90-1 (the Rajasthan Block), is a major oil
field located in Rajasthan. The Mangala area consists of over 16 separate oil and gas
fields of which the majority of the reserves are located in the three fields of Mangala,
Bhagyam and Aishwariya. The Mangala area sits in Barmer basin and is thought to
contain oil in place volumes of 3.6 billion barrels (570,000,000 m3), of which 1 billion
barrels (160,000,000 m3) are thought to be recoverable. Cairon India is the operator
292 Chemical Process Technology

of the field, a subsidiary of Cairon energy. Cairn (and previously Shell) have drilled
184 wells during the exploration stage, of which 22 were discoveries.
• Rajasthan could contribute up to 40% of India’s total oil production by 2014.
• Rajasthan crude waxy in nature (32% wax) with high pour point of around 42ºC.
• Transportation is difficult.
• R&D approach
• Pour point depressants
• Use of diluents like condensates
• 10% Rajasthan crude and 90% regular high sulfur crude various proportions has
been tried.
Although Rajasthan crude can add significantly to crude requirement, but it has
Rajasthan crude waxy in nature (32% wax) with high pour point of around 42ºC, and
its transportation is difficult because of its heaviness.
Shale gas become important source of natural gas because of its availability in
abundant at cheaper cost due to advancement in hydraulic fracturing and horizontal
drilling. Now shale gas revolutionized the petrochemical industry. Shale gas is the
natural gas produced from shale which are mature source rock and rich in organic
matter (TOC = 0.5–25%) and gas is stored onto the organic matter,trapped in fractures
or trapped in pore space (Das, 2011).

19.3 COMPOSITION OF PETROLEUM (CRUDE OIL)

Petroleum (crude oil) consists of mainly carbon (83–87%) and hydrogen (12–14%) having
complex hydrocarbon mixture like paraffins, naphthenes, aromatic hydrocarbons,
gaseous hydrocarbons (from CH4 to C4H10) (Mukhulyonov et al., 1964). Table 19.1
gives more details about composition of petroleum. Besides, crude oil also contains
small amount of non-hydrocarbons (sulfur compounds, nitrogen compounds, oxygen
compounds) and minerals. Heavier crudes contains higher sulfur. Depending on
predominance of hydrocarbons, petroleum is classified as paraffin base, intermediate
base or naphthenic base.

19.3.1 Opportunity Oil and Shale Oil, Shale Gas

Opportunity crudes are hard to process, poor quality, heavy sour crudes having high
TAN. Although opportunity oil are cheap but poses lots of problem during processing.
Production of shale oil and shale gas has increased rapidly in recent years due to
significant advancements in drilling technology and hydraulic fracturing (Wright and
Sandu, 2013).

19.4 PROCESSING OF PETROLEUM (CRUDE OIL)

Processing of petroleum from drilling: When petroleum is drilled and brought to the
surface, the pressure drops resulting in separation of gases from the crude oil. Further
processing of crude involves separation of water and oil and salt. Associated natural
gas is further processed for separation of natural gas, condensate, acid gases. Crude oil
varies in appearance from brownish green mobile liquid to black viscous and sometimes
semisolid. Figure 19.1 illustrates the process of oil and gas processing (Ravindranath
and Habibula, 1992; Mall 2013, 2016, 2017).
Petroleum Refining 293

Fig. 19.1: Oil and gas processing (Source: Ravindranath and Habibula, 1992)

Table1 19.1: Composition of petroleum

Hydrocarbons
Hydrogen family Distinguishing Major hydrocarbons Remarks
characteristics
Paraffins (Alkanes) Straight carbon Methane, ethane, General formula: CnH2n+2
chain propane, butane, Boiling point increases as the
pentane, hexane number of carbon atom increases.
With number of carbon 25–40,
paraffin becomes waxy.
Isoparaffins Branched carbon Isobutane, isopentane, The number of possible isomers
(Isoalkanes) chain neopentane, isooctane increases as in geometric progres­
sion as the number of carbon
atoms increases.
Olefins (Alkenes) One pair of Ethylene, propylene General formula: CnH2n
carbon atoms Olefins are not present in crude
oil, but are formed during process.
Undesirable in the finished pro­
duct because of their high reacti­
vity. Low molecular weight olefins
have good antiknock properties.
Contd...
294 Chemical Process Technology

Table1 19.1: Composition of petroleum (Contd...)

Hydrogen family Distinguishing Major hydrocarbons Remarks
characteristics
Naphthenes 5 or 6 carbon Cyclopentane, General formula CnH2n+2–2Rn
atoms in ring methyl cyclo­ RN is number of naphthenic rings.
pentane, dimethyl The average crude oil contains
cyclopentane, about 50% by weight.
cyclohexane, 1,2 Naphthenes are modestly good
dimethyl cyclohexane components of gasoline.
Aromatics 6 carbon atoms Benzene, toluene, Aromatics are not desirable in
in ring with xylene, ethyl benzene, kero­s ene and lubricating oil.
three around cumene, naphthaline Benzene is carcinogenic and hence
linkage undesirable part of gasoline.
Non-hydrocarbons Compounds Remarks
Sulfur compounds Hydrogen sulfide, Undesirable due to foul odor 0.5–7%
mercaptans
Nitrogen compounds Quinotine, pyradine, The presence of nitrogen com­pounds in
pyrrole, indole, carbazole gasoline and kerosene degrades the color
of product on exposure to sunlight. They
may cause gum formation normally less
than 0.2.
Oxygen compounds Naphthenic acids, Content traces to 2%. These acids cause
phenols corrosion problem at various stages of
processing and pollution problem.
Source: Mall, 2007.

19.5 CRUDE OIL PROCESSES IN INDIA

Both indigenous and imported crude oil are processed in India. Various imported
sources of crude oil are given in Table 19.2 (Mall 2016, 1917). There have been continuous
changes in the crude oil quality. Now imported crude oils are being heavier with higher
sulfur content. Changing worldwide crude oil scenario is given in Table 19.3 (Samanti
2012; Mall 2016, 1917). Indigenous crude oil is also varying in characteristics. Rajasthan
crude oil contains high sulfur and may pose serious challenge to Indian petroleum
refining industry. A typical characteristic of various indigenous crude oil is given in
Table 19.4.
Table 19.2: Imported crude sources
Middle East Kuwait, Dubai, S. Arabia (Arab Mix, Arab medium), Iraq, Abu Dhabi, UAE
(upper Zakum, Murban, UMShaif)
Iran, Kuwait : Ratawai, Egypt (Suez Mix, Zeit mix)
Mediterranean Libya : Es Sider
West Africa Nigeria : Bonny Light (Escravos, Forcados, Penington, Qua lboe)
Angola : Cabinda, Palanca, Girassol
Eq. Guinea : Ceiba, Zaffiro
Congo : Nikossa, Kitina
Far East Malaysia : Labuan, Miri Light
Australia : Barrow Island, Cooper basin, Chalis
Brunei : Seria Light
Petroleum Refining 295

Table 19.3: Worldwide crude quality

Properties 1985 1990 1995 1999 2010
Sulfur, wt.% 1.14 1.12 1.31 1.41 1.51
API gravity 32.7 32.6 32.4 32.2 31.8
Residue in crude, vol.% 19 19.4 19.8 20.2 21.3
‘S’ in residue, wt.% 3.07 3.26 3.61 3.91 4.0
Metals in residue, ppm 275 286 297 309 320
Source: Samanti, RK. “Refining challenges and Trends”. 6th Summer School on “Petroleum refining
and petrochemicals” June 6, 2012.

Table 19.4: Characteristics of various indigenous crude oil

Sources of indigenous crude Salient features
Assam Crude Nahorkatia/Moran 31ºAPI, Sulfur 0.3%, Pour point + 30ºC, High aromatics,
Total distillate yield 65%
ONGC, Lawkwa, Rudrasagar 27º API, Sulfur 0.3%, High aromatics, Distillate yield 57%
Ankleshwar Crude 48ºAPI, Sulfur 0.1%, Pour point +18ºC, Distillate yield
80–82% (Light distillates 24%, Middle distillate 47%),
Wax content 9.9%, total sulfur 0.02%
North Gujarat Crude 28ºAPI, Sulfur content 0.1%, Pour point + 27ºC, Distillate
yield low 33–35%, High organic acidity
Bombay High Crude 38ºAPI, Sulfur 0.2%, Pour point +30ºC, Distillate yield
65–70% (Light distillate 24%, Middle distillates 46%),
High aromatics
Narimanam Crude 46ºAPI, Sulfur 0.1%, Pour point 3ºC, Distillate yield 80%
KG Basin Ravva Crude 36ºAPI, Sulfur 0.1%, Pour point + 30ºC, Distillate yield
61%
Source: Mishra & Unnikrishnan, 1996, p.22.

19.6 REFINERY PROCESSES

Refining of crude oils or petroleum essentially consists of primary separation
processes and secondary conversion processes. The petroleum refining process is
the separation of the different hydrocarbons present in the crude oil into useful
fractions and the conversion of some of the hydrocarbons into products having
higher quality performance. Atmospheric and vacuum distillation of crude oils is
the main primary separation processes producing various straight run products,
e.g., gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the
light and middle distillates, i.e., gasoline, kerosene and diesel are more in demand
than their direct availability from crude oils, all over the world. The typical refinery
operation involves separation processes, conversion processes, finishing processes,
environmental protection processes are given below. Typical refinery process
diagram is shown in Figure 19.2.
296 Chemical Process Technology

Fig. 19.2: Typical refinery processes and products

19.6.1 Types of Petroleum Refining Processes

Primary processes: Separating crude into its various fractions, e.g. CDU/VDU
Secondary processes: Processing residues from primary processes and upgrading them
to distillates, e.g. FCCU, HCU.
Residue upgradation processes: Bottom of the barrel upgradation, e.g. RFCCU, DCU, DCC
Finishing/product quality improvement processes: Processes to improve product quality and
meet stringent product quality specifications, e.g. DHDS, DHDT, CRU

19.6.2 Separation Processes

• Distillation
• Absorption
• Extraction
• Crystallization
• Adsorption
Primary Distillation (Atmospheric Distillation)
• Refinery gases
• Liquefied petroleum gases
Petroleum Refining 297

• Gasoline or naphtha (light/heavy)

• Kerosene, lamp oil jet fuel
• Diesel oil and domestic heating oils
• Heavy industrial fuels
Secondary Distillation (Vacuum Distillation)
• Light distillate
• Middle distillate
• Heavy distillate
• Asphalt/bitumen

19.6.3 Conversion Processes

Process for Improvement of Properties
• Catalytic reforming
• Isomerization
• Alkylation
Thermal processes
• Vis breaking
• Coking
Catalytic Processes
• Catalytic cracking (FCC)
• Hydrocracking
• Steam reforming
• Hydroconversion
Finishing Processes
• Hydrotreatment/hydrogenation
• Sweetening
Environmental Protection Processes
• Acid gas processing
• Stack gas processing
• Waste water treatment process

19.7 CRUDE OIL AND REFINING CAPACITY

As per organization of the petroleum exporting industry (OPEC) expects that India’s
oil demand to increase by over 150% to 10 million barrels per day (bpd) by 2040 from
around 4 million bpd currently. Global oil demand is currently 1.5 million bpd.
According to Vanguard, it is expected that global refining capacity to grow 7 mbd
through 2021. Global have announced new refinery additions to existing capacity from
2017 to 2021 and would add nearly 7 million bpd. According to the 2017 world’s refinery
construction outlook, it is expected that more than 100 capacity expansion projects (about
7 million bpd). [Link]
to-grow-7mbd- through-2021/). Global oil consumption and refining capacity, world
refining capacity country wise 2009 are given in Table 19.5. Present refining capacity
298 Chemical Process Technology

Table 19.5: Key specification of gasoline

Specification BIS 2000 BIS-II Euro-III Eqv. Euro-IV Eqv.
Regular Premium Regular Premium
Sulfur, ppmw (max) 1000 500 150 150 50 50
RON, min 88 88 91 95 91 95
MON, min No spec. No spec. 81 85 81 85
AKI, min 84 84 81 85
Benzene vol% (max) 5 3 1 1 1 1
Aromatics vol% (max) No spec. No spec. 42 42 42 35
Olefins vol% (max) No spec. No spec. 21 18 21 81
Source: Rajgopal S. “Refining Challenges and Trends. 6th Summer School on “Petroleum Defining
and petrochemicals”. June 6, 2012, Organized by New Delhi.

in India is about 230 million tons per annum. The present import of crude in India is
around 180 million tons per annum. India needs to double its refining capacity to about
465 million tons by 2040 from about 232 million tons to meet rising demand of fuel due
to increase in vehicles. Major drivers for fuel growth India will be due to increase in
vehicle population and substitution of LPG as a cooking fuel, growing urbanization and
country’s demand for infrastructure and consumer goods. Indian economy is very fast
developing and oil will be the dominant force of transportation fuels. Transportation
fuels, which currently make up 40% of fuel demand in the world’s third biggest oil
consumer, will increase that share to 55% by 2040 becoming main driver of growth
(Vaidya, 2017).
It is expected that the import of crude oil has to exceed 240 million tons per
annum in the next five years, if GDP growth of around 6–7% were to be sustained
(Venkat, 2012).
India needs to double its refining capacity to about 465 million tons by 2040 from about
232 million tons to meet rising demand of fuel due to increase in vehicles. Major drivers
for fuel growth India will be due to increase in vehicle population and substitution of
LPG as a cooking fuel, growing urbanization and country’s demand for infrastructure
and consumer goods. Indian economy is very fast developing and oil will be the
dominant force of transportation fuels. Transportation fuels, which currently make up
40% of fuel demand in the world’s third biggest oil consumer, will increase that share
to 55% by 2040 becoming main driver of growth (SM Vaidya of IOCL. Hydrocarbon
[Link].2017; Chemical Industry Digest, October 2017, p.10).
IOCL, India’s largest oil company, plans to nearly double refining capacity to
104.5 million tons by 2022 (with an investment of about ` 40,000 crore) and 150 million
tons by 2030 from its present refining capacity of 80.7 million tons per annum (http://
economics [Link]/industry/energy/oil/ioc-plans-to-double-refining-
capacity-by-2030/articlesshow/[Link]). IEA predicts a robust in Indian oil
consumption and expected to touch 10 million bpd from current levels of 4 million bpd
and oil is expected to remain an integral part of our energy. Natural gas which today
accounts for just about 7% of energy basket is expected to increase share of gas in mix
to 15% energy (Sarraf DK. “Special feature on future of oil and gas sector in India. FIPI
Volume 16 (issue 1), Jan–March, 2017).
Petroleum Refining 299

19.7.1 Changing Scenario in Gasoline and Diesel Specifications

There have been continuous changes in the fuel norms to meet the challenges due to
fuel norms standard. Vehicle exhaust is complex mixture of thousands of gases and
fine articles, and more than 40 toxic air contaminants are cancer causing. Diesel exhaust
contains higher sulfur and particulate emission than gasoline exhaust.
Various efforts made by petroleum industry for gasoline quality improvement are
led phase out an RON improvement, sulfur and olefin and benzene reduction and
implementation URO VI norms in some refineries. Efforts made by petroleum industry
for diesel quality improvement is sulfur reduction and cetane improvement, reduction
in particulate emission, especially PM 2.5 particles.
Key specification of gasoline and diesel is given in Table 19.5 and 19.6, respectively.

Table 19.6: Key specification of high-speed diesel (HSD)

Specification BIS2000 BS-II Euro-III Equ.
Density@15ºC kg/m3 820–860 820–860 820–845
Sulfur content Ppm (max) 2500 500 350
Cetane number (min) 48 48 51
Distillation 99% vol. (ºC max) 370 370 360
Polycyclic aromatics hydrocarbons (PAH), % No spec. No spec 11
massmax
Source: Rajgopal S. “Refining Challenges and Trends. 6th summer School on “Petroleum Refining
and Petrochemicals” June 6, 2012, Organized by New Delhi.

Key specification of Euro 6 norms for petrol emission and diesel emission is given
in Tables 19.7 and 19.8, respectively.
Three public sector refiners IOCL, BPCL and HPCL will have to invest about 30,000–
35000 crores over next four years to produce to produce auto fuels that will comply with
VI emission norms. Now country will implement Bharat stage VI fuel requirement by
April 2020 (Chemical Industry Digest, February 2016).

Table 19.7: Petrol emission norms (All figures in g/km)

Emission norm CO HC NOx HC + NOx PM
BS-III 2.30 0.20 0.15 — —
BS-IV 1.00 0.10 0.08 — —
Euro 6 1.00 0.10 0.06 — 0.005

Table 19.8: Diesel emission norms (All figures in g/km)

Emission norm CO HC NOx HC + NOx PM
BS-III 0.64 — 0.50 0.56 0.05
BS-IV 0.50 — 0.25 0.30 0.025
Euro 6/BS VI 0.50 — 0.06 0.17 0.005
Source : Indian Emissions Regulations/ARA
300 Chemical Process Technology

19.7.2 Maximizing Value Addition to Refinery Streams

For a refinery to be successful today, it has to be integrated with petrochemical to benefit
from better realization from value added products and to mitigate the effect of volatile
oil process and highly competitive refining business (Singh and Vaidya, 2012). Some of
the streams which can maximize value addition to the refinery is given in Table 19.9.

Table 19.9: Maximizing value addition to refinery streams

Streams Utilization
Fuel gas H2
FCC
Ethylene Ethyl benzene to styrene
Propylene Cumene, iso-propanol
Butylene Methyl ethyl keton, MTBE, Xylenes
C3 Propylene + H2
C4 Discussed separately
LPG BTX
C5 TAME
Light naphtha LPG, BTX
Heavy naphtha Aromatics
Kerosene n-paraffins to LAB
LCO (FCC unit) Mixed naphthalenes
Coker kerosene a-olefins
Sources: MO. Garg Director Indian Institute of Petroleum, Dehradun 23rd
National Convention of Chemical Engineers IIT Roorkee, October 5–7, 2007.

Natural gas fuels the integration of refining and petrochemicals. Maximizing the use
of natural gas in a refinery–petrochemical complex offers higher margins and Lowe
carbon emissions (Tarapdar, T Yadav, Prasad MKE. Petroleum Technology 2012, p.39).

19.8 EVALUATION OF CRUDE OIL, PETROLEUM PRODUCTS AND PETROCHEMICALS

Indigenous and imported crude oils are being process in India for production of
gasoline, diesel, kerosene and lube oil, wax and Feedstock for petrochemical industry
like naphtha, kerosene, etc.
19.8.1 Sources of Indigenous Crude, Imported Crude
Various sources of indigenous crude are:
• Assam crude
• Bombay high and satellite fields, North Gujarat and Ankhleshwar
• KG basin-Rava crude
• Cauvery basin crude
• Rajasthan crude
Various sources of imported crude are:
• Arab mix
• Lavan blend
• Upper Zakum
Petroleum Refining 301

• Iran mix
• Dubai
• Kuwait crude
• Suez mix
• Zeit bay
• Quaiboe
• Miri light
• Bonny light

19.8.2 Types of Evaluation

Depending on the objective of evaluation, following are the types of evaluation generally
carried out:
• Preliminary assay: It is generally comprised of:
ƒ Key basic properties of crude oil
ƒ Distillation data generated through a semi-fractionating or fractionating distillation
• Short evaluation:
ƒ Physicochemical properties of crude oil fractionating TBP distillation data
ƒ Yield and some key characteristics of major straight run products (Naphtha,
kerosene, gas oil cuts and atmospheric residue)
• Detailed evaluation:
ƒ Physicochemical properties of crude oil TBP distillation assay (Atmospheric and
vacuum range)
ƒ Detailed studies on several straight run cut in fuel oil, lube oil and secondary
processing feedstocks and bitumen.

Crude Oil and Product Evaluation (Joshi and Vijh, 1996)

Quality of crude being processed affect
• Plant capacity
• Feedstock availability and quality for downstream units
• Product pattern
• Overall economics
Significant effect on processing scheme and product pattern.
Effect of change in crude quality
• Change of product pattern
• Change of processing scheme
• Throughput
• Economics
• Effluent quality
Various parameters for prediction of crude oil storage and handling behavior are
viscosity, pour point, H2S, base of the crude (characterization factors, BMCI index,
viscosity index), mercaptans, acidity, salt and BS&W, distillation, RVP, characteristics of
crude, light end analysis, rheology, corrosiveness, impurities, volatility, LPG potential,
sulfur wax, CR, Trace metals, naphthenic acid, asphaltenes, etc. Details description of
parameters are given in Table 19.10.
302 Chemical Process Technology

Table 19.10: Various parameters used for characterization of crude oil

Parameters Significance Description
D e n s i t y a n d A P I Weight to volume and vice Density = Mass/volume
gravity versa calculation, checking
consistency of crude oil, control API gravity = 141.5
= 131.5
of refinery operation and give a [Link] 15.3/15.6ºC
rough estimation of crude oil.
API gravity of lighter crude
oil may be of the order of 45
whereas in heavier asphaltenes
API is 10–12.
Reid vapor pressure Indicates the relative percent­age
and light end of gaseous and lighter hydro­
analysis carbons.
Cloud point and For estimating the relative
pour point amount of wax present in the
crude oil. Cloud point gives a
rough idea above which the oil
can be safely handled.
Viscosity Viscosity indicates the relative Kinematic viscosity = absolute
mobility of various crude oils. viscosity/ density
Temperature has a marked effect Redwood viscometer, Say bolt
on viscosity. Viscometer are used
Aniline point Aniline point indicates the
lowest temperature at which
the oil is completely mixed with
an equal volume of aniline. High
aniline point indicates that the
fuel is paraffinic and hence has a
high diesel index and very good
ignition quality.
Asphaltenes, carbon Carbon residue and asphaltenes It is determined by Conradson carbon
residue and asphalt indicate the presence of heavier residue and Rams bottom carbon residue
content hydrocarbons in the crude. method.
Carbon residue is the measure of
thermal coke forming property.
Flash and fire point Flash point is the lowest tempe­ Penskys Martens open/closed cup is
rature at which application used.
of the test flame causes the
vapor and air mixture above the
sample to ignite. Fire point is the
lowest tempe­­rature at which the
oil ignites and continues to burn.
Smoke point It is an indication of the smoking Smoke volatility index (SKI) = Smoke
tendency of fuel. It is used for point + 0.42 × recovery at 204ºC
evaluating the ability of kerosene
to burn without producing
smoke. It is the maximum flame
height in mm at which the fuel
will burn without smoking.
Contd...
Petroleum Refining 303

Table 19.10: Various parameters used for characterization of crude oil (Contd...)
Parameters Significance Description
Acidity It is an indication of the corrosive
properties of products.
Copper corrosion test This test serves as a measure of
possible difficulties with copper,
brass, bronze part of the fuel
system.
Water, salt and These causes irregular behavior Water content is determined by Dean and
sediments in the distillation and cause Stack. Sediment and water is determined
blocking and fouling of heat by centrifuging a mixture of crude oil and
exchanger and result in corrosion toluene. Salt content is determined by
titrating the water extract with KCNS/
AgNO3.
Base of the crude oil For characterization of the Characterization factor
crude oil base-paraffinic/inter­
K = √ TB/sp. gr at 15.6ºC .
3

mediate/Naphthenic and for

measure­ment of the aromaticity. TB = Mean av. Boiling point in Rankin
Various parameters used are paraffinic base k = >12.1; Intermediate
characteri­zation factor, BMCI, base k= 11.5–12.1; naphthenic k = 11.5;
VGC, etc. aromatics k = 9.8–12.0
Bureau of Mines Correlation Index
(BMCI)
BMCI= 48640/ºK + 473.7 g-456.8
K = avg. boiling point in ºK, g specific
gravity 15.6/15.6ºC
BMCI value:
Paraffinic = <15;
Intermediate = 15–50;
Naphthenic = >50
Viscosity gravity correlation (VGC)
10G – 1.0752 log (V – 38)
VGC =
10 – log (V – 38)
G is sp. gravity and V is say bolt universal
viscosity
Paraffinic base: 0.80–0.83
Intermediate base: 0.83–0.88
Naphthenic base: 0.88–0.95
TBP assay It is done for generating disti­
llation data and for study of
variations of some key properties
throughout the distillation
range.
Gum It is indication of gum at the time
of test and amount of deposition
during service time.
Color Indication of the thoroughness
of the refining process.
Contd...
304 Chemical Process Technology

Table 19.10: Various parameters used for characterization of crude oil (Contd...)
Parameters Significance Description
Antiknock quality Octane number is the percentage Research octane number (RON) and
(octane number) of iso-octane in the reference Motor octane number (MON) are two
fuel which match the knocking methods used.
tendency of the fuel under test Anti-knock index (AKI) = (RON +
MON)/2
Cetane number Cetane number is the percentage
of cetane which must be mixed
with heptamethyl nonane to give
the same ignition performance
as the fuel in question.
Stability test It is used for the evaluation of
stor­age stability and resistance
to oxidation.
Carbon–Hydrogen CH ratio = (74 + 15d)/(26–15d), where d
ratio is sp. gravity at 15ºC
Diesel index It is an indication of ignition Diesel index = (Aniline point in ºF ×
quality of a diesel. API)/100
Diesel index = cetane number – 10/0.72
Weathering test for This test shows the volatility of
LPG the LPG
Frass breaking point This is the temperature below
which the bitumen tends to
break rather than flow.
Source: Mall, 2007; Mall, 2017.

19.8.3 Product Evaluation

Major parameters for gasoline included in Bharat or Euro norms are:
• Lead phase out
• Lower RVP
• Lower benzene and aromatics
• Lower olefin content
• Limited oxygen content
• Lower sulfur content
Other parameters of importance are RON, MON, Lead, gum, oxidation stability,
density, VLI index, FBP. In case of reformulated gasoline aromatics, olefins oxygen,
Antiknock index, vapor lock index.
Major parameters for diesel included in Bharat or Euro norms are:
• Low sulfur
• Low aromatics
• High cetane number
• Lower density
• Lower distillation end point
Other parameters for diesel are density, viscosity, cetane number distillation range,
sulfur, carbon residues, oxidation stability, flash point, acid value, ash and water
contents.
Petroleum Refining 305

19.8.4 Evaluation of Feedstocks for Petrochemicals

(Olefin, Aromatics, and Linear Alkyl Benzene (Lab) Plants)
Olefin, aromatic and LAB production are three major petrochemical building blocks.
Various feedstocks for olefins, aromatics, and surfactants are given in Table 19.11.
Input cost of feed constituents is a major portion of the variable cost of production
in petrochemical plants. Major feed input olefin, aromatics and surfactants are ethane
propane from natural gas, naphtha, kerosene and LPG from refinery, pyrolysis gasoline
from steam crackers, and benzene from aromatic plant. Feed quality monitoring and
improvement efforts are therefore very important aspects having significant impact on
the economics of the operation cost. The precursors and undesirable constituents in feed
including catalyst and adsorbents poisons should be known, analyzed and monitored
continuously.
Table 19.11: Feedstocks for olefin, aromatics and LAB
Plant Feedstock
Ethane, propane, naphtha, gas oil
Naphtha, pyrolysis gasoline, LPG
Kerosene for paraffins, benzene

Detail of evaluation of feedstock for petrochemical feedstock is given in Chapter 20.

19.9 CRUDE OIL BLENDING

Crude blending is done either by blenders or by refineries. The purpose of blending
is to upgrade the chemical and physical properties of crude oil. Blending of crude
oil is accomplished by online blending and tank blending. In online blending two or
components are injected from a separate pipeline and injected in single pipeline where
efficiency of blending depends on the stream Reynold number whether laminar or
turbulent flow, number of pipeline streams and time for mixing. In tank blending, the
two streams are added in a common tank. Common method of transportation of crude
oil is through piping.

19.10 CRUDE OIL DISTILLATION (Mall 2013, 2016, 2017)

Refining of crude oils or petroleum essentially consists of primary separation
processes and secondary conversion processes. The petroleum refining process is the
separation of the different hydrocarbons present in the crude oil into useful fractions
and the conversion of some of the hydrocarbons into products having higher quality
performance. Atmospheric and vacuum distillation of crude oils is the main primary
separation processes producing various straight run products, e.g. gasoline to lube oils/
vacuum gas oils (VGO). These products, particularly the light and middle distillates,
i.e. gasoline, kerosene and diesel are more in demand than their direct availability from
crude oils, all over the world.
19.10.1 Pretreatment of Crude Oils
Crude oil comes from the ground, which contains variety of substances like gases, water, dirt
(minerals), etc. Pretreatment of the crude oil is important if the crude oil is to be transported
effectively and to be processed without causing fouling and corrosion in the subsequent
operation starting from distillation, catalytic reforming and secondary conversion processes.
306 Chemical Process Technology

Impurities: Impurities in the crude oil are either oleophobic or oleophilic.

Oleophobic Impurities: Oleophobic impurities include salt, mainly chloride and
impurities of Na, K, Ca and Mg, sediments such as salt, sand, mud, iron oxide, iron
sulfide, etc. and water present as soluble emulsified and/or finely dispersed water.
Oleophilic Impurities: Oleophilic impurities are soluble and are sulfur compounds,
organometallic compounds, Ni, V, Fe and As, etc. naphthenic acids and nitrogen
compounds.
Pretreatment of the crude oil removes the oleophobic impurities.
Pretreatment
Pretreatment takes place in two ways:
• Field separation
• Crude desalting
Field separation: Field separation is the first step to remove the gases, water and dirt
that accompany crude oil coming from the ground and is located in the field near the
site of the oil wells.
The field separator is often no more than a large vessel, which gives a quieting zone to
permit gravity separation of three phases: gases, crude oil and water (with entrained dirt).
Crude desalting: It is a water washing operation performed at the refinery site to get
additional crude oil clean up.
Crude oil desalting consists of:
• Purifying process
• Remove salts, inorganic particles and residual water from crude oil
• Reduces corrosion and fouling.
Desalting process is used for removal of the salts, like chlorides of calcium, magnesium
and sodium and other impurities as these are corrosive in nature. The crude oil coming
from field separator will continue to have some water/brine and dirt entrained
with it. Water washing removes much of the water-soluble minerals and entrained
solids (impurities). There are two types of desalting: single and multistage desalting.
Commercial crudes, salt contents 10–200 ppb, earlier 10–20 ppb were considered
satisfactorily low. However, many refiners now aim at 5 ppb or less (1–2 ppb), which
is not possible through single stage desalting, hence two-stage desalting is required.
Desalting process consists of three main stages: heating, mixing and settling.
Crude oil is heated up to 135–141ºC in the train of heat exchanger operating in two
parallel section. The temperature in desalting is maintained by operating bypass valve
of heat exchanger.
Single stage desalting with water recycle is usually justified if salt content in crude
is less than 40 ppb. Two stage desalting involves dehydration followed by desalting.
Double stage desalting is better for residuum hydrotreating. Fuel oil quality is better.
Desalting process is two-stage process: forming emulsion of crude and water and
demulsification in which emulsion is broken by means of electric field and demulsifying
chemicals. Desalting is carried out by emulsifying the crude oil and then separating the
salt dissolved in water. Two phases water/oil is separated either by using chemicals
to break down the emulsion or by passing high potential electric current. By injecting
water, the salts dissolved in the water and solutions are separated from the crude by
means of electrostatic separating in a large vessel.
Petroleum Refining 307

Operating Variables in Desalter

Some of the variables in the desalter operation are crude charge rate, temperature, pressure,
mixing valve pressure drop and wash water rate, temperature, and quality, desalting
voltage. Crude oil temperature charged to the desalter is very important for the efficient
operation of desalter. Lower temperature reduces desalting efficiency, because of increased
viscosity of oil while higher temperature reduces desalting efficiency due to greater electrical
conductivity of the crude. Pressure in the vessel must be maintained at a high value to avoid
vaporization of crude oil pressure which result in hazardous condition, erratic operation
and a loss of desalting efficiency. Flow diagram for crude oil desalting is given Figure 19.3.

Fig. 19.3: Crude oil desalting

19.10.2 Crude Oil Distillation

Desalted crude flows to atmospheric and vacuum distillation through crude pre flashing
section. Atmospheric distillation column (ADU) and vacuum distillation column (VDU)
are the main primary separation processes producing various straight run products,
e.g. gasoline to lube oils/vacuum gas oils (VGO). These products, particularly the light
and middle distillates, i.e. gasoline, kerosene and diesel are more in demand than their
direct availability from crude oils, all over the world.
Crude oil distillation consists of atmospheric and vacuum distillation. The heavier
fraction of crude oil obtained from atmospheric column requires high temperature. In
order to avoid cracking at higher temperature the heavier fraction is fractionated under
vacuum. Typical flow diagram of crude oil distillation is given in Figure 19.4. Various
streams from atmospheric and vacuum distillation column are given in Table 19.12.
Atmospheric Column
Various steps in atmospheric crude oil distillation are:
• Preheating of desalted crude
• Reflash
• Distillation
• Stabilization of naphtha.
The desalted crude oil from the second stage desalting process is heated in two parallel
heat exchangers. The preheated crude having temperature of about 180ºC is goes to
preflash drum where about 3–4% of light ends are removed. The preheated crude from
the preheater section is further heated and partially vaporized in the furnace containing
tubular heater. The furnace has two zones: radiant section and convection section. The
radiant zone forms the combustion zone and contains the burners. In convection zone the
crude is further heated (inside the tube) by the hot flue gases from the radiant section.
Heated and partially vaporized crude from the fired heaters enters the flash zone of
the column and fractionated in the atmospheric column. The distillation section consists
of overhead section, heavy naphtha section, kerosene section, light gas oil section, heavy
gas oil section and reduced crude section each section contains circulating reflux system.
308 Chemical Process Technology

Fig. 19.4: Atmospheric and vacuum crude oil distillation

Table 19.12: Various streams from atmospheric and vacuum distillation column
Column Fraction Temperature Carbon Uses
(ºC) range
Atmospheric Fuel gases >40 C1–C2 Fuel
column
LPG C3–C4 Domestic fuel
Straight run gasoline 20–90 C6–C10 Gasoline pool
Naphtha (Medium 130–180 C6–C10 Catalytic reforming and aromatic
and heavy) plant, feedstock, steam cracker,
synthesis gas manufacture
Kerosene 150–270 C11– Aviation turbine fuel, domestic fuel,
C12 LAB feedstock (paraffin source)
Light gas oil 230–320 C13–C17 High-speed diesel component
Heavy gas oil 320–380 C18–C25 High-speed diesel component
Vacuum Light vacuum gas oil 370–425 C18–C25 Feed to FCC/HCU
column
Heavy vacuum gas oil 425–550 C26–C38 Feed to FCC/HCU
Vacuum slop 550–560 RFCCU feed
Vacuum residue >560 >C38 Bitumen/Vis breaking feed

Naphtha stabilizer, caustic wash and naphtha splitting section: The unstabilized naphtha
from the atmospheric distillation column is pumped to the naphtha stabilizer section
for separation of stabilized overhead vapors which is condensed to recover LPG which
Petroleum Refining 309

is treated in caustic and amine treating unit. The stabilized naphtha is further separated
into light, medium and heavy naphtha.
Products of ADU
Major product from atmospheric column are light gases and LPG, light naphtha, medium
naphtha, heavy naphtha, kerosene, gas oil (diesel), atmospheric residue.
• Unstabilized naphtha consists of LPG, naphtha and light gases (C-5 115ºC)
• Intermediate naphtha (Bombay high) (135ºC) solvent naphtha
• Heavy naphtha (130–150ºC) routed to diesel or naphtha.
• Kerosene/ATF (140–270/250ºC)
• Light gas oil (250/270–320ºC)
• Heavy gas oil (320–380ºC)
• Reduced crude oil.
Operating Variables in ADU Unit
• Furnace coil outlet temperature
• Crude distillation column top pressure and top temperature
• Stripping steam flow
• Product withdrawal temperatures.
Vacuum Distillation Column (VDU)
The bottom product also called reduced crude oil, from the atmospheric column is
fractionated in the vacuum column. Reduced crude oil is very heavy compared to crude
oil distilling under pressure requires high temperature. Distillation under vacuum
permits fractionation at lower temperature which avoid cracking of the reduced crude oil
and coking of the furnace tube. Vacuum is maintained using three stage steam ejectors.
The reduced crude oil from atmospheric column at about 360ºC is heated and partially
vaporized in the furnace. The temperature in the flash zone of the tower is controlled by
the furnace coil outlet temperature. The preheated and partially vaporized reduced crude
enters the flash zone of vacuum column where it is fractionated into various streams.
Products from VDU: Various products from VDU are light gasoil, heavy gas oil, light
lube distillate, medium lube distillate, heavy lube distillate, and vacuum column residue.
Operating Pressure of Vacuum Column
• About 90–95 mm Hg at the top and
• About 135–140 mm Hg at the bottom
Chemical Injection System
Chemical injection system consists of caustic injection and ammonia injection and use of
corrosion inhibitor, use of demulsified, addition of trisodium phosphate in boiler feed
water. Corrosion in the atmospheric tower overhead system is a common phenomenon
and the problem is increasing with increasing use of the heavier crude oil. Corrosion is
primarily due to hydrogen chloride, which is produced by hydrolysis of the chloride
salts remaining after desalting. Other sources of corrosion are naphthenic acid and
hydrogen sulfide. High caustic injection is to be avoided as high caustic injection system
may lead to fouling in vacuum and Vis breaker furnaces. Ammonia injection is done
to maintain pH. Corrosion inhibitor in kerosene and naphtha is required to combat the
corrosion. De-emulsifier is used to demulsify the water and crude emulsion. Trisodium
phosphate is used to maintain pH and prevent corrosion in the boiler drums.
310 Chemical Process Technology

Effect of Crude Characteristics

Crude oil characteristics plays important role in the product distribution, processing
scheme and quality of product. Effect of crude characteristics on performance of crude
distillation is given in Table 19.13.

Table 19.13: Effect of crude characteristics on performance of crude distillation

Characteristic Effect
API API A Measure of “heaviness” or “lightness”
API = (141.5/specific gravity) –131.5
API >30 Light crude
API <28 Heavy crude
Viscosity A measure of resistance to flow and is important parameter for
effective desalting and highly dependent on temperature. High-
viscosity crudes need high temperatures for effective desalting. There
is a limit for temperature in desalters.
UOP K (characterization It is measure of paraffin city vis-à-vis aromaticity of crude.
factor) High UOP K is desired for high conversion in FCC.
High UOP K is desired for high conversion in FCC.
Aromatic molecules cannot be cracked in FCC. They will simply take
ride through the plant.
Total acid number (TAN) A measure of naphthenic acid contents in crude leads to corrosion
in various sections of the unit. Over 1,500 known NA species are
present in crude.
All Nap acids are not corrosive. Latest research indicates that TAN is
not a complete corrosion index.
TAN with 2.5 may corrode at higher rate than TAN with say 6!
Detailed metallurgical reviews and monitoring mechanism must be
put in place.
Bottom sediments and Bottom sediments and water is a measure of water, water dissolved
water (BS&W) substances, mud, sand and sludge. Lower the BS&W—the higher the
reliability of the unit. BS&W is one of the major pointer for corrosive
materials in crude.
Sulfur Sulfur is a measure of “sourness” and “sweetness” of crude passed
onto products as much as regulations or market accepts. It is removed
in hydrotreaters by reacting with H2 and recovered as elemental Sulfur
in sulfur recovery unit
S >2.5: Sour crude, S<2: Sweet crude
Total salts Measure of contaminant in crude that will cause overhead corrosion or
foul-up exchangers by settling and scaling. It is removed in desalters
by washing and settling
VGO metals Measure of metals content in VGO fraction Ni and V are known
poisons of VGO hydrotreater catalyst.
Metals in VGO are controlled by controlling wash rate in slop wax
section of vacuum column

19.11 THERMAL CRACKING, VIS BREAKING AND DELAYED COKING

With the continuous depletion in world oil reserves and increasing demand of petroleum
products, the refiners are forced to process more and heavier crude (Tendon, et al. 2007).
Petroleum Refining 311

The cost advantage of heavy crudes over light crudes has incentivized many Indian
refineries to process heavier crude; therefore, increasing the heavy residue produced at a
time when fuel oil demand is declining (Haizmann, et al. 2012). In order to dovetail both
the requirement for processing crude oil of deteriorating quality and enhancing distillates
of improved quality, technological upgradation have been carried out at refineries which
takes care of processing heavy crudes as well as maximizing value added products and
stringent product quality requirements (Sarkar S, Basak, TK.“Heavy oil processing in
IOCL Refineries; Compendium 16th Technology Meet, February 17–19, 2011). Some of
the residue upgradation technologies in Indian refineries are given in Table 19.14.

Table 19.14: Residue upgradation technologies in refineries

Delayed coking and Vis breaking Technology for the bottom of the barrel upgradation;
means of disposing of low value reside by converting part
of the reside to more valuable liquid and gas products.
Unflex technology Technology for processing low quality residue by thermal
cracking to produce high quality distillate products.
Fluidized catalytic cracking (FCC) and A technology introduced to contain generation of black oil
residual fluidized catalytic cracking from refinery and to increase the production of high value
(RFCC) products like LPG, MS and Diesel.
Hydrocracking Processes for residue upgradation FCC process, delayed
coking process and Vis breaking
Deep catalytic cracking (DCC) and For selectively cracking feedstocks to light olefins.
IOCL’s INDMAX

19.11.1 Cracking
Cracking of heavy residue is most commonly used method for upgradation of residues.
This involves of decomposition of heavy residues by exposure to extreme temperatures
in the presence or absence of catalysts.
Thermal Cracking: Cracking at elevated temperatures in the absence of catalyst, e.g. Vis
breaking, delayed coking, fluid coking, etc.
Catalytic Cracking: Cracking in presence of catalyst, e.g. FCC, hydrocracking, DCC

Cracking Mechanism
Cracking takes place by free-radical mechanism.
Initiation
C6H14 C2H5O + C4H9O

Propagation
C2H5O + C6H14 C2H6 + C6H13O
C4H9O + C6H14 C4H10 + C6H13O
C4H9O C3H6 + CH3O
C6H13O C4H8 + C2H5O (many other products)
Termination
C2HO + CH3O C3H8
312 Chemical Process Technology

During the cracking operation, some coke is usually formed. Coke is the end product
of polymerization reaction in which two large olefin molecules combine to form an even
larger olefinic molecule:
C10H21 – CH = CH2 + CH2 = CH – C10H21 C10H21 – CH = CH – CH2 – CH2 – C10H21

Development of Cracking Processes

Year Process
Thermal cracking
Batch thermal cracking
1912 Burton cracking
1914–22 Continuous cracking process.

19.11.2 Thermal Cracking

Thermal cracking process for upgradation of heavy residue has been used since long
and still it is playing an important role in the modern refinery through upgradation
of heavy residue and improving the economics of the refinery through the production
of lighter distillate and other valuable product like low value fuel gas and petroleum
coke. Although petroleum coke was first made by North Western Pennsylvanian in the
1860s using cracking, however, a real breakthrough in the thermal cracking process was
with development of the first cracker by William Burton and first used in 1913. Heavy
residues are a mixture molecule consisting of an oil phase and an asphaltene phase in
physical equilibrium with each other in colloidal form.
Asphaltenes are high molecular weight, relatively high atomicity molecules containing
high levels of metals. During thermal cracking, the long molecules thus depleting the
oil phase in the residue. Asphaltene cracking is the most difficult component to process
and asphaltenes in the feed remain unaffected, additional asphaltenes may be formed
by secondary polymerization reactions. At a certain condition, asphaltenes is disturbed
and asphaltenes precipitate. At this stage of conversion, the product residue becomes
unstable.
Under condition of thermal cracking, hydrocarbons, when heated, decompose into
smaller hydrocarbon molecules. The UOP thermal cracking process is based on two
coil designs for selective cracking of topped or reduced crudes into valuable products
>350°C. Table 19.15 shows the various thermal cracking process and process conditions.
Thermal treatment: Medium, High, Ultra High (Cracking with higher temperature and
with very short residence time).

Table 19.15: Various thermal cracking process and process conditions

Process Process conditions
Vis breaking Mild thermal cracking (low severity)
Mild (470–500ºC) heating at 50–200 psig
Improve the viscosity of fuel oil
Low conversion (10%) to 430ºF
Residence time 1–3 min
Heated coil or drum
Contd...
Petroleum Refining 313

Table 19.15: Various thermal cracking process and process conditions (Contd...)
Process Process conditions
Delayed coking Operates in semi batch mode
Moderate (900–960ºF) heating at 90 psig
Soak drums (845–900ºF) coke walls
Coked until drum solid
Coke (removed hydraulically) 20–40% on feed, Yield 430ºF, 30%
Fluid coking Server (510–520ºC) heating at 10 psig
Oil contact refractory coke
Bed fluidized with steam–even heating, Higher yield of light ends (<Cs),
Less coke yield
Flexi coking A continuous fluidized bed technology which converts heavy residue to
lighter more valuable product. The process essentially eliminates the coke
production. Temperature 525ºC

Reactions
• Cracking of side chains free aromatic group
• Dehydrogenation of naphthenes to form aromatics
• Condensation of aliphatic to form aromatics.
• Condensation of aromatic to form higher aromatics
• Dimerization or oligomerization.
Process Variables: Major variables in thermal cracking process are feedstock properties,
cracking temperature, residence time, pressure, thermal cracking: medium, high, ultra-
high (cracking with higher temperature and with very short residence time).
Vis Breaking
Vis breaking is essentially a mild thermal cracking operation at mild conditions wherein
long chain molecules in heavy feedstocks are broken into short molecules thereby
leading to a viscosity reduction of feedstock. Now all the new Vis breaker units are of
the soaker type. Soaker drum utilizes a soaker drum in conjunction with a fired heater
to achieve conversion (Sieli, 1998).
Vis breaking is a non-catalytic thermal process. It reduces the viscosity and pour point
of heavy petroleum fractions so that product can be sold as fuel oil. It gives 80–85%
yield of fuel oil and balance recovered as light and middle distillates. The unit produces
gas, naphtha, heavy naphtha, Vis breaker gas oil, Vis breaking fuel oil (a mixture of
vis breaking gas oil and vis breaking tar). A given conversion in vis breaking can be
achieved by two ways:
• High temperature, low residence time cracking: Coil Vis breaking.
• Low temperature, high residence time cracking: Soaker Vis breaking.
Reaction in Vis breaking
CH3 – CH2 – CH2 – CH2 – CH3 – CH2 – CH3 CH3 – CH2 – CH = CH2 + CH3 – CH2 – CH3

Soaker Vis Breaking Process: The furnace operators at a lower outlet temperature and
a soaker drum is provided at the outlet of the furnace to give adequate residence time
to obtain the desired conversion while producing a stable residue product, thereby
increasing the heater run and reducing the frequency of unit shut down for heater
314 Chemical Process Technology

decoking (Sieli, 1998). The products from soaker drum are quenched and distilled in
the downstream fractionator. Process diagram for Vis breaking with soaker is shown
in Figure 19.5.
Objective: To lower the viscosity of heavy residues under relatively milder cracking
condition than the conventional cracking processes.
Feed atmospheric residues to get gasoline and diesel oil
Vacuum residues to reduce viscosity
Reaction:
• Splitting of C–C bond.
• Oligomerization and cyclization to naphthenes of olefinic compounds
• Condensation of the cyclic molecules to polyaromatics.
Side reactions: Formation of H2S, thiophenes, mercaptans, phenol.
Products: The cracked product contains gas, naphtha, gas oil and furnace oil, the
composition of which will depend upon the type of feedstock processed. A typical yield
pattern may be gas 1–2%, naphtha 2–3%, gas oil 5–7%, furnace oil 90–92%.
Vis breaking conditions:
Inlet temperature: 305–325ºC (15–40 bar)
Exit: 480–500ºC (2–10 bar)
With soaking 440–460ºC (5–15 bar)
Feed: 90ºC pretreated with VB tar to 335ºC.
Vis breaking furnace:
Convection zone top to thermal efficiency
Radiation zone bottom tubes
Avg. heat flow 22–30 kW/m2

Fig. 19.5: Vis breaking with soaker

Variables: Variables in Vis breaking are feed rate, furnace transfer temperature, Vis
breaking tar quench to transfer line, fractionation pressure, fractionation top temperature,
circulation, reflux flow, Vis breaking tar quench to fractionator bottom, Vis breaking tar
quench to Vis breaking tar stripper bottom, stabilizer temperature and pressure.
The purpose of Vis breaking is to produce lower viscosity fuel oil.
Petroleum Refining 315

Soaking Drum
Soaking drum is used to lengthen the feed residence time so that the furnace can
operate at lower temperature. Soaker results in saving of energy, because of the lower
temperature with less coke tendency, larger gas oil yield.
Advantages
• 15% reduction in fuel oil
• Larger running time between two decoking operations. coke deposit rate 3–4 times
slower than in conventional units.
• Better selectivity toward gas and gasoline productivity.
Coil Vis breaking: In coil Vis breaking process, the desired cracking is achieved in the
furnace at high temperature and the products of cracking are quenched and distilled
in a downstream fractionator. Advances in Vis breaking coil heater design now allows
for the isolation of one or more heater passes for decoking, eliminating the need of shut
the entire Vis breaking down for furnace decoking. Integration of the coil in Vis
breaking process with vacuum units is also being considered in many areas of the world
(Sieli, 1998).
Coking
Coking is very severe form of thermal cracking and converts the heaviest low value
residue to valuable distillates and petroleum coke. It is relatively severe cracking
operation to convert residual oil and represents the complete conversion of petroleum
residues to coke and lighter products. Recycle is used to further convert heavy distillate
fractions to lighter products.
Mechanism of coke formation: The colloidal suspension of the asphaltenes and resin
compounds is distorted, resulting in precipitation of highly cross-linked structure of
amorphous coke. The compounds are also subjected to cleavage of the aliphatic groups.
Polymerization and condensation of the free aromatic radicals, grouping a large number
of these compounds to such a degree that dense high-grade coke is eventually formed.
The process involves thermal conversion of vacuum residue or other hydrocarbon
residue resulting in fuel gas, LPG, naphtha, gas oil and coke and essentially a complete
rejection of metals. Various types of coking processes are delayed coking, fluid coking
and flexi coking.
Delayed Coking
Delayed coking process is used to crack heavy oils into more valuable light liquid
products with less valuable gas and solid coke as by-products. Although first delayed
coking plant was built in 1930, delayed coking process has been evolving for 78 years,
the past few years have seen changes in feedstock that has major impact on the design
and operation of delayed coking (Catala, 2009). Refineries are adding cookers due to use
of more and more heavy sour feedstock. The delayed cookers produce large quantity of
solids which create problems in the solid handling system. A typical large scale delayed
cooker produces well over 1 million ton per year (Hull, et al. 2011).
Delayed coking consists of thermal cracking of heavy residue in empty drum where
deposition of coke takes place. The product yield and quality depend on the typed
feedstock processed. Typical delayed coking consists of a furnace to preheat the feed,
coking drum where the fractionation of the product takes place.
316 Chemical Process Technology

The feed is first preheated in furnace where the desired cooking temperature is
achieved and fed to the coking drums normally installed in pairs where the cracking
reaction takes place and the coke is deposited in the bottom of the reactor. The coke
drums overhead vapor flows to the fractionating column where they are separated into
overhead streams containing wet gas LPG and naphtha and two side gas oil streams.
Recycled stream from the fractionating column combines with the fresh feed in the
bottom of the column and is further preheated in coke heaters and flows to the coke
drums. When a coke drum is filled, the heated streams from the coke heated are sent
to the other drum. Process flow diagram for delay coking is shown in Figure 19.6.
The reaction involved in delayed coking is partial vaporization and partial
cracking, cracking of two vapor phase in the coke drum and successive cracking used
polymerization of liquid phase resulting in formation of coke in the drum.
Feed: Vacuum residue, FCC residual, or cracked residue. Studies show that feedstock
quality and severity on conversion impact the stability of Vis breaking residue (Stative,
et al. 2008).
Product: Gases, naphtha, fuel oil, gas oil and coke.

Fig. 19.6: Process flow diagram of delayed coking

Operating variables
Feedstocks variables: Characterization factor, degree of reduction, Conradson carbon,
sulfur content, metallic constituents. Low feedstock characterization factor and high
carbon residue increase coke yield and quality of gas oil end point.
Engineering variables: Batch, semi-continuous or continuous, capacity and size factors,
coke removal equipment, coke handling, storage and transportation.
Operating variables: Various operating variables in delayed coking are temperature,
pressure, recycle ratio, transfer temperature, and coke chamber pressure.
Higher temperature: Results in more vaporization of the inlet material causing low coke
yield. A furnace outlet temperature of 485–505°C is maintained. High temperature
results in hard coke while coke is soften when too low temperature is maintained.
Higher pressure: Results in an increase in coke and gas yields which is undesirable as
basic objective is to improve the yield of distillation with less coke.
Petroleum Refining 317

Higher recycle ratio: Results in higher coke and gas yields. Lower recycle ratio is always
desirable for higher yield of liquid product.
Coke yield = 1.6 CCR (Conradson carbon residue)
Gas yield = 7.8 + 0.144 × CCR
Naphtha yield = 11.29 + 0.343 CCR
Gas yields = 110-coke-gas yield-naphtha yield
Low feedstock characterization factor and high carbon residue increase coke yield
and quality of gas oil end point.
Fluid coking: Fluid coking is non-catalytic fluid bed process where residue is coked by
spraying into a fluidized bed of hot, fine coke particles. Higher temperature with shorter
contact time than delayed coking results in increased light and medium hydrocarbons
with less cake generation. Shorter residence time can yield higher quantities of liquid
less coke, but the product has lower value (Rana, et al. 2007).
Flexi coking: It is continuous process involves thermal cracking in a bed fluidized coke
and gasification of the coke produced at 870ºC. This process contains an additional step
of gasification (Temp: The gases leaving the gasifier is low calorific value fuel gas at
800–1500 kcal/m3 (4200–5000 kJ/std m3 and is burned in the furnace or power plants.
It can be applied to wide variety of feedstocks.
UOP Uniflex™™ Process (Haizmann, et al. 2010): It is high conversion, commercially
proven technology, that processes low quality residue streams, like vacuum residue,
to make very high-quality distillate products. The process utilizes thermal cracking
to reduce molecular weight of the residue in the presence of hydrogen and a proven
proprietary, nano-sized catalyst to stabilize the cracked products and inhibit the
formation of coke precursors. The main products from unflex are naphtha and diesel
with a yield of greater than 80 vol.%.

19.11.3 Catalytic Cracking

Catalytic cracking process was developed in1920 by Eugene Houdry for upgradation
of residue was commercialized latter in 1930. Houdry process was based on cyclic fixed
bed configuration. There has been continuous up-gradation in catalytic cracking process
from it incept of fixed bed technology to latter fluidized bed catalytic cracking (FCC).
The feedstock for catalytic cracking is normally light gas oil from vacuum distillation
column. Catalytic cracking cracks low value high molecular weight hydrocarbons to
more value-added products (low molecular weight) like gasoline, LPG diesel along
with very important petrochemical feedstock like propylene, C4 gases like isobutylene,
isobutane, butane and butane. Main catalytic cracking reaction is given in Table 19.16.

Main reactions involved in catalytic cracking

• Cracking
• Isomerization
• Dehydrogenation
• Hydrogen transfer
• Cyclization
• Condensation
• Alkylation and dealkylation
318 Chemical Process Technology

Major primary reactions taking place in catalytic cracking are given in Table 19.16.
Paraffins Smaller paraffins + olefins
Alkyl naphthene naphthene + olefin
Alkyl aromatic aromatic + olefin
Multiring naphthene alkylated naphthene with fewer rings

Fluid Catalytic Cracking

Fluid catalytic cracking is now major secondary conversion process in petroleum refinery
since 1942. There are more than 400 FCC units in world. The process provides around
50% of all transportation fuel and 35% of total gasoline pool. Major landmarks in the
history of FCC are (Ghosh, 2002):
• Introduction of zeolite catalyst during 1960 which has resulted in lower residence time
• Introduction of ultra-stable Y-zeolite in mid-1960s
• Switch over from bed cracking to riser cracking
• Introduction of large number of additives for boosting of gasoline octane/yield of
light naphtha
• SOX control
• Nickel and vanadium passivation.
FCC is a multi-component catalyst system with circulating fluid bed reactor system
with reactor Regenerator system configuration. Figure 19.7 shows details of FCC process
and FCC reactor.

Table 19.16: Main catalytic cracking reactions

Paraffins Cracking → Paraffins + Olefins
Olefins Cracking LPG olefins
Cyclization Naphthenes
Isomerization Branched olefins H transfer Branched paraffins
H transfer Paraffins
Cyclization Coke
Condensation Coke
Dehydrogenation Coke
Naphthenes Cracking Olefins
Dehydrogenation Cyclo-olefins Dehydrogenation Aromatics
Isomerization Naphthenes with different rings
Aromatics Side chain cracking Unsubstituted aromatics + Olefins
Trans alkylation Different alkyl aromatics
Dehydrogenation Polyaromatics Alkylation, dehydrogenation,
condensation Coke
Hydrogen transfer Naphthene + Olefin Aromatic + Paraffin
Petroleum Refining 319

Fig. 19.7: Fluid catalytic cracking process and FCC reactor

Feedstock: Vacuum gas oil (VGO), hydro-treated VGO, hydro-cracker bottom, coker
gas oil (CGO), de-asphalted oil (DAO), reduced crude oil (RCO), vacuum residue (VR).
• Typical feedstock consists of vacuum and atmosphere gas oil but may include other
heavy stream.
320 Chemical Process Technology

• Major contaminant in the feed includes carbon residue and metals.

• While FCC process feed containing up to 4% Conradson carbon MSCC can process
all kinds of feed.
Process steps: Three basic functions in the catalytic cracking process are:
Reaction: Feedstock reacts with catalyst and cracks into different hydrocarbons.
Regeneration: Catalyst is reactivated by burning off coke and recirculated to reactor.
Fractionation: Cracked hydrocarbon stream is separated into various products like LPG
and gasoline, like light cycle oil and heavy cycle oil are withdrawn as side stream.
Reactor and regenerator section: Catalyst section consists mainly of the reactor and
regenerator.
• The feed to unit along with recycles streams is preheated to temperature of 365–370ºC
and enters the riser where it comes in contact with hot regenerated catalyst at a
temperature of about 640–660ºC. Finely divided catalyst is maintained in an aerated
or fluidized state by the oil vapors.
• The catalyst section contains the reactor and regenerator and catalyst re-circulates
between the two.
• Spent catalyst is regenerated to get rid of coke that collects on the catalyst during
the process. Spent catalyst flows through the catalyst stripper to the regenerator,
where most of the coke deposits burn off at the bottom where preheated air and
spent catalyst are mixed. Fresh catalyst is added and worn-out catalyst removed to
optimize the cracking process.
Fractionation: Cracked hydrocarbon stream is separated into various products. LPG
and gasoline are removed overhead as vapor. Unconverted product like light cycle
oil and heavy cycle oil are withdrawn as side stream. Overhead product is sent to
stabilization section where stabilized gasoline is separated from light products from
which LPG is recovered.
Typical operating parameter of FCC
Raw oil feed at heater inlet: 114 cubic meter/h
Furnace outlet temperature: 291ºC
Reactor feed temperature: 371ºC
Reactor vapor temperature: 549ºC
Product obtained:
• Light gas –H2, C1, and C2s
• LPG C3s and C4s – includes light olefins
• Gasoline C5 + high octane component for gasoline pool or light fuel
• Light cycle oil (LCO) blend component for diesel pool or light fuel
• Heavy cycle oil (HCO) Optional heavy cycle oil product for fuel oil or cutter stock
• Clarified oil (CLO) or decant oil: slurry for fuel oil
• Coke by-product consumed in the regenerator to provide the reactor heat demand.
FCC catalysts: Major breakthrough in the catalytic cracking process was development
zeolite catalysts which demonstrated vastly superior activity, gasoline selectivity, and
stability characteristics compared to original amorphous silica alumina catalyst (Hemler
and Smith, 2004).
Petroleum Refining 321

Year 1950 1970 1990

Zeolite content, wt.% 0 10 Up to 40
Particle density, g/cc 0.9 1 1.4
Relative attrition index 20 5 1

Today’s FCC catalysts porous spray dried microspherical powder (Bhatacharya D, 2011).
• Particle size distribution of 20–120 microns and particle density ~1400 kg/m3
• Comprising Y zeolite in many derivatives of varying properties
• Supplied under various grades of particle sizes and attrition resistance
• Continuing improvement metal tolerance, coke selectivity.
New breeds of catalyst are high metal tolerance with high matrix catalyst having
better accessibility, renderability and strip ability (Ghosh, 2006).
Options for clean fuel: For upgrading FCC products into acceptable blending
components, the following three steps are being used (Letzsch, 2005):
• Severe hydroprocessing of feed to FCC
• Treating each of the products in hydrotreater
• Combination of both upstream and downstream processing.
Modified catalytic cracking processes
Resid FCC (RFCC) process: The RFCC process uses similar reactor technology as the FCC
process and is targeted for residual feeds greater than 4 wt.% Conradson carbon. A
two-stage regenerator with catalyst cooling is typically used to control the higher coke
production and resulting heat.
Deep catalytic cracking (DCC)
Millisecond catalytic cracking (MSCC) process: Improvements in riser termination devices
have led to significant decreases in post-riser residence time and post-riser cracking.
The benefits of shorter catalyst-and oil contact time have been lower dry gas yields,
lower delta coke on catalyst and more selective cracking to gasoline and light olefins.
• Due to improvement in reactor design, there is lower regenerator temperature and
higher catalyst recovery.
Petro FCC process: The petro FCC process targets the production of petrochemical feed­
stock rather than fuel products. This new process, which utilizes a uniquely designed
FCC unit, can produce very high yields of light olefins and aromatics when coupled
with aromatics complex. The catalyst section of the petro FCC process uses a high-
conversion, short-contact time reaction zone that operates at elevated reactor riser
outlet temperatures.
Indmax technology: Residue to Olefin was developed by IOC R&D center and has been
successfully commissioned in IOC Guwahati Unit (Bhattacharya, 2011) and new bigger
capacity plant is coming at IOCL Paradip refinery. Some of the special features of the
technology are:
Operational features of Indmax technology are:
• Very high cat/oil ratio (15–25)
• Higher riser temperature (>550ºC)
• Higher riser steam rate
• Relatively lower regeneration temperature.
322 Chemical Process Technology

Benefits
• LPG 35–65 wt.%
• Propylene 17–25 wt.% feed
• High octane gasoline (95+)
Multifunctional proprietary catalyst
• Higher propylene selectivity
• Superior metal tolerance
• Lower coke mate.
Maximizing propylene output in FCC
New FCC processes are being operated to maximize the yield of propylene due to
growing demand of propylene. Significant scope exists in the refinery in Asia region
to enhance the production of propylene in Asia region (Ghosh, 2006). Maximizing
propylene yield from FCC is typically accomplished by combining a low rare earth
catalyst system with severe reaction condition (Amano T, Wilcox J, and Pauwels C, 2012.
“Process and catalysis factors to maximize propylene output”. Petroleum Technology
Quarterly 3, 2012, p.17). Some of the olefin maximizing technology are deep catalytic
cracking (DCC) based on riser bed catalytic cracking, Propylene–Max technology by
ABBS Lummus global, Maxo fin process by Mobil-MW Kellogg.

19.12 HYDROCRACKING
The development of upgrading technology for heavier stocks having high sulfur,
nitrogen and heavy metal (Ni, V) are becoming important. Hydrocracking is one of the
most versatile processes for the conversion of low-quality feedstocks into high quality
products like gasoline, naphtha, kerosene, diesel, and hydro wax which can be used as
petrochemical feedstock. Its importance is growing more as a refiners search for low
investment option for producing clean fuel. New environmental legislations require
increasing and expensive efforts to meet stringent product quality demands.
Hydrocracking processes uses a wide variety of feedstocks like naphtha, atmospheric
gas oil, vacuum gas oils, coke oils, catalytically cracked light and heavy cycle oil, cracked
residue, DE asphalted oils and produces high quality product with excellent product
quality with low sulfur contents. Comparison of catalytic cracking and hydrocracking
is given in Table 19.17.
The history of the hydrocracking process goes back to late 1920 when hydrocracking
technology for coal conversion was developed in Germany. During World War II,
two-stage hydrocracking was applied in Germany, USA and Britain. However, real
breakthrough in hydrocracking process was with the development of improved catalyst
due to which processing at lower pressure. Hydrocracking can process wide variety of
feedstocks producing wide range of products.
Feed: Straight run gas oil, vacuum gas oils, cycle oils, coker gas oils, thermally cracked
stocks, solvent DE asphalted residual oils, straight run naphtha, cracked naphtha.
Product: Liquefied petroleum gas (LPG), motor gasoline, reformer feeds, aviation turbine
fuel, diesel fuels, heating oils, solvent and thinners, lube oil, FCC feed.
To improve the economics of fixed bed resid hydrocracker, the fed quality is very
important and solvent DE asphalted feed is used to protect the unit from impurities.
(Sayles and Romero, 2011).
Petroleum Refining 323

Table 19.17: Comparison of catalytic cracking and hydrocracking

Catalytic cracking Hydrocracking
Carbon rejection Hydrogen addition
Riser-regenerator-configuration Downflow packed bed
LPG/gasoline Kerosene/diesel
Product rich in unsaturated components Few aromatics, low S- and N-content in product

19.12.1 Recent Development

There has been continuous development in the hydrocracking technology both in process
and catalyst. Some of the important development in hydrocracking has been mild
hydrocracking and resid hydrocracking. Mild hydrocracking (MHC) is characterized by
relatively low conversion (20–40%) as compared to convention hydrocracking which give
70–100% conversion of heavy distillate at high pressure. MHC route produces low sulfur
(10 ppm sulfur as desired by future diesel specification) diesel. New mild hydrocracking
route produces 10 ppm sulfur diesel which is produced by hydro-cracking under mild
pressure. MHC allows increasing diesel production through VGO hydro-conversion.
During the last decayed ebulliated bed residue hydrocracking has gained increasing
interestdue to high quality light and middle distillates with higher run length, lower
maintenance cost and better conversion (Kunnas, et al. 2010).
The yield of middle distillates obtained from hydrocracker is much more than that
obtained from other processes also; hydrocracker does not yield coke or pitches as by-
product. The increased demand for environmentally acceptable products forced the
refiners to accept stringent specifications for gasoline and diesel necessitating the use
of hydrocracking technology to limit sulfur and aromatic in petroleum products. No
posttreatment is required for the hydrocracker products.
Hydrotreatment and Hydrocracking Catalyst
Hydrocracking processes involved two types of catalyst:
• Hydropretreatment catalyst
• Hydrocracking catalyst
Hydrotreating (pretreat) catalyst: The main objective of pretreat catalyst is to remove
organic nitrogen from the hydrocracker feed allowing:
• Better performance of second stage hydrocracking catalyst, and
• The initiation of the sequence of hydrocracking reactions by saturation of aromatic
compounds.
Pretreat catalyst must have adequate activity to achieve above objectives within the
operating limits of the hydrogen partial pressure, temperature and LHSV.
Hydrocracking catalyst: Hydrocracking catalyst is a bifunctional catalyst and has a
cracking function and hydrogenation–dehydrogenation function. The former is provided
by an acidic support whereas the latter is imparted by metals. Acid sites (crystalline
zeolite, amorphous silica alumina, mixture of crystalline zeolite and amorphous oxides)
provide cracking activity. Metals (Noble metal (Pd, Pt) or non-noble metal sulfides (Mo,
Wo or Co, Ni) provide hydrogenation dehydrogenation activity. These metals catalyze
the hydrogenation of Feedstocks making them more reactive for cracking and hetero-
atom removal as well reducing the coke rate.
324 Chemical Process Technology

Zeolite-based hydrocracking catalysts have the following advantages: greater acidity

resulting in greater cracking activity, better thermal/hydrothermal stability, better
naphtha selectivity, better resistance to nitrogen and sulfur compounds, low coke
forming tendency, and easy regenerability.
Once-through hydrocracking process: The unit consists of the following sections:
• Furnace
• First stage reactor section
• Second stage reactor section
• High pressure separator
• Fractionation section
• Light ends recovery section.
In single stage process both treating and cracking steps are combined in a single
reactor. Single stage hydrocracking flow diagram is shown in Figure 19.8 (Mall, 2007).
In this process, the feed along with recycle unconverted residue from the fractionator
is first hydrotreated in a reactor and then the combined stream gases are fed to second
reactor where cracking takes place in the presence of hydrocracking catalyst.
In the single stage process the catalysts work under high H2S and NH3 partial pressure.
Two-stage hydrocracking process: The unit consists of the following sections:
• Furnace
• First stage reactor section
• Second stage reactor section
• Third stage reactor
• Fractionation section
• Light ends recovery section

Fig. 19.8: Sigle stage hydrocracking

Preheated feed is first hydrotreated in a reactor for desulfurization and denitrogenating
in presence of pretreat catalyst followed by hydrocracking in the second reactor in
presence of strong acidic catalyst with a relatively low hydrogenation activity. In
the first stage reactor the sulfur and nitrogen compounds are converted to hydrogen
sulfide and ammonia with limited hydrocracking. The two-stage process employs
inter stage product separation that removes H2S and NH3. In case of two stage process,
hydrocracking catalyst works under low H2S and NH3. Process flow diagram for two
stage hydrocracking process is shown in Figure 19.9 (Mall, 2007).
Petroleum Refining 325

Fig. 19.9: Two-stage hydrocracking process

Hydrocracking chemistry: Hydrocracking process is a catalytic cracking process which
takes place in the presence of an elevated partial pressure of hydrogen and is facilitated
by biofunctional catalyst having acidic sites and metallic sites. During hydrocracking
process, hydrotreating reactions and hydrocracking reactions are two major reactions
which take place.
A typical hydrocracking reaction is as follows.
C22 H46 + H2 = C16H34 + C6H14
Various hydrotreating reactions are hydrodesulfurization, denitrogenating, hydro­
deoxygenation, hydrometallization, olefin hydrogenation partial aromatics saturation.
Various hydrocracking reactions are splitting of C–C bond and or C–C rearrangement
reaction (hydrisomerization process), hydrogenation and dehydrogenation catalyst.
Effect of operating parameters: Various operating parameters affecting hydrocracking
are:
• Reaction temperature
• Hydrogen partial pressure
• Hourly feed velocity of the feed
• Hydrogen recycle ratio.
Temperature increase accelerates cracking reaction on acid sites and displaces the
equilibrium of hydrogenation reactions toward dehydrogenation. Too high temperature
limits the hydrocracking of aromatic structure (Raseev, 2003).
The pressure influences significantly the equilibrium of dehydrogenation–
hydrogenation reactions that take place on the metallic sites. The increase in pressure for
a given molar ratio H2/feed corresponds to increase in the partial pressure of hydrogen,
will produce an increase the conversion of the aromatic structures to saturated products
which will improve the quality of jet fuel, diesel fuel and oil with very high viscosity
index.
Effect of feedstock: A higher content of aromatic hydrocarbons requires higher pressure
and higher hydrogen/feed ratio, the lowest possible temperature and a higher hydrogen
consumption of hydrogen and the severity of the process.
Effects of feed impurities: Hydrogen sulfide, nitrogen compounds and aromatic molecules
present in the feed affect the hydrocracking reactions. Increase in nitrogen result in
lower conversion.
326 Chemical Process Technology

Ammonia inhibits the hydrocracking catalyst activity, requiring higher operating

temperatures. Polymeric compounds have substantial inhibiting and poisoning effects.
Polynuclear aromatics present in small amount in the residue deactivate the catalyst.
Effect of various parameters on catalyst life:
Variable Change/effect on catalyst life
Feed rate Increase–Decrease
Conversion Increase–Decrease
Hydrogen partial pressure Increase–Increase
Reactor pressure Increase–Increase
Recycle gas rate Increase–Increase
Recycle gas purity Increase–Increase
Hydrocracking technology provider
• Chevron: Isocracking
• UOP: Uni-cracking
• IFP: Hydrocracking
• BP, UK: Hydrocracking
• Shell: Hydrocracking
• Standard Oil: Ultra-cracking
• Linde: Hydrocracking
• Union Oil Co.: Uni-cracking
Catalyst deactivation: Catalyst activation may occur due to coke deposition and metal
accumulation. Coke depositions may be due to condensation of poly-nuclear and olefinic
compounds into high molecular weight which cover active sites. Metal accumulation
occurs at the pore entrances or near the outer surface of the catalyst.
Catalyst regeneration: Catalyst regeneration is done by burning off the carbon, and
sulfur and circulation of circulate nitrogen with the recycle compressor, injecting a
small quantity of air and maintaining catalyst temperature above the coke ignition
temperature.
Advanced hydrocracking: Advance hydrocracking process is hydrogen addition
process and yields middle distillate while zeroing fuel oil and coke production from
vacuum residue. The process involves slurry phase hydrocracking using a nano dispered
(slurry) nonaging catalyst (Rispoli, et al. 2009).

19.13 CATALYTIC REFORMING

Catalytic reforming is a major conversion process in petroleum refinery and petro­
chemical industries. The reforming process is a catalytic process which converts low
octane naphtha into higher octane reformate products for gasoline blending and aromatic
rich reformate for aromatic production. Basically, the process re-arranges or re-structures
the hydrocarbon molecules in the naphtha feedstocks as well as breaking some of the
molecules into smaller molecules. Naphtha feeds to catalytic reforming include heavy
straight run naphtha. It transforms low octane naphtha into high-octane motor gasoline
blending stock and aromatics rich in benzene, toluene, and xylene with hydrogen and
liquefied petroleum gas as a by-product. With the fast-growing demand in aromatics
Petroleum Refining 327

and demand of high-octane numbers, catalytic reforming is likely to remain one of the
most important unit processes in the petroleum and petrochemical industry. Various
commercial catalytic reforming processes are given in Table 19.18.

Table 19.18: Various catalytic reforming processes

Process Licensor
Rheniforming Chevron oil
Power forming ESSO oil/EXXON
Magna forming Atlantic richfield oil
Ultra forming British petroleum
Houdriforming Houdry process
CCR plate forming UOP
Octanizing Axen

19.13.1 Octane Number of Hydrocarbons

Octane number is a measurement of antiknock characteristics of fuels.
• Among the same carbon number compounds, the order of RONC is (Research Octane
Number)
Paraffins < Naphthenes < Aromatics
• Branched paraffins also have high octane. It increases with degree of branching.
Therefore, octane number of naphtha can be improved by reforming the hydrocarbon
molecule (Molecular rearrangement). Octane number of various hydrocarbons is
mention in Table 19.19. Such rearrangement takes place in reforming reactors in presence
of catalyst by way of numerous complex reactions.

Table 19.19: Octane number of various hydrocarbons

Hydrocarbon Octane number
n-Butane 94.0
i-Butane 102.0
n-Pentane 61.8
i-Pentane 93.0
Octane 100.0
Toluene 119.7

Feed consists of heavy straight run gasoline (HSR), naphtha, heavy hydrocracker
naphtha and naphtha containing (C6–C11) chain paraffins, olefins, naphthenes and
aromatics.

19.13.2 Process Steps in Catalytic Reforming

Basic steps in catalytic reforming involve:
• Feed preparation: Naphtha hydrotreatment
• Preheating: Temperature control
• Catalytic reforming and catalyst circulation and regeneration in case of continuous
reforming process
328 Chemical Process Technology

• Product separation: Removal of gases and reformate by fractional distillation

• Separation of aromatics in case of aromatic production.

Naphtha Hydrotreatment
Naphtha hydrotreatment is important steps in the catalytic reforming process for
removal of the various catalyst poisons. It eliminates the impurities, such as sulfur,
nitrogen, halogens, oxygen, water, olefins, diolefins, arsenic and other metals presents in
the naphtha feedstock to have longer life catalyst. Figure 19.10 illustrates hydrotreatment
of naphtha.
• Sulfur: Mercaptans, disulfide, thiophenes and poison the platinum catalyst. The
sulfur content may be 500 ppm.
• Maximum allowable sulfur content 0.5 ppm or less and water content <4 ppm.
• Fixed bed reactor containing a nickel molybdenum where both hydro-desulfurization
reactions and hydro-de-nitrification reactions take place.
• The catalyst is continuously regenerated. Liquid product from the reactor is then
stripped to remove water and light hydrocarbons.
Various sections in the naphtha hydrotreatment unit are:
Charge heater: Preheating reactor feedstock to reaction temperature of 340ºC. Charge
heater has four passes and four gas burners. Heater tubes are made up of SS-321.
Reaction section: The reactor consists of two catalyst beds.
Stripping section: Stripping section uses air for stripping the light ends mainly hydrogen
sulfide from reactor product, stripper temperature 14 kg/cm2 and temperature 172ºC.
Stripper reboiler: Stripper reboiler supplies heat required for stripper.
Operating variables in the naphtha hydrotreatment are:
• Reactor temperature
• Space velocity
• Hydrogen partial pressure
• H2/HC ratio, feed quality
• Stripper bottom temperature

Fig. 19.10: Hydrotreatment of naphtha

Petroleum Refining 329

19.13.3 Classification of Processes

• Semi-regenerative catalytic reforming
• Cyclic catalytic reforming
• Continuous catalytic reforming (CCR)
Various Types of Catalytic Reformers
1. Semi-regenerative fixed-bed reactors: In this type of reformers the catalyst generally
has a life of one or more years between regeneration. The time between two regene­
rations is called a cycle. The catalyst retains its usefulness over multiple regeneration.
2. Cyclic fixed-bed reformers: Cyclic reformers run under more severe operating
conditions for improved octane number and yields. Individual reactors are taken
offline by a special valving and manifold system and regenerated while the other
reformer unit continues to operate.
3. Continuous reformers: In these reformers, the catalyst is in moving bed and
regenerated frequently. This allows operation at much lower pressure with a resulting
higher product octane, C5+, and hydrogen yield. These types of reformers are radial
flow and are either separated as in regenerative unit or stacked one above the other.
4. Semi-regenerative catalytic reforming process: A semi-regenerative process uses
low platinum and regeneration is required only once a year. The process consists of
typically three reactor beds and furnace preheaters. The dehydrogenation is highly
endothermic and large temperature drop as the reaction proceeds. Multiple reactors
with intermediate preheat is required. Dehydrogenation of naphthene takes place in
first reactor and requires less catalyst. Last reactor is for isomerization of paraffins.
Typical catalyst distributions in three reactors are 20%, 30% and 50%. Figure 19.11
shows typical catalytic reforming process (Mall, 2007).

Fig. 19.11: Catalytic reforming process

330 Chemical Process Technology

Catalyst Regeneration
Performance of the catalyst decreases with respect to time due to deactivation. Reasons
for deactivation are:
• Coke formation
• Contamination on active sites
• Agglomeration
• Catalyst poisoning
Activity could be restored if deactivation occurred because of coke formation or
temporary poisons.
Objective of regeneration
• Surface area should be high
• Metal Pt should be highly dispersed
• Acidity must be at a proper level
• Regeneration changes by the severity of the operating conditions
• Coke formation can be offset for a time by increasing reaction temperatures.
Reactions in Catalytic Reforming
Following are the most prevalent main reactions in catalytic reforming:
Desirable
• Dehydrogenation of naphthenes to aromatics
• Isomerization of paraffins and naphthenes
• Dehydrocyclization of paraffins to aromatics.
Non-desirable: Hydrocracking of paraffins to lower molecular weight compounds.

Dehydrogenation and Dehydrocyclization

Highly endothermic, cause decrease in temperatures, highest reaction rates, aromatics
formed have high BP so end point of gasoline rises.
Dehydrogenation reactions are very fast, about one order of magnitude faster than
the other reactions. The reaction is promoted by the metallic function of catalyst.
Methyl cyclohexane toluene + H2
MCP benzene + H2

Dehydrocyclization: It involves a dehydrogenation with a release of one hydrogen

mole followed by a molecular rearrangement to form a naphthene and the subsequent
dehydrogenation of the naphthene.
i-paraffins to aromatics of paraffins
n-heptane toluene + H2
Favorable conditions: High temperature, low pressure, low space velocity, low H2/HC
ratio.
Isomerization: Branched isomers increase octane rating, small heat effect, fairly rapid
reactions.
Favorable conditions: High temperature, low pressure, low space velocity, H2/HC ratio
no significant effect
n-hexane neohexene
Petroleum Refining 331

Naphthenes dehydro-isomerization: This is a ring re-arrangement reaction, forms

alkyl-cyclo-hexane dehydrogenate to aromatic. Octane increase is significant; reaction
is slightly exothermic.
Coking: Coking is very complex group of chemical reaction. Linked to heavy unsaturated
products such as poly-nuclear aromatics. Traces of heavy olefins and di-olefins promote
coking. High feed FBP favors coking. Poor feed distribution in the reactor promotes
coking favored by high temperature.
Hydrocracking: Exothermic reactions, slow reactions, consume hydrogen, produce light
gases, lead to coking. Causes are high paraffin concentration in feed.
Process Variables
Following variables affect the reformate yield and quality of the product (Little, 1985;
Raseev, 2003; Mohan, 2011). Favorable conditions for different reforming reactions are
mentioned in Table 19.20.
• Reaction temperature
• Space velocity
• Reaction pressure
• H2/HC ratio
• Feedstock characteristics

Table 19.20: Favorable conditions for different reforming reactions

Reaction Pressure Temperature
Dehydrogenation of naphthenes to aromatics Low pressure High temperature
Isomerization of naphthenes Indeterminate Indeterminate
Dehydrocyclization of paraffins to aromatics Low pressure High temperature
Hydrocracking High pressure High temperature

Feed quality
• Naphthenes dehydrogenate very fast and give rise to aromatics. Therefore, N + 2A
is taken as index of reforming. Higher the N + 2A, better the quality to produce high
aromatics.
N = Naphthenes % A = Aromatics %
• Lighter fractions have poor naphthene and aromatic content, therefore poor feed for
reforming. Low IBP feed results in lower aromatics and H2 yield.
• Heavy fractions have high naphthene and aromatic hydrocarbon content. Therefore,
good reforming feed but tendency of coke formation is high.
Reaction temperature: Temperature is the most important operating parameter.
• By simply raising or lowering reactor inlet temperature, operators can raise or lower
the octane number of the product.
• Since all the reactor inlet temperatures are not necessarily identical; it is commonly
accepted to consider the weighted average inlet temperature (WAIT).
Space velocity:
• Liquid hourly space velocity (LHSV)
• Weight hourly space velocity (WHSV)
332 Chemical Process Technology

Vol/hour of reactor charge (60°F and 14.7 psia)

LHSV =
Vol. of catalyst

Weight/hour of reactor charge

WHSV =
Weight of catalyst

Reforming LHSV range = 1.0–3.0 L/hr

Below 1.0 LHSV, undesired side reactions, namely hydrocracking occurs which
reduce reformate yield, i.e. for every rise in LHSV of 0.1 between 1 and 2, about the
2ºC rise in temperature is required. The lower the space velocity (i.e. higher contact
time), the higher the severity assuming all other conditions unchanged. Lowering the
space velocity has the same effects as increasing temperature, i.e. increase the octane,
decrease the product yield, decrease H2 purity, increase coke deposit.
Reaction pressure: Reforming reaction pressure ranges (5–35 kg/cm2). Decreasing
pressure increases dehydrogenation of naphthenes and dehydrocyclization of paraffins
which favors an increase in production of aromatics and hydrogen (increase catalyst
coking and shorter cycle life). Higher pressure causes higher rates of hydrocracking
reducing reformate yield but decreases coking of catalyst resulting in longer cycle
life.
Hydrogen to hydrocarbon ratio
Moles of H2 in recycle gas
Hydrogen: Hydrocarbon ratio =
Moles of hydrocarbons
Main purpose of hydrogen recycle is to increase hydrogen partial pressure in the
reaction. H2 reacts with coke precursors removing them from the catalyst reforming
polycyclic aromatics. Higher the H2/HC ratio, higher the cyclic length. Two main
reasons for reducing H2, HC ratio are:
• Reduction in energy costs for compressing and circulating H2.
• Favors naphthene dehydrogenations and dehydrocyclization reaction.
Lowering of H2/HC ratio, from 8 to 4 carbon increase in 1.75 times and from 4 to 2
carbon increase 3.6 times.
19.13.4 Catalyst in Catalytic Reforming
Monometallic: (Pt),
Bimetallic: (Pt, Rhenium)
Acid activity: Halogens/silica incorporated in alumina base.
Metallic function: It promotes dehydrogenation and hydrogenation. It also contributes
to dehydrocyclization and isomerization.
Acid function: It promotes isomerization, the initial step in hydrocracking, participate
in paraffin dehydrocyclization.

Stages in Historical Development of Reforming Catalyst in Indian Scene

• Development of lows Pt monometallic catalyst IRC-1002 by IPCL for BT production.
• Commercialization of IRC-1001 catalyst in the first reactor of IPCL’s three reactor
system for xylenes production-1987.
Petroleum Refining 333

• Scale up and manufacture of bimetallic catalyst IPR-2001 at IPCL’s catalyst division

• Commercialization of bimetallic catalyst at MRL for gasoline production-1990
• Commercialization of bimetallic catalyst IRC-1002 by IPCL for BT production
• Commercialization of monometallic catalyst at IRC-1002 in BPCL reformer for BT
production-1990
• Development of improved versions of reforming catalysts:
ƒ High rhenium catalyst—Recipe ready for scale up.
ƒ Multimetallic catalyst—Recipe ready for commercial trial.
• Spheroidal catalyst—CCR operations recipe in advanced stage:
ƒ Catalyst used nowadays is platinum on alumina base.
ƒ For lower pressure stability is increased by combining rhenium with platinum.
ƒ Pt serve as a catalytic site for hydrogenation and dehydrogenation reactions
• Chlorinated alumina provides acid site for isomerization, cyclization, and hydro­
cracking reactions.
• Catalyst activity reduced by coke deposition and chlorine loss
• As catalyst age’s activity of the catalyst decreases, so temperature is increased as to
maintain the desired severity.
Advantages of Bimetallic and Multimetallic Catalyst over Monometallic Catalyst
Enhanced Resistance to Coking
• Lower fouling
• Higher coke tolerance
• Longer cycle length for S–R units
• Low pressure and low H2/HC ratio.
Operation
• High octane
• High aromatics
• High yields of desirable products
Better yield stability
Lower temperature requirement
Better tolerance to high temperature
Better regenerability
High ultimate life
Catalyst Poisons
Temporary poisons: Temporary poisons are those impurities which can be removed during
various pretreatment process like sulfur, nitrogen.
Permanent poisons: Permanent poisons are those impurities present in the feed which is
irreversible damage to the catalyst.
Source and maximum level of catalyst poisons are given in Table 19.21.
Table 19.21: Source and maximum level of catalyst poisons
Poisons Max. level wt% Source
Arsenic 1 PPB SR or cracked naphtha
Lead 5 PPB Recycle
Contd...
334 Chemical Process Technology

Table 19.21: Source and maximum level of catalyst poisons (Contd...)

Poisons Max. level wt% Source
Copper 5 PPB Corrosion
Mercury 5 PPB Naphtha condensate
Iron 5 PPB Corrosion
Silicon 5 PPB Foaming additives
Nickel 5 PPB Corrosion
Chromium 5 PPB Corrosion

19.14 ALKYLATION, ISOMERIZATION, AND POLYMERIZATION ALKYLATION

Alkylation process commercialized in 1938, since then there has been tremendous
growth in the process. In US and Europe, about alkylate is about 11–12% and 6% in
the gasoline pool respectively. Alkylate is a key component in reformulated gasoline.
Alkylation processes are becoming important due to growing demand for high octane
gasoline and requirement of low RVP, low sulfur, low toxics. Alkylate is an ideal blend
stock to meet these requirements (D’Aquino and Mavridis, 2007).
The process of alkylation in different iso-paraffins using olefins were developed
during thirties using aluminum chloride catalyst, however, later catalyst was replaced
by HF and sulfuric acid. Although butylenes alkylation is one of the most commonly
used processes, however, alkylation of amylenes obtained from C5 fraction of FCC can
be another route to increase the availability of alkylate. Alkylation of C5 cut from FCC
can significantly reduce RVP of finished gasoline pool.

19.14.1 C5 alkylate
Amylene alkylation has twofold advantage. It increase the volume of alkylate available
while decreasing Reid vapor pressure and olefinic content of gasoline blend stocks.
The process of HF alkylation produces high octane blend stock for isoparraffin (mainly
isobutane) and olefin (propylene, butylene and amylenes) in the process of HF catalyst
to meet all the criteria of reformulated gasoline. Replacing high-risk toxic liquid acids,
such as hydrofluoric acid (HF) and sulfuric acid with solid acid catalysts is challenging
goal isoparraffin alkylation technology.
Process
The reaction involved in aliphatic alkylation consists of conversion of isobutane and
butylenes to iso-octanes using HF catalyst. Commonly alkylation process used are
mentioned in Table 19.22.
i–C4H4 + i–C4H4 C8H18
The side reaction results in increased isobutane consumption increased acid
consumption increased acid soluble formation, equipment handling and for the
corrosion problem. Figure 19.12 gives the details of isoparaffin alkylation mechanism
(Mukherjee and Nehlsen, 2006).
Some of the other side reaction is the formation of paraffin, which boils above
and below the desired product. Impurities in the feed acid and normal operating
practices all can contribute to additional side reactions. Comparison of Alkyclean
technology with modern sulfuric acid and hydrofluoric acid technologies is shown in
Table 19.23.
Petroleum Refining 335

Table 19.22: Common alkylation processes

Process Description
CONOCO Phillips process Alkylation of propylene, butylenes, pentenes and isobutane to high
(Reva Process) quality motor fuel using HF catalyst
Stratco INC Alkylation of propylene, butylenes and amylenes with isobutane
using strong sulfuric acid to produce high-octane branched-chain
hydrocarbons using effluent refrigeration alkylation process
UOP HF Alkylation Process Alkylation of isobutane with light olefins (propylene, butylenes
and amylenes to produce branched-chain parafinic fuel) using
hydrofluoric acid catalyst. More than 100 commercial processes
UOP AlkyleneTM UOP Alkylene process is based on solid catalyst (HAL-100) for
alkylation of light olefins and isobutane to form a complex mixture
of isoalkanes which are highly branched trimethyl pentanes (TMP)
that have high octane blend values of approximately 100
Exxon Alkylation Alkylation of propylene, butylenes and penrylene with isobutene in
the presence of sulfuric acid catalyst using autorefrigeration
Products: A low sensitivity, highly iso, low RVP, high octane gasoline
blend stock paraffinic
Alkyl clean solid acid The alkylation process uses a robust zeolite solid acid catalyst
alkylation technology formulation coupled with a novel reactor processing scheme to yield
a high quality alkylate product. The catalyst contains no halogen.
Source: ABB Lumus Global [Link]/lumus.

Fig. 19.12: Isoparaffin alkylation mechanism (Source: Mukherjee and Nehlsen, 2006).
The key factors to be controlled in alkylation process are (Jezak, 1994):
• Maintaining proper composition of reaction mixture which include isobutene olefins
and the HF acid
• Maintaining the proper reaction environment which includes adequate contacting,
controlled temperature, and freedom from surges
• Making a proper separation of the reactor effluent into its various components

19.14.2 Isomerization
Petroleum fractions contain significant amounts of n-alkanes and the isomerization
of alkanes into corresponding branched isomers is one of the important processes in
refining (MastudaT, sakagami H, Takahashi N. Catalysis Today 81, 2003;p.31). The
highly branched paraffins with 7–10 carbon atoms would be the best to fulfill the recent
requirements of the reformulated gasoline (Rossini S. Catalysis Today 2003;p.77, 467).
The production of paraffin bases high–octane gasoline blend stock, such as isomers
from isomerization of light and mid cut naphtha might be a key technology for gasoline
supply to cope with future gasoline regulation (Visanandham and Garg, 2010).
336 Chemical Process Technology

Table 19.23: Comparison of Alkyclean technology with modern sulfuric acid and
hydrofluoric acid technologies
Parameter Modern sulfuric acid Modern hydrofluoric Alkyclean
technology acid technology
Base condition C4 feedstock C4 = feedstock C4 = feedstock
Product RON 95 95 95
Product MON Base Base or better Base or better
Alkylate yield Base Base 90% of base
Total installed cost Base 85% of base 50% of base
Total installed cost, Base Less None
including OSBL
(regeneration,
facilities, and /or
safety installations)
ASO yield Base Less None
Equipment High High Much lower
maintenance
Corrosion problems Yes Yes Higher
reliability and on- Base Base Match FCC or better/
stream factor shorter
Safety Unit specific safety Safety precautions No special precautions
pre­cautions as well as required that extend other than those for
transport precautions throughout refinery any refinery process
unit specific precautions very specific unit
Catalyst H2SO4 HF Zeolite
Environmental Significant waste Significant waste No emissions to air,
streams generated streams generated water, or ground
Source: Refining processe 1998. Hydrocarbon Processing. November 1998, 53, Graves, 2003,
Rroseseler, 2003, Himes, et al. 2003, Gravely, 2004.

Light naphtha and paraffin isomerization recognizes emerging technologies in order

to boost octane in light gasoline fractions. Recent pricing trends show isomerization
could be a significant contributor to octane pool which will offset the loss from gasoline
desulfurization and aromatic reduction. Isomerate as % of gasoline used is USA 8%,
Western Europe 16%. Isomerization involves:
• Isomerization of light paraffins
• Isomerization of C5–C6 paraffins
• Isomerization of n-butane.
Isomerization of C5–C6 paraffins: Allow low octane number paraffins 5 and 6 carbon
atoms into higher octane number paraffins
n-pentanen-isopentane:
n-hexane to 2-methyl pentane, 3 methyl pentane (low octane 75)
2,2 dimethyl butane, 2,3 dimethyl butane
Isomerization of n-butane; to produce isobutene feed for alkylation or as source of
isobutane dehydrogenation to manufacture MTBE.
Petroleum Refining 337

Isomerization Catalyst
Two types of isomerization catalyst, zeolite and chlorinated alumina, have been used.
Zeolite catalyst requires higher temperatures and provides lower octane boost while
chlorinated alumina results in highest octane; however, it has higher sensitivity to
feedstock impurities requiring strict feed pretreatment to eliminate oxygen, water,
sulfur and nitrogen containing compounds (Doumergue and Matthews, 2001).
• Zeolite
• Chlorinated alumina
Zeolite catalyst requires higher temperatures and provide lower octane boost.
Chlorinated alumina results in highest octane; however, it has higher sensitivity
to feedstock impurities requiring strict feed pretreatment to eliminate oxygen, water,
sulfur and nitrogen containing compounds.
Isomerization of Light Naphtha
C5/C6 feed either from straight run crude distillation or from catalytic reforming.
Table 19.24 gives details of isomerization of light paraffins catalyst.
Reformate: Separated in lighter mostly benzene and heavier containing C7.
Catalyst: Zeolite or Pt on chlorinated alumina (Table 19.25).

Table: 19.24: Isomerization of light paraffins catalyst

Isomerization catalyst
1st generation Friedel and Crafts AlCl3 catalysts, exhibit very high activity at low temperature
(980–100ºC)
2nd generation Metal/support bifunctional catalyst essentially Pt/alumina sensitivity to
poisons are less acute, however, require higher temperature (350–550ºC)
3rd generation Metal/support bifunctional catalysts with increased acidity by halogenation
of the alumina support. Sensitive to poisons and need pretreatment, corrosion
problem. High activity at low temperature (120–160ºC)
4th generation Bifunctional zeolite catalysts, very resistant to catalyst poison and feed does
not need pretreatment

Table 19.25: Operating condition: Pt on chlorinated alumina and Pt on zeolite

Pt on chlorinated alumina Pt on zeolite
Temperature (ºC) 120–180 250–270
Pressure 20–30 15–30
–1
Space velocity (h ) 1–2 1–2

H2/HC ratio 0.1–2 2–4

Product RON 83–84 78–80

Once-through Process
1. Recycle process: Unconverted n-paraffins and any single branched isomers from
double branched isomers
2. Recycling with distillation: Deisohexanizer
3. Recycling with adsorption: Adsorption on molecular sieve: n-paraffins are adsorbed
and separated by desorption.
338 Chemical Process Technology

Isomerization of n-butane
To produce isobutene feed for alkylation or as source of isobutene dehydrogenation
to manufacture MTBE.

UOP butamar process

• Catalyst: Pt/chlorintated Al2O3
• Operating condition: Temperature: 180–220ºC
• Pressure: 15–20 bar
• Soacevel: 2h–1
• H2/HC: 0.5–2.

UOP isomerization technologies: Some of the UOP light paraffin isomerization

technology are (Rajaram Panchapakesan, 2005):
• Penex™: Higher octanes, higher product yields more than 120 licensed units.
• Par-ISOM™: UOP introduced par-ISOM™ in 1996 using zeolite chloride sulfate
of zirconium catalyst. It is chracterized by lower equipment cost, multiple catalyst
approach. Some advantages of Penex process are maximum octane balls, high octane,
best long-term profitability, and higher investment cost. It can handle undesired
feedstocks including feed and process high benzene content feeds. It has wide range
of operation. Penex once through Penex plus™ for extra high benzene levels DIH,
DIP/DIH, MDEX™.
• Penex: Para-ISOM process with PI-242 catalyst: Best LPG production, good octane,
rapid payback, low investment cost.

19.14.3 Polymerization
Polymerization processes have received considerable interest in petroleum refining
because of the higher requirement of reformulated gasoline and phasing of MTBE. The
process may be attractive in two main areas (Leprince, 1998).
• Upgrading of C2 and C temperature: 150–200ºC, Pressure: 30–50 bar, space velocity
0.3–0.5 m3/h per m3 cuts from catalytic cracking for oligomerization ethylene and
propylene to olefinic gasoline.
• Producing high quality middle quality.

19.14.4 Lube Refinery

Large number of natural lubricating and specialty oils are produced by blending a
small amount of lubricating oil base stocks and additives. Important properties of
lubricating oils are: viscosity index (VI), pour point, oxidation resistance, flash point,
boiling temperature, acidity (neutralization number). Undesirable characteristics in
lubricating oil are high pour points: large viscosity changes with temperature (low VI),
poor oxygen stability, poor color, high cloud points, high organic acidity, high carbon,
and sludge-forming tendencies.
Lubricants consist of base stocks and additives. Crude oils are single common
source of base stocks. Lubricating characteristics of base stocks are influenced by crude
source, base oil properties. Lube processing requirement is a function of hydrocarbon
composition of feed and target base oils properties.
Petroleum Refining 339

Three main steps in production of lubricating oil are refining, dewaxing, deasphalting,
and finishing step to improve color and oxidation stability.

Dewaxing
It helps the lube oil to flow properly at ambient temperatures. There are two processes:
Refrigeration to crystallize the wax and selective hydrocracking.
Solvent dewaxing is used to remove the wax so that lubricating oil can be used at low
temperature. The process involves extraction and crystallization followed by filtration
and recovery of solvent. Propane is used for dewaxing.
Additives required to impart or enhance the properties of oil are dispertants,
detergent, dust, oxidation corrosion and foam inhibitors, viscosity improvers, pour
point depressment and friction modifiers.
Improving the cold flow properties of paraffinic feedstocks in a selective way by
catalytic dewaxing has become important in petroleum refining. Catalytic dewaxing
using recent developments in dewaxing catalyst provides an alternative method for
clod flow improvement in diesel and lube oil (Szynkarczuk, et al. 2014).

Deasphalting
Propane is used as the solvent to extract the lube oil from the asphalt. The heavier
the feedstock, the higher the ratio of propane is required. UOP solvent deasphal­-
ting process is unique separation process in which residue is separated by boiling
point and produces low contaminant deasphalted oil rich in paraffinic type molecules
([Link]).

19.15 DESULFURIZATION PROCESSES AND RECOVERY OF SULFUR

The level of sulfur in the past two decades has steadily increased due to use of more
and more heavier crude, use of cheaper high sulfur crude which has forced the refining
industry to go for additional facilities like ultra-desulfurization for gasoline and
diesel to meet the requirement of the stringent sulfur emission standards. Require­-
ment of sulfur content for MS and HSD is given in Table 19.26. Sulfur is one of the major
impurities in heavy crude resulting higher concentration of sulfur compounds in the
undesulfurized product stream. Sulfur content in the crude varies widely depending on
the origin. Table 19.27 shows sulfur content in crude oil. The variation is considerable
and this impacts the processing scheme as well as the product slate (Goel, et al. 2008).
Sulfur contents commonly used are sweet and sour crudes. Due to increasing environ-
mental concerns, stringent limits on sulfur levels in fuel are being implemented world
over to achieve target of sulfur below 100 ppm. Deep hydrodesulfurization is required
which is an additional capital cost as well as an energy intensive step (Garg, 2010).
Table 19.28 gives the details of reactivity of sulfur compounds present in crude oil.

Table 19.26: Sulfur requirement in different gasoline diesel in PPM

BIS 2000 Bharat stage-II Euro-III equivalent Euro-IV equivalent
MS 1000 500 150 50
HSD 2500 500 350 50
340 Chemical Process Technology

Table 19.27: Sulfur content in crude oil

Crude name ‘S’ Content, (wt%) Crude name ‘S’ Content, (wt%)
Bombay high 0.17 Doba 0.16
Bonny light 0.14 Ratawi 3.88
Arab heavy 2.87 Miri light 0.078
Arab light 1.09 Tapis blend 0.028

Table 19.28: Reactivity of sulfur compounds present in crude oil

Sulfur compound Relative reaction rate Boiling pounts
Thiophene 100 185
Benzothiphene 50 430
Dibenzothiophene 30 590
Dimethyldibenzothiophene 5 600–620
trimethyldibenzothiophene 630–680
Source: Nakamura, 2004.

19.15.1 Sulfur Output

Sulfur output from the refinery takes places as one of the followings (Goel, 2008):
• Sulfur content in finished product
• Sulfur emission into atmosphere in the form of SO2
• Sulfur recovery in sulfur recovery unit
Sulfur distribution in typical refinery is given below:
• Sulfur in various products 58%
• Product sulfur 41%
• Sulfur emission 1%
19.15.2 Future Demand in Indian Refineries
• Use of more sour crudes
• More stringent sulfur specifications for distillate products
• More stringent specifications for SOx emission through flue gas
• Leading to enhancement in sulfur recovery and capacity augmentation
• Estimated sulfur recovery capacity in Indian Refineries to be more than double in
near future
• Environmental regulations have been the major driving force for reducing sulfur in
refinery products.
19.15.3 Process Used to Remove Sulfur from Different Products
• LPG: LPG treating unit
• Gasoline: Hydrotreating unit
• ATF: Merox/hydrotreating
• Diesel: Hydrotreating
• Sulfur lands up in the fuel gas as H2S during hydrotreating
• H2S in fuel gas produces SOx while burning in the fired heater
• Environmental norm for SOx: 50 ppm while burning fuel gas
Petroleum Refining 341

19.15.4 Hydrotreatment Processes

Hydrotreatment of the various streams from refinery and petrochemical industries has
become integral part in order to meet the feed standards of various processes in order
to avoid catalyst poisoning, improving quality of products and meet the environmental
standards. Hydroprocessing technologies consist of any one of the following processes:
Pretreatment (hydrotreatment) of naphtha and gas oil, residue for catalytic reforming,
catalytic cracking and hydrocracking in order to remove the impurities of sulfur, nitrogen,
heavy metal, etc. These processes have been discussed separately in the chapters on
catalytic reforming, catalytic cracking, and hydrocracking. Various hydrotreament
processes removes sulfur compound which must be recovered in sulfur recovery units.
Figure 19.13 illustrates the major sources of sulfur and recovery processes in refinery.

Fig. 19.13: Major sources of sulfur and recovery processes in refinery. (Source: Tarapdar T.
Sulfur recovery technologies: Present and future development. June 2011 Petrotech.)

Main reaction involved in desulfurization is removal of sulfur compounds in form of

H2S. Degree of desulfurization varies from feed to feed with nearly complete removal
to about 50–70% for heavier residual materials.
Relative desulfurization reactivity is in order of increasing difficulty is given below
(Kokayeff, 2003):
Thiphenol > ethyl mercaptan > diethyl sulfide > diphenylsulfide > 3-metrhyl-1
butanethiol > diethylsulfide > di(ropylsulfide > diisomylsulfide > thiophene
Sulfur recovery units characteristics:
• Small to medium size sulfur recovery units
• From a few tons to a few hundred tons/day
• Guwahati refinery, IOCL: 5 TPD
• Reliance refinery, Jamnagar: 2025 (3 × 675) TPD
• Feed composition varies, linked to refinery operating mode and crude feedstock
• High flexibility required, multiple trains
• Acid gas always rich (high H2S content)
• Ammonia (from sour water stripper) always present, sometimes in relatively high
quantities
342 Chemical Process Technology

19.16 SULFUR RECOVERY UNIT

Sulfur recovery unit consist of recovery of sulfur from H2S present in acid gas from
amine treating/regeneration unit and H2S from sour water stripper section. Hydrogen
sulfide content of the feed gas is converted to elemental sulfur. Typical sulfur recovery
unit is shown in Figure 19.14.
1. Amine absorption and regeneration: Absorption of H 2S-bearing stream and
regeneration of amine. H2S-rich stream from amine regeneration is sent to sulfur
recovery unit.
2. Sour water stripping: Sour water is tripped off its sulfur and recycled. H2S is sent to
sulfur recovery unit.
3. Amine absorption unit: Various hydrodesufurization processes in the refinery
and hydrocracker unit generate large quantity of H2S. H2S-bearing gases from
various unit is sent to amine treating unit which uses amine as a solvent for
absorbing H2S and subsequently releasing H2S as H2S-rich stream in the amine
generator.

Fig. 19.14: Typical sulfur recovery unit

19.16.1 Merox (Mercaptan Oxidation Unit)

Merox process is used in the refinery for controlling the mercaptan sulfur in gases, LPG,
naphtha and other petroleum fractions. The Process is used for the chemical treatment
of LPG, gasoline and distillates from FCCU, OHCU, etc. to remove mercaptans.
Mercaptans are either extracted from the stream or sweetened to acceptable disulfides.
For treatment of light feedstocks such as LPG, no sweetening is required as mercaptans
are nearly removed by extraction. However, feed containing higher molecular weight
mercaptans and may require a combination of Merox extraction and sweetening
using catalyst. Catalysts promote the oxidation of mercaptans to disulfide using air as
the source of oxygen. Merox treatment can in general be used in following ways
(Dziabis, 2003):
• To improve lead susceptibility of light gasoline
• To improve the response of gasoline stocks to oxidation inhibitors added to prevent
gum formation during storage
• To improve odor of all stocks
• To reduce the mercaptans content to meet product specifications
Petroleum Refining 343

• To reduce the sulfur content of LPG and light naphtha products

• To reduce sulfur content of coker FCC olefins to save acid consumption in alkylation.
Process
Pretreatment (remove H2S and naphthenic acids by dilute alkali solution)
Extraction (remove caustic soluble mercaptans)
Sweetening (Oxidation of mercaptans to disulfides)
RSH + NaOH RSNa + H2O
4NaSR + O2 + H2O RSSR + NaOH

Posttreatment (remove caustic haze)

(Caustic settler, wash water, sand, clay filters)
Sulfur Recovery from H2S
Sulfur recovery now has become one of the most critical aspects of sulfur management
and affects emission sulfur dioxides significantly in the refinery. There are two sulfur
recovery processes are:
• Claus process (used earlier)
• Super Claus process
Conventional Claus process has only 99% sulfur recovery. In order to meet the
sulfur emission standards now Claus process has been improved substantially to meet
the standards. Modern Claus process is shown in Figure 19.15. New processes are
characterized by:
• New catalysts
• COS and CS2 hydrolysis (increased recovery)
• Direct conversion of H2S to sulfur by oxidation (Super Claus Process)
• Direct conversion of H2S to sulfur by reduction (Pro Claus Process)
• High efficiency burners (NH3, BTEX destruction)
• Analyzers based control
• Enriched air or oxygen blown thermal reactors.
Super Claus Process
The Super Claus process was developed to catalytically recover elemental sulfur
from H2S containing Claus tail gas to improve the overall sulfur recovery level. The
Super Claus process was commercially demonstrated in 1998, and today now more
than 160 units are under license and over 140 are in operation. Super Claus process
achieves high sulfur recover levels by suppressing SO2 formation in claus stages
and selectively oxidizing H2S in presence of oxygen using proprietary catalyst (Scheel,
2011).
A typical Super Claus sulfur recovery unit consist of following sections:
• Combustion chamber
• Claus reactor
• Super Claus reactor
• Incinerator
• Degassing section
344 Chemical Process Technology

Function of Claus Reactors

• Claus reaction at catalytic region
2H2 + SO2 3/xSx + 2H2O + 93 k
(Where x = 6 and 8 mainly)
• Hydrolysis of COS and CS2 at tempe­
ratures above 300ºC
COS + H2O CO2 + H2S
CS2 + 2H2O CO2 + 2H2S

Function of Super Claus Reactor

H2S + 0.5O2 1/8S8 + H2O + 208 kJ

Super Claus process use selective oxi­da­

tion catalyst minimizes side reactions and
increase sulfur recovery.

Claus Process Limitations

• Thermodynamically limited conversion: Fig. 19.15: Modified Claus process
the ‘air to clean gas’ ratio’s is maintained (Source: Taraphdar, 2011)
to produce ratio of exactly 2/1 (optimum
ratio) in the burner effluent gases.
• Increases H2O content to 30 vol.% decreasing H2S and SO2 concentrations.
Formation of non-recoverable S-compounds due to side reactions.
The big difference between Super Claus catalyst and Claus catalyst is that the reaction
is not equilibrium based. Therefore, the conversion efficiency is much higher than
the equilibrium limited Claus reaction. Super Claus is a non-cyclic process that has
repeatedly shown simplicity in operation, high online reliability and sulfur guarantees
up to 99.3 % (Scheel, 2011).

Super Sour Process

Stringent environmental regulations have necessitated higher recovery of H2S from
sour water stripper unit design. Super Sour process ensures minimum H2S loss. The
process employ additional hot feed flash drum upstream of cold feed surge drum. The
H2S rich vapors from hot feed flash drum upstream of cold feed surge drum is routed to
a small amine scrubber to absorb liberated H2S. The H2S lean gas containing primarily
hydrocarbons is then routed to incinerator of the sulfur recovery unit. The absorbed
H2S rich amine is recovered in the amine regenerator and is fed to the sulfur unit for
converting it to sulfur (Sharma and Nag 2011).

INDE Treat and INDE Sweet Technology (Indian Oil Technologies 2001)
INDE Treat and INDE Sweet Technology is based on the continuous film contactor (CFC)
for effective removal of undesirable compounds at lower cost. It can remove H2S from
LPG, mercaptans from LPG, naphtha, gasoline and ATF/Kerosene, naphthenic acid
from diesel, acid gases from natural gases, fuel gases and can regenerate spent caustic
if required. CFC technology which is the heart of process. Salient features of CFC are:
• Non-dispersive contacting
• Enormous surface
Petroleum Refining 345

• High mass transfer efficiency

• Based on caustic/amine
• Efficient removal of contaminants
• No aqueous phase entrainment
• Low caustic/amine consumption
• Low cost
• Can be easily retrofitted in existing mixer settler units.
Merichem Fiber Film Contactor Technology
The process is based on continuous film contactor (CFC), fiber film contactor technology
for removal of impurities from hydrocarbon streams. The process achieves non-
dispersive phase contact without problem inherent in conventional dispersive mixing
devices (Mall 2016).

BIBLIOGRAPHY
1. Amano T, Wilcox J, Pouwels C. “Process and catalysis factors to maximize propylene output”.
Petroleum Technology Quarterly, 3, 2012, p.17.
2. Bhatnagar AK. “Analytical Development in crude oil and product characterization”. In Challenges
in crude oil evaluation: Ed. Nagpal, JM. New Delhi: Tata McGraw-Hill Publishing Company
Ltd, 1996, p.1.
3. Bhatachrya D.”Fluid catalytic cracking: process fundamentals” 6th Summer School on Petroleum
refining & Petrochemicals June 6–10, 2011.
4. Catala KA, Karrs MS, Sieli G. “Advances in delayed coking heat transfer equipment”.
Hydrocarbon Processing. February 2009, p.45.
5. Chemical Industry Digest. February 2016, p.23.
6. Das T.”Shale gas” JOP March, 2011,p.35.
7. Dave RR, Khurana ML. “Evaluation of Feedstocks for aromatics olefins and surfactants Plants”. In
Nagpal JM (editor): Challenges in crude oil evaluation. New Delhi: Tata McGraw- Hill Publishing
Company Ltd, 1996, p.139.
8. Daziabis “UOP Merox process”. Hand book of Petroleum refining Processes edited by Meyers,
RA. Third edition. The McGraw-Hill Publication data 2004, p.11.31.
9. Debasis Bhattacharyya. “Fluid Catalytic Cracking: Process Fundamentals”, 6th Summer School
on Petroleum Refining & Petrochemicals 6th–10th June, 2011.
10. Domergue B, Matthews R. “Advanced recycle paraffin isomerisation technology”. Petroleum
Technology quarterly, Spring 2001, p.29.
11. (http:// economics [Link]/industry/energy/oil/ioc-plans-to-double-refining-
capacity-by-2030/articlesshow/[Link])
12. Garg MO. Invited talk 23rd National Convention of Chemical Engineers IIT Roorkee, 5–7 October,
2007.
13. Ghosh S. “Fluid catalytic cracking: An overview & future scenario”. Indian Chemical Engineer
special Issue, Vol 1,2002, p.27.
14. Ghosh S. “Recent advances in fluid catalytic cracking”. Petrotech society’s summer school
program on advances in Petroleum Refining industry, 3–8 July 2006 held at IIPM, Gurugram.
15. Goel SK, Khanna S, Zutshi DK. “Suplhur management in Refineries”. Chemical Industry Digest.
May 2008, p.80.
16. Gravely ML. “CONOCO Phillips reduced volatility Alkylation Process” (ReVAP) in Hand Book
of Petroleum Refining Process 2nd edition, edited by Meyers RA. McGraw Hill Companies, 2004,
p.1.79.
346 Chemical Process Technology

17. Graves DC. “STRACTO Effluent refrigerated H2SO4 alkylation system” in Hand Book of
Petroleum Refining Process 2nd edition, edited by Meyers RA. McGraw Hill Companies, 2004,
p.1.33.
18. Haizmann RS, Hunt P, Srinivas A, Banerjee S. “Maximize return from every barrel: Proven
residue upgrading technology” J. of Petrofed, Jan–March 2012, Vol.11, p.38.
19. Hemler CL, Smith LF. “UOP fluid catalytic cracking Process” in Hand book of Petroleum refining
Processes edited by Meyers RA. Third edition. The McGraw-Hill Publication data 2004.
20. Himes JF, Meister JM, Nowak, Franz-Marcus. “UOP HF alkylation technology”. In Hand Book
of Petroleum Refining Process, 2nd edition, edited by Meyers RA. McGraw Hill Companies,
2004, p.1.33.
21. Hobson GD, Pohl W. “Modern Petroleum Technology”, Vol. I & II, 5th edition, John Wiley &
Sons, New York, 1986.
22. [Link] [Link]
23. [Link]
24. [Link] [Link]
25. [Link]
through-2021/
26. Hull R, Stewart S, TeetsJ. “ Improving solids handling in delayed coker” PTQ 2011 p. 2011.
27. “INDE Treat and INDE Sweet Technology” Indian Oil Tech/T/2003/2004.
28. Jezak A. “C5 Alkylate: A Superior blending component”. Hydrocarbon processing/February
1994, p.47.
29. Joshi MK, Vijh LK. “Effect of crude quality on processing scheme and product slate” in Challenges
in crude oil evaluation: ed. Nagpal JM. New Delhi: Tata McGraw-Hill Publishing Company Ltd,
1996, p.39.
30. Kokayeff P. “UOP Unionfining Technology” Chapter 8.3, p.8.31, in Hand book of Petroleum
refining Processes edited by Meyers, RA. Third edition. The McGraw-Hill Publication data 2004,
Chapter 11.1, p.11.1.
31. Lapinski ML, Baird L, James. “Handbook Petroleum refining”. Ed. Meyers [Link] McGraw Hill
Companies, R. 4.3 2004.
32. Leprince P. “Oligmerisation” in IFP Petroleum refining Part 3 conversion processes” edited by
Leprince P. Editions Technip, 1998, p.321.
33. Letzsch W. “Improve catalytic cracking to produce clean fuels”. Hydrocarbon processing.
February 2005, p.77.
34. Kunnas J, OsvaskinenO, Respini M.”Mitigate fouling in ebullated-bed hydrocrackers”.
Hydrocarbon processing. October 2010, p.59.
35. Litle DM. “Catalytic Reforming”. Penn well, Tulsa, Okla, 1985, p.2.
36. Mall ID. NPTEL lecture Organic Chemical Technology, 2013
37. Mall ID. “Petrochemical processes technology”. First edition. Macmillan India 2006, reprint 2015,
New Delhi, second edition 2017, Laxmi Publication.
38. Mall ID.” Petroleum Refining Technology”. CBS Publisher, 2016.
39. Mandal KK. “Improve desalter control”. Hydrocarbon Processing, April, 2005,p.77.
40. MastudaT, Sakagami H, Takahashi N. Catalysis Today. 81, 2003, p.31.
41. Mishra AK, Unnikrishnan A. “Overview of the quality of crude oils processed in India” 1996,
p.22.
42. Nagpal JM (editor). Challenges in crude oil [Link] Delhi: Tata McGraw-Hill Publishing
Company Ltd, 1996, p.1.
43. Mohan Lal. “Catalytic Reforming” Process, Catalysts and Reactors. 6th Summer School on
Petroleum Refining & Petrochemicals, Indian Institute Of Petroleum Management, Gurugram,
June 6–10, 2011.
Petroleum Refining 347

44. Mukherjee M, Nehlsen J. “Consider catalyst developments for alkylation production”.

Hydrocarbon Processing, Sep., 2006, p.85.
45. Mukhulyonov IU, Kuznetsov D, Averbukh A, Tumarkina [Link].r “Chemical Technology”.
Mir Publishers, Moscow,1974.
46. Nakamura DN. “Product sulfur spec will determine future refining configurations”. Oil & Gas
Journal, Oct. 18, 2004.
47. Pathan MA. “Special feature on future of oil & gas sector India”. FIPI Volume 16 issue 1 Jan-
March 2017.
48. Prasada TSR. “Catalytic Reforming and recent Indian achievements”. Oncology Vol. 6, No.12,
May 1992, p.1.
49. Rajaram Panchapakesan. “Latest development UOP isomerisation catalysts”, National workshops
on catalysts in hydrocarbon processing, Nov 25–26, 2005, organised by memorial trust New Delhi
-110001.
50. Rajgopal S. “Petroleum refining and petrochemicals”. Refining Challenges and Trends. 6th
Summer School on June 6,2012, Organised by New Delhi.
51. Rana MS, Samano V, Ancheyta J, Diaz JAI. “A review of recent advances on process technologies
for upgrading of heavy oils and residua”. Fuel, vol. 86, (9), June 2007, 1216–1231.
52. Raseev S. “Hydrocracking in Thermal and Catalytic Processes in Petroleum refining” Marcel
Dekker, Inc2003, p.681.
53. Raseev S. “Thermal and catalytic Processes in Petroleum Refining”. Marcel Dekker, Inc: New
York, 2003.
54. Ravindranath K, Habubula M. “Hydro carbon condensate Fractionation in oil and gas processing
complex”. Chemical Engineering World. Vol 27, No.10, 1992, p.43.
55. Refining processes”. Hydrocarbon Processing. November 1998, p.53.
56. Rispoli G, Sanfilippo D, Amoroson A. “ Advanced hydrocracking technology upgrades extra
heavy oil”. Hydrocarbo Processing. December 2009, p.39.
57. Roeseler. “UOP AlkyleneTM process for motor fuel alkylation”. Hand Book of Petroleum Refining
Process. 2nd edition, edited by Meyers, RA McGraw Hill Companies, 2004, p.125.
58. Rosini S. Catalysis Today. 2003, 77, 467.
59. Sayles S, Romero S. “ Understanding differences between thermal and Hydrocracker”.
Hydrocarbon Processing. September 2011, p.2011.
60. Samanti RK. “Refining challenges and Trends” 6thSummer School on “ Petroleum refining and
petrochemicals” June 6, 2012, Organised by New Delhi.
61. Samtani RK. DGM (Exploration & Production) IOC Ltd. 6th June, 2011.
62. Sarkar S, Basak TK. “Heavy oil processing in IOCL Refineries”, Compendium 16th Technology
Meet, Feb 17–19, 2011.
63. Sarraf DK. “Special feature on future of oil & gas sector India” FIPI Volume 16 issue 1 Jan–March
2017.
64. Saxena AK. “Catalytic reforming” Advances in Petroleum Refining. Petrotech Summer School,
IIPM Gurugram, 5th July 2006.
65. Scheel F. “Innovative approach to sulfur recovery unit emissions Reductions”. Compendium
16th Refinery Technology Meet, Feb 17–19, 2011, organized by Centre of High Technology and
Indian Oil Corporation Ltd, Kolkata, West Bengal, India.
66. Sharma MK, Nag A. “Super sour Process” J. of Petrotech. July–September 2011, p.49.
67. Sieli GM. “Vis breaking the next generation”. Foster Wheeler Publication, 1998.
68. Singh S, Vaidya SM. “The benefits from refinery and petrochemical Integration”. Chemical
Industry Digest. August 2012, p.67.
69. SM Vaidya of IOCL. Hydrocarbon [Link]., 2017.
70. Speight JG. “The chemistry and technology of Petroleum”. Marccel Decker, Inc, New York, 1999.
348 Chemical Process Technology

71. Stratiev D, Kirilov K, Belchev Z, Petkov P. “How Feedstocks affect vis breaking operations”.
Hydrocarbon Processing. June 2008, p.105.
72. Subbul AH, Lauritzen JE, Heramco Hemblingn DE, Majdpour A, Saudi Aramco, Raffin AG,
Zeybek M, Moen T. “ Improved horizontal well cleanup and sweep efficiency with nozzle based
inflow control devices in sansone and cabonate reservoirs” Petrotech Journal. December issue
2009, p.13.
73. Szynkarczzuk Robinson, Michelle Huve Laurent. “Dewaxing challenging paraffinic feeds”.
Catalyst 2014, p.43.
74. Taraphdar T. “Sulfur Recovery Technologies–Present & Future Demand of Refineries”.Technip
KT India Ltd., Noida, June, 2011
75. Tondon D, Dang GS, Garg MO. “Vis breaking: a flexible process to reduce the pour point of
heavy crude oils”. J Petrotech Soc. June 2007, p.44.
76. Venkatraman NS. “Algae biofuel could be India’s savior”. Chemical News. July, 2012, p.40.
77. Verma, RP. “Hydroprocessing: Indian scenario”. Indian Chemical Engineer Special issue, Vol
1, 2002.
78. Visanandham N, Garg MO. “A novel catalyst for Improved C+ isomerisation of naphtha”.
Chemical Industry Digest. May 2010, p.65.
79. Watkins RN. “Petroleum refinery distillation”, Second edition, 1979, Gulf Publishing Company,
Houston.
20
Petrochemical Industry

20.1 INTRODUCTION
Petrochemical industries have revolutionized our life and are providing the major
basic needs of rapidly growing, expanding and highly technical civilization as a source
of fertilizers, synthetic fibers, synthetic rubbers, polymers, intermediates, explosives,
agrochemicals, dyes, and paints, etc. Modern petrochemical industry fulfill the
requirement of large number of products which are being used in some or other form
in daily life and also closely linked with the socioeconomic aspiration of people which
includes packaging to agriculture, automobiles to telecommunication, construction
to home appliances, health care to personal care, pesticides to fertilizer, textile to
tyre cord, chemicals to dyes, pharmaceuticals and explosives (Mall, 2007). Linkage of
socioeconomic of petrochemical in our life has been given in Table 20.1. There is hardly
any area of our life that is not impacted by petrochemicals.

Table 20.1: Petrochemical socioeconomic linkage

Group of product Areas
Plastics and polymers Agricultural water management, packaging, automobiles, telecommu­
nications, health and hygiene, education, transportation, building.
Synthetic rubber Transportation industry, chemical, electrical, electronics, adhesives,
sealants, coatings.
Synthetic fiber Textile, transportation, industrial fabrics, geotextiles, nonwoven fabrics.
Synthetic detergents Health and hygiene.
Industrial chemicals Drugs and pharmaceuticals, pesticides, explosives, surface coating, dyes
and intermediates, lubricating oil additives, adhesives, oil field chemicals,
antioxidants, chemicals, metal extraction, printing ink, paints, corrosion
inhibitors, solvents, perfumes, food additives.
Fertilizers Agriculture, polymers.
Source: Mall 2007, 2013, 2015, 2017.

The petrochemical industry is highly technological and capital intensive.

Developments in petrochemical technology are taking place very fast. Tremendous
resources and efforts are being continuously spent on increasing size of the plant, the
yield through continuous upgradation of catalyst, reducing energy consumption and
cost reduction through novel process rate, new chemistries or scale up approaches.
349
350 Chemical Process Technology

Due to huge population, the per capita consumption of petrochemicals in India is

about 506 kg compared to global weighted average 25 kg and China’s consumption of
around 25–30 kg. Oil refining and steam cracking of naphtha and natural gas (ethane
and propane) are the common routes of producing petrochemicals. Many Indian
refineries are now entering petrochemicals in a big way through green field projects
and expansions. Major ethylene complexes in India are given in Table 20.2. Top 10
global ethylene complexes are given in Table 20.3. Global regional capacity breakdown
of ethylene capacity is given in Table 20.4.

Table 20.2: Major ethylene complexes in India (metric tons)

Name of the complex Location Capacity Feedstock
Reliance (formerly IPCL) Vadodara 1,30,000 Naphtha
Reliance (formerly IPCL) Nagothane 4,00,000 Gas
Reliance (formerly IPCL) Gandhar 3,00,000 Gas
Reliance Hazira 2,50,000 Naphtha/Gas
Haldia petrochemicals Haldia 5,20,000 Naphtha
GAIL Auria 4,00,000 Gas
Oswal Agro Mumbai 23,000 Naphtha
Indian Oil Corporation Limited Panipat 8,00,000 Naphtha
Sources: Annual Report (2010–11, 2019–20), Department of Chemicals and Petrochemicals (Ministry
of Chemicals and Fertilizer, Govt. of India)

Table 20.3: Top 10 global ethylene complexes

Company Location Capacity, tpy
1 Formosa Petrochemical Corp. Mailiao, Taiwan, China 29,35,000
2 Nova Chemicals Corp. Joffre, Alta 28,11,792
3 Arabian Petrochemical Co. Jubai, Saudi Arabia 22,50,000
4 Exxon Mobi Chemical Co. Baytown, Tex. 21,97,000
5 Chevron Philips Chemical Co. Sweeny, Tex. 18,65,000
6 Dow Chemical Co. Terneuzen, Netherlands 18,00,000
7 Ineos Olifins & Polymers Chocolate Bayou, Tex. 17,52,000
8 Equistar Chemicals LP Channelview, Tex. 17,50,000
9 Yanbu Petrochemical Co. Yanbu, Saudi Arabia 17,05,000
10 Equate Petrochemical Co. Shuaiba, Kuwait 16,50,000
Source: Oil and Gas Journal, July 4, 2011.

Table 20.4: Regional capacity breakdown

Ethylene capacity, tpy
Asia-Pacific 4,26,31,000
Eastern Europe 79,71,000
Middle East, Africa 2,33,57,000
Contd...
Petrochemical Industry 351

Table 20.4: Regional capacity breakdown (Contd...)

Ethylene capacity, tpy
North America 3,45,08,000
South America 50,83,500
Western Europe 2,49,04,000
Total Capacity 13,84,54,500
Source: Oil and Gas Journal, July 4. 2011.

The potential possible in India can just be imagined, now with growth in various
sectors of economy like automotives, construction, textiles, etc. taking off well (Chemical
Industry Digest, August 2010, p.5). Polymers accounts for around 50% of total basic major
petrochemicals for the year 2019–20. The production of basic major petrochemicals in
2019–20 was about 8054 thousand metric tons (Annual Report 2019–2020, Department
of Chemicals and Petro-Chemical, Ministry of Chemicals and Fertilizer, Government
of India).

20.2 STRUCTURE OF PETROCHEMICAL COMPLEXES

The petrochemical complexes involve one or a combination of the following operations
(Table 20.5) (Mall, 2007).

Table 20.5: List of intermediate chemicals and target products

First generation intermediates Hydrogen, ammonia, methanol, olefins and dienic hydro­
carbons, ethylene, propylene, butadiene, isoprene, etc.
Aromatic hydrocarbons, benzene, toluene, xylenes, styrene, etc.
Second generation intermediates Introduction of various heteroatoms into final molecule
including oxygen, nitrogen, chlorine and sulfur by various
unit process intermediates
Target product Plastics, synthetic fiber, fertilizers, solvents, elastomer, drugs,
dye stuff, detergent, explosive, pesticides

The manufacture of basic raw materials like syngas, methane, ethylene, propylene,
acetylene, butadiene, benzene, toluene, xylene, etc. The basic building processes
include partial oxidation, steam reforming, catalytic and thermal cracking,
alkylation, dealkylation, hydrogenation, disproportionation, isomerization, etc. The
commonly used unit operations are distillation, extractive distillation, azeotropic
distillation, crystallization, membrane separation, adsorption, absorption, solvent
extraction, etc.
Manufacture of intermediate chemicals derived from the above basic chemicals by
various unit processes like oxidation, hydrogenation, chlorination, nitration, alkylation,
dehydrogenation along with various unit operations like distillation, absorption,
extraction, adsorption, etc.
Manufacture of target chemicals and polymers that may be used in the manufacture of
target products and chemicals to meet the consumer needs. It includes plastics, synthetic
fibers, synthetic rubber, detergents, explosives, dyes, intermediates, and pesticides.
Product profile of a typical petrochemical complex is given in Figure 20.1.
352 Chemical Process Technology

PE: Polyethylene, PP: polypropylene, PVC: polyvinyl chloride, EO: ethylene oxide, MEG: monoethylene glycol,
ABR: acrylobutadiene rubber, LAB: Linear alkylbenzene, VCM: vinylchloride monomer
Fig. 20.1: Product profile of typical petrochemical complex

20.3 INDIAN PETROCHEMICAL INDUSTRY

Petrochemicals are backbone of chemical industry. Although the origin of petrochemical
industry in world was in 1920, however, 1960s marks the era of petrochemicals in
India when Union Carbide set up first ethylene complex with capacity 20,000 TPA in
1963 in Mumbai. It was followed by NOCIL with 60,000 TPA ethylene complexes in
1968 in Thane near Mumbai and PSF plant of Chemical and Fibers India Ltd. (CAFI)
at Thane–Belapur Road. Indian Petrochemical Corp. Ltd. (IPCL) set up first integrated
petrochemical complex in 1970 in public sector at Vadodara. With the modest beginning
in 1960 by setting up of 20,000 tons naphtha cracked by Union Carbide in Mumbai,
Indian petrochemical industry has sustained a high and steady rate of growth during
last four decades and has entered the world market. The petrochemical industry has
been the fastest growing sectors in India and become a major segment of chemical
industry, which is growing faster than industries overall and within chemicals. It has
posed serious threat to chemical industry based on natural feedstock—biomass and
coal. The petrochemical industry is major supplier of chemical inputs to a large and
growing number of downstream.
Petrochemicals sector in India is growing at 13% and is projected to reach $100 billion
by 2020 (Chate, 2016). Projected demand of some of the important petrochemicals
in MMTTPA from 2012 to 2020 is: ethylene 38.5, propylene 29.8, butadiene 30,
benzene 124, and xylkenes 145. The above rising demands require more production of
petrochemicals (Sarin, 2016).
Indian oil to invest 1.8 trillion to expand refineries and biuld new business in the next
5–7 years (Singh 2017). Indian oil has 20% market share in the petrochemical business.
Petrochemical Industry 353

In view of growing demand for petrochemicals especially polymers Indian oil has plans
to invest about 32000 crore more in petrochemical business.
Reliance industries 9RIL0 will add $300 million–$400 million in operating this fiscal
by replacing naphtha with ethane which will be imported. Ethane imported in very
large ethane carriers and is building pipe line to transport ethane to the petrochemical
plants at Dahej and Nagothane where the crackers will run at full capacity using ethane
as feedstock as feedstock. It is also planning to to producing 33% of ethylene from
Hazira cracker in place of expensive naphtha. RIL uses 2.5 million tons of naphtha as
feedstock in petrochemical crackers and by use of ethane, naphtha use as feedstock will
be reduce by 500,000 tons. IOC will go for expansion of its Paradip refinery capacity
by 5 million tons and also set up a polypropylene plant and MEG production facility
(Chemical Industry Digest, September 2017, p.11).
GAIL to setup petrochemical industry at its Godavari region of Andhra Pradesh. IG
petrochemicals to increase its capacity by 53000 tons per annum. Assam petrochemicals
will invest about 1337 crore to set up second unit of methanol 600 TPD and 325TPD
formalin (Chemical Industry Digest vol. 30, October 2017).
A profile of Indian petrochemical industry is shown in Table 20.6.

Table 20.6: Profile of Indian petrochemical industry: Installed capacity and

production of major petrochemicals 2015–16 (in thousand tons)
Installed capacity Production
Organic chemicals
Acetic acid 177.43 157.91
Acetic anhdride 118.30 92.99
Acetone 47.14 24.96
Phenol 76.75 40.42
Methanol 474.30 163.62
Formaldehyde 411.30 252.09
Nitrobenzene 91.8 68.37
Malic anhydride 5.40 3.54
Pentaerythritol 13.72 13.97
Aniline 60.10 39.40
Chloromethanes 221.10 220.18
Isobutylene 13.80 7.24
ONCB 30.00 19.26
PNCB 30.0 31.27
MEK 5.0 5.75
Acetaldehyde 189.01 58.96
Ethanol amine 17.60 13.25
Ethyl acetate 545.83 360.40
Menthol 33.65 14.73
Contd...
354 Chemical Process Technology

Table 20.6: Profile of Indian petrochemical industry: Installed capacity and

production of major petrochemicals 2015–16 (in thousand tons) (Contd...)
Installed capacity Production
Orthonitrotoluene 16.4
Pesticides
292.00 187.52
Dyes and intermediate
452.37 304.06
Fiber intermediate
Acrylonitrile 41 2
Caprolactam 120 86
Monoethylene glycol (MEG) 1153 1001
Purified terephthalic acid 3753 3432
Total fiber intermediates 5067 4079
Building blocks (Olefins)
Ethylene 4283 3727
Propylene 4746 4457
Butadiene 433 343
Total olefins 9462 8528
Building blocks (aromatics)
Benzene 1566 1333
Toluene 288898 116
Mixed xylenes 898 269
o-xylene 420 500
p-xylene 3132 3266
Total aromatics 6304 5484
Major petrochemicals
Butanol 26 11
C4 raffinate 292 429
Diethylene glycol (DEG) 85 107
Diacetone alcohol 10 0
Ethylene dichloride 593 277
2–Ethyl hexanol 55 44
Epicichlorohydrine 0 0
Iso-butanol 3 2
Isipropynol 70 71
Methyl methacrylate 4 2
Phthalic anhydride 349 306
Propylene oxide (PO) 36 37
Prolpylene glycol 20 14
Contd...
Petrochemical Industry 355

Table 20.6: Profile of Indian petrochemical industry: Installed capacity and

production of major petrochemicals 2015–16 (in thousand tons) (Contd...)
Installed capacity Production
Polyvinyl acetate resin 17 0
Vinyl acetate monomer 30 0
Vinyl chloride 541 791
Plyol 142 72
PBT 1.0
Synthetic detergent intermediates
Linear alkyl benzene 547 377
Ethylene oxide 140 188
Performance plastics
ABS resin 128 117
Nylon 6 and Nylon 6,6 28 21
Polymethyl methacrylate (PMMA) 4 1
Styrene acrylonitrile (SAN) 136 99
PET chips/polyester chips 2199 1453
PTFE (Teflon) 20 9
Source: Annual Report 2015–16. Department of Chemicals and Petrochemicals, Ministry of Chemicals
and Fertilizer, Government of India.

20.3.1 Basic Petrochemicals

C1 group Methane, CO–H2 synthesis, synthesis gas derivatives
C2 group Ethane, ethylene, ethylene derivatives, acetylene
C3 group Propane, propylene and propylene derivatives
C4, C5 group Butadiene, butanes, butenes, pentane, pentene, isoprene, cyclopentadiene
Aromatic Benzene, toluene, xylene, naphthalene, BTX derivatives

20.3.2 Major End Products

Polymer, synthetic fiber, synthetic rubber, synthetic detergent, chemical intermediate,
dyes and intermediates chemical intermediates, pesticides.

20.3.3 Basic Building Block Process

Petrochemical manufacturing involves building block processes for the manufacture
of building blocks and intermediates.
Cracking: Steam cracking, catalytic cracking for olefins pyrolysis gasoline by-product
Steam reforming and partial oxidation: Synthesis gas
Catalytic reforming: Aromatic production
Aromatic conversion processes: Aromatic production
Alkylation: Linear alkyl benzene
Oxo process: Oxo-alcohols
Polymerization process: Polymer, elastomers, and synthetic fiber.
356 Chemical Process Technology

20.4 PETROCHEMICALS FEEDSTOCK

One of the major issues, which have directed the worldwide growth of petrochemical
industry, has been the availability of feedstock, which has led to replacement of the
natural resources coal, molasses, fats, etc. Basic feedstock used in petrochemical
industry for manufacture of olefins and aromatics are derived either from natural gas
or petroleum fractions and includes natural gas (associated or non-associated), condensate,
naphtha, kerosene, catalytic cracking and reformer gases, waxes, pyrolysis gasoline. Natural
gas and petroleum fractions as petrochemicals feedstock is given in Table 20.7 (Mall, 2007,
2015, 2017). Alternative routes to principal petrochemicals are given in Table 20.8 (Masood,
2002). Some of the alternative feedstock choice for petrochemical industry is:

Table 20.7: Natural gas and petroleum fractions as petrochemicals feedstock

Petroleum
Intermediate Intermediate
fractions and Source Composition
processes feedstock
natural gases
Refinery Distillation, Methane, ethane, Liquefaction, LPG, ethylene,
gases catalytic cracking, propane, butane, cracking propylene, butane,
catalytic reforming BP up to 25ºC butadiene
Naphtha Distillation and C4–C12 Cracking, Ethylene,
thermal and hydrocarbon, reforming, propylene,
catalytic cracking, BP 70–200ºC alkylation, dispro- butane, butadiene,
Vis breaking portionation, benzene, toluene,
isomerization xylene
Kerosene Distillation C9–C10 Fractionation Linear
and secondary hydrocarbon, to obtain nC10–nC14 alkanes
conversion BP 175–275ºC C10–C14 range
processes hydrocarbon
Gas oil Distillation of C10–C25 Cracking Ethylene,
crude oil and hydrocarbons, propylene,
cracking BP 200–400ºC butadiene,
butylenes
Wax Dewaxing of C8–C56 Cracking C6–C20 alkanes
lubricating oil hydrocarbon
Pyrolysis Ethylene cracker Aromatic, Hydrogenation Aromatics
gasoline alkenes, dienes, distillation,
alkanes, extraction,
cycloalkane crystallization,
adsorption
Natural Gas fields Hydrogen, Cracking, Ethylene,
gases and and crude oil methane, ethane, reforming, propylene, LPG,
natural gas stabilization propane, pentane, separation aromatics, etc.
condensate aromatics
Petroleum Crude oil Carbon Residue Carbon-
coke upgradation electrode,
processes, acetylene, fuel
gasification
Source: Mall, 2013, 2017.
Petrochemical Industry 357

Table 20.8: Alternative routes to principal petrochemicals

Chemicals Petroleum source Alternate source
(Europe, except where stated)
Methane Natural gas: Coal, as by-product of separation of coke
Refinery light gases (demethanizer oven-gases (1920–30) or of coal hydro­
overheads) genation (1930–40)
Ammonia Methane: Light liquid hydrocarbons From coal via water gas (1910–20)
Methyl alcohol Methane: Light liquid hydrocarbons From coal via water-gas (1920–30); from
methane (from coal) by methane-stream
and methane oxygen processes (1930–40)
Ethylene Pyrolysis of gaseous liquidhydro­ Dehydration of ethyl alcohol (original
carbons route). By-product in fractional distil­
lation of coke-oven gas (1925–35). Hydro­
genation of acetylene (1940–45)
Acetylene Ethylene Calcium carbide (original process).
Methane from coal by partial combustion
and by arc process (1935–45)
Ethylene glycol Ethylene From ethylene made as above (1925). In
America, from coal via carbon-monoxide
and formaldehyde (1935–40)
Ethyl alcohol Synthetic ethyl alcohol co-product Fermentation of molasses (original route)
Acetaldehyde Paraffin gas oxidation Fermentation of ethyl alcohol, or acetylene
Direct oxidation of ethylene from carbide (1900–10)
Acetone Propylene Wood distillation (original process). Pyro­­
lysis of acetic acid (1920–30) or by acety­
lene-stream reaction (1930–40)
Glycerol Propylene By-product of soap manufacture (original
process)
Butadiene 1-and 2-butenes, butane, synthetic Ethyl alcohol (1915); acetaldehyde via
ethyl alcohol, by-product of ethylene 1:3-butanediol (1920–30); acety­lene and
by pyrolysis of liquid hydrocarbons formaldehyde from coal via 1:4-butanediol
(1940–45); from 2:3-butanediol by fermen­
tation (1940–45)
Aromatic Aromatic-rich and naphthenic-rich By-products of coal-tar distillation
hydrocarbons fractions by catalytic reforming
and direct extraction or by hydro-
alkylation

• Naphtha from coal via direct liquefaction or indirect liquefaction by FT process

• Plastic waste to naphtha and other hydrocarbons through liquefaction, pyrolysis
and separation processes
• FT naphtha from biomass
• Methanol routes: Synthesis gas from methane, coal and biomass; conversion of
synthesis gas to methanol and production of olefin by methanol to olefin technology.
• Conversion of methanol to dimethyl ether
• Product recovery and separation: Recovery of C4 and C5 stream from FCC and steam
cracker
358 Chemical Process Technology

• Oxidative coupling of methane

• Ethanol from biomass: Direct fermentation of sugar rich biomass, hydrolysis of
lingo-cellulosic biomass
• Gasification of lingo-cellulosic biomass followed by fermentation or chemical catalysis
to ethanol.
• Carbon dioxide to liquid fuel by engineered bacteria
• Gasification of petrocoke to hydrogen.
Demand for natural gas in India is likely to increase in power generation to transport
and feedstock for the fertilizer and petrochemical industry which heavily dependent
on naphtha as feedstock. Growth of natural gas based fertilizer and petrochemical will
be major driver for natural gas consumption in India (Joshi, 2017).
Gasification of coal, biomass, petcoke and other refinery residue offers a promising
option to convert these low value feedstocks to produce wide range of products from
syn gas like fuels, methanol and derivatives like a formaldehyde, acetic acid, ammonia,
urea, hydrogen, petcoke-based ethanol, olefins and polymers, etc. CO2 generated in
gasification can be separated with various available advanced technologies and can be
utilized for enhanced oil recovery, coal bed methane recovery, algae growth and other
industrial usage, such as dry ice, beverage, etc. (Chate, et al. 2016).
20.4.1 Evaluation of Feedstocks for Aromatics, Olefins and Surfactant Plants
Aromatics — Naphtha, pyrolysis gasoline, LPG
Olefins — Ethane, propane, naphtha, gas oil
Surfactant plants — Kerosene for paraffins, benzene
• Input cost of feed constituents is a major portion of the variable cost for production
in petrochemical plants.
• Major feed input naphtha/kerosene from the refinery
• Feed quality monitoring and improvement efforts are therefore very important
aspects having significant impact on the economics of the operation cost.
• The precursors and undesirable constituents in feed including catalyst and adsorbents
poisons should be known, analyzed and monitored continuously.
20.4.2 Evaluation of Feedstock for Olefin Production
Olefins playing important role in petrochemical industry by providing raw materials
for chemical intermediates like ethylene oxide ethylene glycol, acetaldehyde, vinyl
chloride, and poly olefins, etc. Olefin production requires more paraffinic naphtha.
Desired components in feed for olefins productions (Dave and Khurana, 1996):
• Naphthenes: Naphthene yield olefins of higher carbon number. Butane yield increases
appreciable with naphthenic feed. Naphthenes also enhance production of aromatics.
• Aromatics: The aromatics feed are highly refractory and they pass through the
furnace unreacted.
• Sulfur: The sulfur in feed suppresses stream reforming reaction catalyzed by nickel
present in radiant coil. Optimum level of sulfur is 1 ppm.
• Physical properties: Density, distillation ranges are useful and give a rough
assessment of feed quality.
• Ethylene: The following components in feed give ethylene in decreasing order:
ƒ Ethane, butane to decane, 3- and 2-methyl hexane, 2-methyl pentane/2,2 dimethyl
butane, isopentane
Petrochemical Industry 359

• Propylene: The following components in feed give propylene in decreasing order:

ƒ Isobutane, n-nutane, n-propane, 3 methyl pentane, 2,3 dimethyl butane, 2 methyl
hexane, n-pentane, 3 methyl hexane, isopentane.
• Butadiene: The following components of feed give butadiene is decreasing order:
ƒ Cyclohexane, methyl cycloentane.
Some of the key properties for evaluation of naphtha for olefin production are density,
ASTM distillation, TBP, FBP, Saybolt color, sulfur, RVP and paraffin, naphthanes and
aromatic contents.
Aromatic Plant
Aromatics especially benzene toluene, xylenes (p- and o-xylenes) are important
petrochemical feedstocks for manufacture of synthetic fiber, pesticides, explosive,
surfactants, synthetic rubber. Aromatics are either processed in refinery. Catalytic
reforming are processed separately in petrochemical complex for manufacture of
p-xylene required for DMT/PTA plant. Quality of naphtha and impurities present in
naphtha are very crucial in quality of aromatics as well as long life of catalyst.
Naphtha cut C6–C9
Paraffin, napthenes, aromatics 110–140ºC
Dehydrogenation of C8 Napthene yield C8 aromatics. Most desirable component 90%
of C8 napthalene in feed get converted to C8 aromatics
• C8 Paraffins: Dehydrocyclization of C8 paraffins yield aromatics difficult to 20% C8
paraffins gets converted to C8 aromatics.
• C8 Aromatics: Pass as refractory and directly contribute to C8 aromatic production.
• C8 Aromatic precursors: It is useful to monitor aromatic precursors = 0.2* C8 P + 0.9
* C8 N + 1.0 C8 A.
Some of the key properties of naphtha aromatic production are density, ASTM
distillation, IBP, FBP sulfur, nitrogen, chloride, metallic poisons, component analysis
for paraffins, naphthenes and aromatics (PNA) (Dave and Khurana, 1996):
Surfactants
Linear alkyl benzene is one of important feedstock for production of surfactant whose
demand is increasing with increasing population all over the world. LAB requires
paraffins for production of olefins of carbon range C10–12 to have more biodegradable
detergent. Benzene is required for alkylation of olefin to produce LAB. Feedstocks
for paraffins are kerosene feed 150–265ºC cut from refinery containing mainly nC7–
nC18 components which is fractionated to remove lighter and heavier fractions. The
fractionated cut is hydrotreated for removal of sulfur and nitrogen catalysts which are
poisonous to molex adsorbent molecular sieve.
Desirable: LAB requires olefin and benzene. At present trend is for manufacture of
biodegradable low molecular weight LAB. Paraffins containing nC10 to nC13 carbon
atoms are required in LAB manufacture which is obtained by fractionation of kerosene.
nC12 improve the flammability of LAB product (Dave and Khurana 1996).
Some of the undesirable components in the feed which are sensitive to molex
molecular sieves are contaminants like water, sulfur, nitrogen, oxygen, chlorides,
metallic poisons. Key properties of LAB feedstocks are density, ASTM distillation, IBP,
FBP, sulfur, bromine index, aromatics, Saybolt color, smoke point, flash point, nitrogen
component analysis for nC10–nC13, total normal paraffins.
360 Chemical Process Technology

20.5. INTEGRATION OF REFINERY WITH PETROCHEMICAL

Refinery and petrochemical integration is considered one of the best ways to improve
refinery margin due to high projected demand of primary petrochemicals, with
relatively higher margins comparison to refined product (Sarin, 2016). Advances
in processing technologies are playing a larger role in integrating refining and
petrochemical facilities (Kapur, et al. 2009). In the changing scenario, petroleum refining
and petrochemical production integration will be of vital importance for maximizing
the use of byproducts and improving the overall economy of a petroleum refinery. A
great deal of synergy exists between the refinery, aromatic complexes and steam cracker
complex. Off gases from the FCC unit and coker containing ethylene and propylene
can be integrated with the cold section of steam cracker. Pyrolysis gasoline is a good
source of aromatics which can be integrated with the catalytic reforming process.
Propylene from FCC and benzene from aromatics are feedstocks for the production of
cumene and phenol (Taraphdar, et al. 2012). A new concept of refinery petrochemical
integration (Kapoor, et al. 2007) is:
• Low to moderate level of integration: uses 5–10% of crude
• High level integration: These complexes convert 10–25% of the crude oil
• Petrochemical refinery: These complexes produce a significant amount of
petrochemicals as compared to fuels.
Petrochemical processes within refinery which will help in integration of refinery
and petrochemicals (Handa, 2010):
• Propylene recovery from FCC gases
• Ethylene from FCC gases
• C4 and C5 recovery from FCC
• C4S from naphtha cracker and refinery to LPG pool as well as feed to cracker
• Aromatic recovery and conversations
• Light ends and light naphtha conversion
• Residue and coke gasification
• Hydrogen production
• Butane to maleic anhydride and derivative
• Benzene–cumene–phenol–acetone
• Benzene–cyclohexane–caprolactum
• n-Paraffins extraction from kerosene for LAB
• Valorization of refinery streams—LCO, LCGO, HCGO
• Recovery of valuable chemicals cyclopentadiene, diclopentadiene, isoprene,
propolyene
• Isobutylene for alkylation
• Use of C7–C8 stream from benzene extortion for separation of p-xylene for PTA
• Maximizing the use of natural gas in a refinery-petrochemicals complex offers higher
margins and lower carbon emissions.
Off gas from FCC and delayed coking units contains a good quantity of ethane,
ethylene, propylene and some propane and recovery of these hydrocarbons may be
economical in the refinery.
Petrochemical Industry 361

20.5.1 Indamax FCC

Indmax FCC developed by IOC R&D is a breakthrough in FCC technology for converting
heavy feedstocks to propylene and other olefins. The operation is quite flexible to
maximize propylene plus ethylene or propylene and gasoline (Sarin, 2016). Indmax is a
novel patented technology to produce high yield of LPG, light olefins and high-octane
gasoline from various petroleum fractions ranging from hydrotreated VGO to residue
and mixture thereof. It can also upgrade olefinic naphtha from coker, Vis breaker or
FCC (Chemical Engineering World, February 2011, p.71).
20.5.2 Indalin Process
Indalin is a versatile indigenous technology adding value to upstream and downstream
oil industry. Indalin is a catalytic cracking process for upgradation of low value naphtha
to very high yield of LPG, containing high olefins such as propylene, ethylene butylenes
etc. Surplus kerosene and gas oil range fraction can also be processed along with
naphtha. Indalin can integrate a refinery with petrochemicals complex and therefore
offers a tremendous opportunity for value addition through upgradation of low value
streams to petrochemical feedstock (Bhatacharya, et. al. 2011).

20.5.3 Naphtha and Gas Cracking for Production of Olefins

Olefins are major building blocks for petrochemicals. Because of their reactivity
and versatility, olefins especially the light olefins like ethylene, propylene, butenes,
butadiene, etc. there has been tremendous growth in the demand of the olefins. Olefins
are finding wide application in the manufacture of polymers, chemical intermediates,
and synthetic rubber. Ethylene itself is basic building block for large number of
petrochemicals and is quoted as king of chemicals. The global ethylene capacity at
January 1, 2011, net additions and closings was more than 138 million tons compared
with nearly 130 million tons in 2008 (Oil and Gas J. Vol. 129, 2011).
The steam cracker remains the fundamental unit and is the heart of any petrochemical
complex and mother plant and produces large number of products and byproducts
such as olefins–ethylene, propylene, butadiene, butane and butenes, isoprene, etc.,
and pyrolysis gasoline. The choice of the feedstock for olefin production depends on
the availability of raw materials and the range of downstream products. Naphtha
has made up about 50–55% of ethylene feedstock sources since 1992. Although basic
steam cracking technology remain same for naphtha, gas oil and natural gas, different
configurations of steam cracking plant are available from various process licensors
(Petrochemical processes, 2003).

Naphtha/Gas Cracking
Requirement of steam will depend upon the type of feedstock; the lighter hydrocarbon
requires less steam as compared to heavier feedstock. Steam cracking relative cost
according to feedstock is given in Table 20.9. Steam requirement in steam cracker is
given in Table 20.10 (Wiseman, 1986). Energy requirement pattern for olefin production
is given in Table 20.11 (Gupta, 2000).
Modern ethylene plants incorporate the following major process steps: cracking,
compression and separation of the cracked gas by low temperature fractionation.
The nature of the feedstock and the level of pyrolysis severity largely determine the
operating conditions in the cracking and quenching section. Various steps involved in
362 Chemical Process Technology

Table 20.9: Steam cracking relative cost according

to feedstock
Table 20.10: Steam requirement in
Feedstock Relative investment cost steam cracking
Ethane 1.00 Feed kg steam/kg of
Propane 1.15 hydrocarbon
Butane 1.20 Ethane 0.2–0.4
Naphtha 1.45 Propane 0.3–0.5
Atmospheric gas oil 1.65 Naphtha 0.4–0.8
Vacuum gas oil 1.84 Gas oil 0.8–1.0

Table 20.11: Energy requirement for olefin production

Feedstock Specific energy consumption
Kcal/kg of ethylene Kcal/kg of olefin
Ethane 310 3,050
Propane 4,100 3,050
Ethane/Propane 3,600 3,300
Naphtha 5,000 3,050

Fig. 20.2: Typical naphtha cracker plant

the pyrolysis of naphtha and separation of the products are discussed below. In case
of gas cracking, separation of ethane and propane from natural gas is involved. Flow
diagram for pyrolysis of naptha is given in Figure 20.2.
Petrochemical Industry 363

Quench section: To avoid subsequent reaction the effluent is fixed in their kinetic
development by sudden quench first by indirect quench by water to 400–450ºC in
transfer line exchanger or quench boiler. This is a large heat exchanger that is a bundle
of metal tubes through which the gases pass and around which is circulated water
under pressure. The hot water produced is used to generate steam for use in the plant.
In the next step the quench is done by heavy product of pyrolysis.
Hot section: It consists of convection zone and radiant zone. In the convection
zone, hydrocarbon feedstock is preheated and mixed with steam and heated to high
temperature. In the convection zone the rapid rise in temperature takes place and
pyrolysis reaction takes place. The addition of dilution steam enhances ethylene yield
and reduces the coking tendency in the furnace coils. The production of the pyrolysis
reaction consists of a wide range of saturated and unsaturated hydrocarbons.

Descriptions of Hot Section

Convection zone Feedstock is pyrolized and the effluent conditioned.
Radiation zone The product formed are separated and purified.
Quench To avoid subsequent reaction the effluents are fixed
in their kinetics development by sudden quench.
Indirect Indirect quench by water to 400–500ºC generation
of high-pressure steam.
II Direct Direct quench by heavy residue by-product of
pyrolysis.
Primary fractionation column Separation of light products of pyrolysis as top and
bottom as pyrolysis product.
Compression Compression of light products.
Caustic scrubbing and drying Scrubbing with caustic followed by molecular
sieve adsorption to remove sulfur compounds,
mercaptan, etc.
Cold section: After compression, caustic scrubbing and drying the light effluents enter
the cold section of the unit which performs the separation of (i) hydrogen to various
concentration, (ii) ethylene containing 99.4%, (iii) 95% propylene, (iv) A C4 cut containing
25–50% butadiene, and (v) pyrolysis gasoline which is rich in aromatic hydrocarbons.
The complexity of the separation section of a cracker increases markedly as the feed
changes from ethane.
Descriptions of Cold Section • Hydrogen separation·
• Ethylene separation 99.9%·
• Propylene separation·
• A C4 cut containing 25–50% butadiene
• Complementary fraction of pyrolysis gasoline rich in
aromatic hydrocarbons.
Demethanizer Methane condensed at top around –100ºC, pressure 32 Pa.
Deethanizer Separation of C2 cut (Ethane and ethylene).
Acetylene eliminated by selective hydrogenation.
Catalyst: Palladium or Nickel 40–80ºC, 3 kPa.
364 Chemical Process Technology

Separation of ethylene Ethylene is fractionated and unreacted ethane recycled.

Depropanizer C3+ cut from bottom of deethanizer is fractionated.
C3 cut from top of depropanizer is selectively hydrogenated
to remove methyl acetylene and propadience.
Propylene content 95%.
Separation in supplementary column for more pure
propylene.
Removal of propane from Separation in supplementary column for more pure
propylene propylene.
Debutanizer Separation of C4 stream from C5+ stream.

Reactions in Steam Cracking

The reactions involved in thermal cracking of hydrocarbons are quite complex and
involve many radical steps. The thermal cracking reaction proceeds via a free radical
mechanism. Two types of reactions are involved in the thermal cracking: (i) primary
cracking reaction where the initial formation of paraffin and olefin takes place and
(ii) secondary cracking reaction where light products rich in olefins are formed. The
total cracking reactions can be grouped as follows:
• Initiation reaction
• Propagation reaction
• Addition reaction
• Isomerization reaction
• Termination reaction
• Molecular cyclization reaction.

Operating Variables of Steam Cracking

The main operating variables in the pyrolysis of hydrocarbon are composition of
feedstock, reaction temperature, residence time, hydrocarbon partial pressure, and
severity.

20.5.4 Composition of Feedstock

Naphthas are mixture of alkanes, cycloalkanes, and aromatic hydrocarbons depending
on the type of oil from which the naphtha was derived. The group properties of
these components greatly influence the yield pattern of the pyrolysis products. A full
range naphtha boiling range approximately 20–200°C would contain compound, with
4–12 carbon atoms. Short naphtha boiling point range from 100 to 140°C and long
chain naphtha boiling point lies around 200–220°C. The steam cracking of the naphtha
yields wide variety of products, ranging from hydrogen to highly aromatic heavy
liquid fractions. The thermal stability of hydrocarbons increases in the following order:
paraffins, naphthenes, aromatics. Yield of ethylene as well as that of propylene is higher
if the naphtha feedstock is rich in paraffins. It may be seen that relative production
of ethylene decreases as the feedstock becomes heavier. The percentage of pyrolysis
gasoline C5–200°C cut increases. Simultaneously, butadiene yield varies slight with
feedstock in the treatment of liquid petroleum fractions.
Petrochemical Industry 365

Furnace Run Length

Furnace run length can be calculated from the equation (Chamber and Potter, 1974):
Tmd – Tmc
Run length = ; Tmd = Maximum allowable tube skin temperature
DTm/day
DTm /day= Average rise in tube skin temperature per day
Tmc = Maximum metal skin temperature in the clean, uncoked condition
For any feedstock the heater section run length depends on the pyrolysis coil
selectivity, cracking severity and transfer line exchanger design. Run length varied
between 21–60 days for gas-based furnaces and 21–40 days for liquid feed-based furnace
(Wysiekierski and Fisher, 1999).

Pyrolysis Temperature and Residence Time

The effluent exit temperature is generally considered a significant indicator of the
operation of a furnace. As the furnace exit temperature rises, the yield also rises, while
the yields of propylene and pyrolyis gasoline (C5–200ºC cut) decrease with respect of
ethylene yield, each furnace exit temperature, correspond to an optimum. The highest
ethylene yield achieved by operating at high severely, namely, around 850ºC with
residence time ranging from 0.2 to 0.4 sec. However, operating at high temperature
results in high coke formation.

Partial Pressure of Hydrocarbon and Steam to Naphtha Ratio

Pyrolysis reaction producing light olefins are more advanced at lower pressure. Decrease
into the partial pressure of hydrocarbons by dilution with steam, reduces the overall
rate reaction rate, but also help to enhance the selectivity of pyrolysis substantially in
favor of the light olefins desired. Other role of steam during pyrolsis is (i) to increase
the temperature of feedstock, (ii) reduction in the quantity of heat to be furnished per
linear meter of tube in the reaction section, and (iii) to remove partially coke deposits
in furnace tubes.
The ethylene yield decreases as the partial pressure of hydrocarbon increases. For
economic reason, a value of 0.5–0.64 of steam per ton of naphtha is generally adopted
as the upper limit.

Severity and Selectivity Concept

Severity is often used to describe the depth of cracking or extent of conversion. The
definition of severity varies with the different manufactures and may differ accordingly
to the type of hydrocarbon treated. In the case of steam cracking of the ethane and
propane, it is convenient to express the severity of the operating conditions in terms
of feed conversion. At very high severities, the methane and ethylene yield level off,
while those of propylene and C4 cut reach a peak and then decline consequently. The
ratio of ethylene and propylene yield increases with severity, which hence favors the
formation of ethylene. The relative production of C5+ cut passes through a minimum
and at the very high severity tends to increase.
Modern ethylene plants are normally designed for near maximum cracking severity
because of economic considerations.
366 Chemical Process Technology

Ethylene Furnace Design

Pyrolysis furnace design during the last three decades made significant development.
Prior to 1960, the ethylene pyrolysis furnaces were box type with horizontal radiant
tubes. The capacity of these furnaces were small capacity (40 MM lb/y) today standards
(250 MM/lb/y). High thermal efficiency furnace design can contribute greatly to
minimum overall plant utility costs. Higher efficiency can be achieved by: (i) upgrading
of pyrolysis furnace capacity, (ii) increasing cracking severity, (iii) improving ethylene
selectivity, (iv) improving thermal efficiency, (v) reducing downtime for decoking,
and (vi) reducing maintenance cost. This can be achieved by radiant coil with shorter
residence time and lower pressure drop, combustion air preheating and short residence
time. Small diameter coils coupled with increased dilution steam, with use of booster
compressors to reduce furnace outlet pressure can increase efficiency ethylene selectivity.
Radiant coils with a short residence time and low hydrocarbon partial pressure give
higher ethylene selectivity.
Coke Formation during Pyrolysis and Decoking Measures
Pyrolysis of any hydrocarbon feedstock is always accompanied by coke formation, which
deposits on the walls of the tubular reactor. Under typical operating conditions, the coke
formation in naphtha pyrolysis is about 0.01 wt.% of the feed (Towfighi et al., 2001).
The coke deposits on the walls of reactor reducing the overall heat transfer coefficient
and increasing the pressure drop across the reactor. This results in gradual decrease
with run time of both the reactor tube metal temperature and the pressure drop across
the reactor necessitating periodic shut down. The coke formation inside the tube will
depend upon (i) characteristics of feedstock and the coking precursor, (ii) hydrocarbon
partial pressure, (iii) thermal condition of coil, and (iv) mass velocity which controls the
dynamics of gas film close to the wall. Controlling coking rate permits increasing the
severity of the furnace to increase conversion rate, reducing the cycle rate and unloading
downstream limiting equipment which increases throughput (Burns, et al. 1991).
Frequent decoking operating result in loss of production, affect the coil life and
increase fuel and utility costs. Run length between two successive decoking varies
according to the installation and the type of feedstock, but can be estimated at a few
weeks on the average. In ideal conditions, a furnace operating on naphtha can run
for go days without decoking. However, run length is always shorter due to the
inevitable fouling of the quench boiler. In practice, run length is as long as 90 days
on ethane feedstock, 65 days naphtha and 40 days with gas oil (Chauvel A, Lefebvre
G. “Petrochemical Process” Vol. 1, Institute Francais du Petrole Publications Editions
Technip, 27 Rue Ginwux, Paris, 1989).
Various approaches for coke mitigation are based on reduced coke production in the
coils and increased rates of coke removal or removal of coke precursors during pyrolysis
(Wysiekierski, et al. 1999). By using improved metallurgy and innovative coating
systems, ethylene producers seek to improve unit reliability, increase carburization
resistance, extend processing run length, reduce downtime and plant shut downs,
increase yields and throughput, extend furnace tube life (Wysiekierski and Fisher, 1999).
Mechanical decoking, steam air decoking is the method used for decoking. Mechanical
decoking processes take 4–7 times longer than steam air decoking. The principal method
of decoking with steam air are spalling and burning. The coke is burnt in the presence
of steam and air at temperature from (600–800ºC).
Petrochemical Industry 367

20.5.5 Trends in Technological Developments of Steam Crackers for Production of

Ethylene (Mall, 2017)
From the late 1960s through the 1970s, the petrochemical industry built a generation of
new steam crackers with an ethylene capacity of several million tons capacity. Older
plant consists of typically 10–17 small furnaces with radiant coils having residence
time 0.4–0.6 sec., thermal efficiency below 90%, central waste heat recovery system and
nitrogen oxide (NOX) emissions 75–100 ppm. Present day olefin plants have capacity
more than 1,000,000 tons per year; ethylene produced with 5–7 modern cracking furnaces
using twin-cell designs. Short residence time and radiant coil smaller diameters increase
yields. The higher selectivity of modern coils reduces specific energy consumption.
The modern olefin plants have better ethylene selectivity and improved health, safety
and environment standards by incorporating current emission and safety standards
(Feigl and Schmidt, 2007).
Major energy improvements by revamp or by replacing the existing furnace sections
can be achieved by (Fiegel and Schmidt, 2007):
• Increased thermal efficiency
• Higher radiant efficiency and less excess air by new burner technology and better
instrumentation
• Reduced heat losses due to fewer and bigger furnace units or new refractory
• Higher yields by new radiant coils, reducing specific energy demand
• Higher availability by application of new and highly reliable technology, reducing
losses due to unplanned shutdowns.
Performance of the steam cracking furnace can be upgraded by: (i) increasing
furnace capacity, (ii) increasing cracking severity, (iii) improving ethylene selectivity,
(iv) improving thermal efficiency, and (v) reducing downtime for decoking and reducing
maintenance.

Recovery of Chemicals from FCC and Steam Cracker

With the rising demand of ethylene and propylene, there has been a tremendous
growth in the steam cracking of hydrocarbons during the last four decades. Similarly,
fluid catalytic cracking (FCC) has developed into a major upgrading process in the
petroleum refinery industry for the conversion of heavy fuel oil into more valuable
products ranging from light olefins to naphtha and middle distillate. Large amounts
of C4 and C5 compounds are produced along with the production of ethylene in steam
cracking and gasoline in FCC. C4 and C5 streams are an important source of feedstock
for synthetic rubber and many chemicals.
With increasing demand of C5 hydrocarbons and oxygenates, upgrading of C4 and
C5 streams from steam crackers and catalytic cracker is important to the economic
performance of the above processes. It also provides a rich resource of reactive mole­
cules, which forms the backbone of the synthetic rubber industry. The quantity and
composition of the C4 and C5 stream depends on the severity of the steam cracker
operation and feedstock processed.
Product profiles of C4 and C5 hydrocarbons are given in Tables 20.12 and 20.13.
368 Chemical Process Technology

Table 2012: Product profile of C4 hydrocarbon

C4 chemicals Products
Butadiene Styrene butadiene (SB), rubber (emulsiom/solution), SB latex, caprolactam,
polybutadiene rubber, nitrile rubber, nitrile lsatex, pyridine vinyl SB rubber,
n-octanol, telomers, ABS resin, MBS resin, HMDA, lauryl lactam, cyclo-
octadiene, tetrahydrofuran, 1,4-butanedol 1-octene
Isobutylene Butyl rubber, polyisobutylenes, methyl methacylate, isoprene monomer,
peroxide intermediate, tertbutyl mercaptan, tertbutyl alcohol, tertbutyl amine,
alkylphenol MTBE, polybutyliene, diisobutylene, triisobutylene
1-butene LLDPE comonomer, n-butyl mercaptan,1-polybutene
Mixed butylene 2-Butanol, methyl ethyl ketone, maleicanhydride, C4 alkylate, C4 polygasoline,
2-propyl heptanol, higher oxoalchols
Butanes 1-butene, maleic anhydride, 1,4 butanediol, tetrahydrofuran, butyrolactone,
propylene oxide, tertbutyl alcohol, C4 alkylate

Source: Morgan “C4 industry beyond 2000”. Chemistry and Industry. February 2, 1998 p.90; Mall
2013, 2017.

20.5.6 Product Profile of C5 Hydrocarbon

C5 hydrocarbons are an important source of synthetic rubber, solvents, chemical
intermediate, MTBE, plasticizers, TAME, rubber chemicals, herbicides, lube oil additives,
and pharmaceuticals.

Table 20.13: Product profile of C5 hydrocarbons

C5 hydrocarbon Isoprene Polyisoprene, as the cross-linking agent in butyl rubberAs
co-monomer in styrene-isoprene copolymers
Isopentane Solvent, chlorinated derivative, blowing agent for polystyrene
1-Pentene Organic synthesis, blending agent for high octane fuel
2-Pentene Polymerization inhibitor, organic synthesis
Cyclopentene Organic synthesis, polyolefins, epoxies cross-linking agent
2- Methyl-1- Synthetic mark, amyl benzene hydrogen synthetic mark,
butene amyl benzene hydrogen peroxide catalyst, 2,4-diamyl phenol
(photographs color complex), pinacolone (crop protection
chemicals)
3- Methyl-1- Monomer for specialty homo-polymer
butene
Cyclopentadiene Chlorinated insecticides, chemical intermediate, antiviral
agent
Piperylene Polymers, maleic anhydride, chemical intermediate

Fluid Catalytic Cracking

Fluid catalytic cracking (FCC) converts low value crude oil into a variety of higher value
products which include gasoline, diesel, heating oil and valuable gases containing LPG,
Petrochemical Industry 369

propylene and C4 and C5 gases. Various products from fluid catalytic cracking and their
uses are given in Table 20.14. FCC units are versatile and can be operated in three main
modes which are aimed at maximizing middle distillate, gasoline, or olefins respectively
by means of the adequate combination of various parameters such as catalyst type,
catalyst to oil ratio, rise of outlet temperature and recycle of fractionators bottom. FCC
is the second largest source of propylene supplied for petrochemical application.
• Conventional FCC 4–7% propylene and 1–2% ethylene
• High severity FCC:10% propylene
• Petro FCCTM (UOP): Ethylene 6%, propylene 20–22%, higher aromatics (18%) in
naphtha
• Higher C4–8 olefins yield which can be cracked to yield lower olefins by total
petrochemicals ATOFINA/UOP olefin cracking process
• Although FCC is an important petroleum refining process, however, FCC gases have
now become important petrochemical feedstock for production of LPG that can be
converted to aromatics and C3, C4, and C5 hydrocarbons, i.e., propylene, butene,
isobutene, pentene, etc.
Product distribution from FCC depends on:
• Reactor temperature
• Feed preheat temperature
• Catalyst activity
• Catalyst circulation rate
• Catalyst activity
• Recycle rate

Table 20.14: Various petroleum products from FCC and their uses
Product Composition and uses
Light gases Primarily H2, C1 and C2S, ethylene can be recovered
LPG C3S and C4S containing light olefins suitable for alkylations
Gasoline C5 + high octane component for gasoline pool or light fuel
Light cycle oil (LCO) Blend component for diesel or light fuel
Heavy cycle oil (HCO) Fuel oil or cutter oil
Clarified oil Carbon black feedstock
Coke Used in regenerator to provide the reactor heat demand

Propylene Recovery from FCC

FCC gases has important source of propylene from refinery and now FCC units are
being operated both in gasoline mode and propylene mode. Propylene from FCC may
be as high as 25% with new FCC based propylene technologies. Increased production of
olefins from FCC units has been achieved through changes in operations, base cracking
catalyst and additive catalysts and in hardware designs (Teng and Xie, 2006).
Upgrading OF C4 and C5 Streams
C4 and C5 streams from steam cracker and FCC contain C4 and C5 hydrocarbons, recovery
of which has become important steps for improving the overall economy of these
370 Chemical Process Technology

processes. Some of the important C4 streams from cracker and FCC butadiene (from
cracker plant only), butene-1, 2-butane, isobutylene, mixed n-butene, and isobutene.
C4 stream of steam cracker contains appreciable amount of butadiene which is being
recovered from naphtha cracker plants. Typical composition of C4 stream of naphtha
cracker and FCC is given Table 20.15. The distribution product will depend on the
feedstock, cracking severity and catalyst in case of FCC.

Table 20.15: Typical compositions of C4 fractions

Component FCC Steam cracking
Isobutane 37.0 2.0
Isobutene 24.0 26.0
1-Butene 15.0 13.6
1,3-Butadiene 0.2 36.0
2-Butenes (cis and trans) 11.0 12.0
n-Butane 12.0 9.8
Others Balance Balance

Typical C5 cuts from steam cracking contain C4 (1%), n-pentene (26%), isopentane
(24%), n-pentene (4.5%), methyl butenes (12%), cyclopentenes (1.5%), isoprene (13.5%),
pentadiene (piperylene) (9.0%), cyclopentadiene (7.5%), C6+ (1%) (Chauvel and Lefebvre,
1989). Cyclopentadiene is easily dimerized to higher boiling dicyclopentadiene and
separated from C5 stream by simple distillation. Typical composition of C5 cuts from
catalytic cracking may be C4 (2%), n-pentane (5.5%), isopentane (31.5%), n-pentenes
(22.5%), methyl butenes (37.5%), C6+ (1%) (Chauvel and Lefebvre, 1989). Naphtha feed
gives higher yield of C4 (8–10%) than ethane feed (2–3%).
Upgrading of C4 olefins:
• Production of chemical intermediates
• Butene-1, isobutylene, mixed n-butene
• Production of motor fuel component (alkylate, dimate, MTBE)

Processing of C4 Cut from Steam Cracker and FCC

There is not much difference in the processing of C4 streams after the recovery of
butadiene from the steam cracker and C4 streams from the FCC. Butadiene fromC4 stream
of naphtha cracker/gas cracker is first recovered, followed by separation of isobutylene,
isobutane, butane, butane-1 and butene-2 from C4 stream/FCC and cracker using
various processes like etherification, hydrolysis, cracking, adsorption distillation, etc.
C4 cut from steam cracker and FCC is shown in Figure 20.3 (Briggs, et al. 1987;
Convers, 1987; Vermilion and Niclaes, 1977; Chauvel and Lefebvre, 1989). Isobutene
recovery includes either hydration of the C4 stream and subsequent decomposition
or etherification with methanol to yield MTBE, which is cracked to give isobutene.
Separation of 1-butene is done by selective hydrogenation followed by adsorption for
separation of 1-butene and further processing for separation of isobutene and 2-butene
by distillation. Separation of 2-butene involves hydro-isomerization and subsequent
distillation for separation of isobutene and 2-butene.
Petrochemical Industry 371

Fig. 20.3: Separation of C4 hydrocarbons from FCC and steam cracker plants

After separation of butadiene, the C4 streams from cracking and FCC is processed
for production of n-butene, 1-butene, 2-butene, and isobutene.

20.5.7 Butadiene
Butadiene is important raw material for production of larger number of synthetic
rubber and polymers such as styrene butadiene rubber (SBR), polybutadiene,
chloroprene rubber, nitrile rubber, acrylonitrile butadiene styrene plastic. Other
fastest growing use is in the manufacture of adiponitrile used in the manufacture
of nylon 6, 6. Steam cracker and catalytic dehydrogenation of butenes are the two
major sources of butadiene. Butenes can be recovered from C4 stream or produced
by dehydrogenation of butanes.
372 Chemical Process Technology

According to SRI consulting global production and consumption of butadiene in

2009 was approximately 9.2 million tons and 9.3 million tons, respectively. Butadiene is
expected to average growth of 4.9 per year from 2009–2014. Styrene–butadiene rubber
accounted for more than 33% of global butadiene consumption in 2009 and butadiene
rubber for about 25%.
Polymerization Grade Butadiene
1,3 Butadiene % min. 99.6%
Butenes ppm max. 4000
Methyacetylenes [Link]. 25
Vinyl acetate ppm, max. 200
C5 dimers ppm max. 2000
Carbonyl compounds (as aldehyde) max. 50
Inhibitor (p-tert-butylcatechol) 100–200
Non-volatile residue ppm. 2000
There are four major routes for production of butadiene:
1. Steam cracking of naphtha
2. Catalytic dehydrogenation of butenes
3. Catalytic dehydrogenation of butanes
4. Dehydrogenation-dehydration of ethanol (molasses route).

Butadiene from C4 Stream of Cracker Plant

C4 cut from the steam cracker is first sent for butadiene recovery, which includes selective
hydrogenation of acetylenics in presence of palladium catalyst, then separation of buta­
diene extractive distillation process steps involved are (Chavel and Lefebvre, 1989):
• Extractive distillation in which acetylenic compound and butadiene are extracted
in one or two stages
• Recovery of solvent
• Super fraction of butadiene stream for removal of acetylenic impurities
• Water scrubbing butadiene depleted cut to recover the solvent.
• Various solvents used for separation of butadiene are furfural, dimethyl formamide
(DMF), n-methyl pyrrolidone (NMP), and dimethyl acetamide. Selective
hydrogenation results in overall improvement in the economy with higher butadiene
yield.

Catalytic Dehydrogenation of Butenes

Reaction: Catalytic dehydrogenation of butanes is two-stage process:
1. Catalytic dehydrogenation of butanes to butenes
Petrochemical Industry 373

2. Catalytic dehydrogenation of butenes to butadiene

20.5.8 Isobutylene
Isobutylene is present in the C4 stream naphtha cracker and FCC. Major application of
isobutene is in the manufacture of gasoline blending component, such as MTBE, ETBE,
alkylation, polymer gasoline. Polymer grade isobutylene can be made by cracking
MTBE or for manufacture of polyisobutylene. Isobutylene is used in manufacture of
butyl rubber which is made by copolymerization of isobutylene with small amount
of isoprene.
Various Routes for Isobutylene
Extraction of C4 cuts from steam cracking/FCC: Isobutylene is separated from C4 cuts
from naphtha cracker after extraction of butadiene and from FCC gases after propylene
recovery. First isobutylenes are converted to MTBE by etherification and recovered by
cracking of MTBE to get polymer grade isobutylene it is also obtained by hydration of
isobutylene containing stream and then cracking.
Isomerization of butene: Isobutylene can also be produced from butane by isomerisation
using zeolite ferrierite (zeolite of medium pore size) (Maulijan, et al. 2001).
Dehydrogenation of Isobutene
Butene-1: Butene-1 is co-monomer in the production of low-density polyethylene and
high-density polyethylene. Butene-1 can be separated from C4 stream of cracker after
extraction of butadiene SHB-CB process: This process selectively hydrogenates the
butadiene in the C4 cut by converting it to butane-1 and butane-2. Acetylenes and dienes
are likewise hydrogenated. If the process is optimized to produce butane-1, about 60%
of butadiene is converted to butane-1. The process is operated in the liquid phase mild
temperatures and moderate pressures.
Upgrading OF C5 Cuts
The steam cracker C5 stream is a rich resource of olefins and diolefins which can be
upgraded to produce elastomers, resins and fine chemical intermediates. In steam
crackers during cracking process along with ethylene, propylene, C4 stream, aromatics
and pyrolysis gasoline bare also formed. Apart from aromatics, pyrolysis gasoline stream
also contains C5 stream (Morgan, 1996). The quantity and composition of the stream
depend on the nature of the cracked product and severity of cracker operation C5 stream.
Various steps in the recovery of C5 chemicals are (Chauvel and Lefebvre, 1985):
• Separation of C5 stream from pyrolysis gasoline by distillation
• Separation of cyclopentadiene: In first stage cycolpentadine is dimerized to
dicyclopentadiene followed by cracking of dicylopentadiene to cyclopentadiene.
• Extractive distillation of cyclopentadiene free C5 stream produce isoprene–piperylene
stream. Distillation removes the light acetyelenes.
374 Chemical Process Technology

• Separation of isoprene and piperylene extract by distillation.

• Absorption at atmospheric pressure in the presence of NMP.
• Purification of isoprene rich paraffin.
• Periodic regeneration of solvent.
Solvents used in extraction of isoprene are acetonitrile, N-methylpyropedone, and
dimethylformamide.
Oxygenates from Refinery C4 and C5 Stream
Several oxygenated fuel components have figured prominently in refinery reformulated
gasoline planning are methyl tertiary butyl ether (MTBE), tertiary amyl methyl ether
(TAME) and ethyl tertiary butyl ether (ETBE). All oxygenated fuels reduce hydrocarbons
in the automobile exhaust. MTBE was considered one of the most important oxygenates
used in the production of lead-free gasoline and was used produced on a large scale
throughout the world. There has been because of environmental problem. The oxygenated
MTBE and ETBE are produced by the reaction of methanol/ethanol and isobutylene.

20.5.9 Methyl Tertiary Butyl Ether (MTBE)

MTBE is one of the important oxygenates and originally its use started as a substitute of
tetraethyl lead. MTBE increases the oxygen content of gasoline results in the reduction
of harmful emissions. MTBE which is made by etherification of C4 gases from cracker
and FCC is also used for production of polymer grade isobutylene for synthetic rubber.
MTBE is produced by the reaction of methanol with isobutylene contained in C4
streams from thermal crackers in the presence of ion exchange resin at 40–90ºC and a
pressure of 5–10 kg/cm2g. Catalytic cracking butylenes and field butanes are additional
possible source of isobutylene. Convention process and catalytic distillation are the two
commercial processes available. Figure 20.4 shows the process flow diagram for MTBE
conventional methods.

Fig. 20.4: MTBE conventional methods

Petrochemical Industry 375

20.5.10 Ethyl Tertiary Butyl Ether (ETBE)

ETBE is made by etherification of isobutylene with ethanol similar to MTBE.
Isobutylene + Ethanol ETBE

20.5.11 Tertiary Amyl Methyl Ether (TAME)

TAME is produced by etherification of isoamylenes recovered from C5 stream of FCC
and steam crackers. Two reactive components of isoamylenes are 2-methyl butene-1
and 2-Methyl butene-2. Catalytic distillation process is used for the manufacture
of TAME.
Reactions: Reactions are as follows:

20.6 SYNTHESIS GAS AND ITS DERIVATIVES: HYDROGEN, CO, METHANOL,

FORMALDEHYDE, METHANOL TO OLEFIN TECHNOLOGY

Methane and synthesis gas are important petrochemical feedstocks for manufacture
of large number of chemicals, which are used directly or as intermediates, many of
these products are number of which are finding use in plastic, synthetic fiber, rubber,
pharmaceutical and other industries. ‘Synthesis gas’ is commonly used to describe two
basic gas mixtures—synthesis gas containing CO, hydrogen and synthesis gas containing
hydrogen and nitrogen for the production of ammonia. Major requirements of synthesis
gas in world scale petrochemical are given in Table 20.16.
Some of the emerging technologies in utilization of synthesis gas and methane for
the production of petrochemicals are Fischer–Tropsch synthesis, oxidative coupling
of methane with chlorine to yield ethane and ethylene, methanol to olefin technology
(MTO). Fischer–Tropsch synthesis is being studied in great detail world over and
it is promising to be a future technology for manufacture of olefins from synthesis
gas. CO can be separated from synthesis gas either by cryogenic or by pressure
swing adsorption, is a promising feedstock for production of variety of products.
Product profile of methane, synthesis gas and CO-based building blocks are given in
Figure 20.5 (Mall 2007).
376 Chemical Process Technology

Table 20.16: Synthesis gas requirements for major world scale petrochemicals
Product Required Typical world-scale capacity, Syn. gas required, Nm3/hr.
H2: CO TPA
Methanol 2:1 1,60,000–12,75,000 48,000–1,90,000
Acetic acid 0:1 2,75,000–5,45,000 18,000–36,000
Acetic anhydride 0:1 90,000 3500
Oxo alcohol 2:1 1,15,000–2,75,000 12,000–25,000
Phosgene 0:1 4,800–1,60,000 3,500–12,000
Formic acid 0:1 45,000 3,500
Methyl formate 0:1 9,000 600
Propionic acid 0:1 45,000–68,000 2,400–3,500
Methyl methacrylate 1:1 45,000 4,700
1,4-Butandiol 2:1 45,000 4,700
Source: Hydrocarbon Processing, Gunadson and Abrardo, 1999.

Fig. 20.5: Methane, synthesis gas and CO building blocks (Source: Mall, 2017)
Petrochemical Industry 377

20.6.1 Synthesis Gas

Methane and synthesis gas are important petrochemical feedstocks for the manufacture
of a large number of chemicals, which are used directly or as intermediates, a number
of which are finding use in plastic, synthetic fiber, rubber, pharmaceutical and other
industries. ‘Synthesis gas’ is commonly used to describe two basic gas mixtures—
synthesis gas containing CO + hydrogen and synthesis gas containing hydrogen +
nitrogen for the production of ammonia.
Petrochemical derivatives based on synthesis gas and carbon monoxide have
experienced steady growth due to large scale utilization of methanol and development
of a carbonylation process for acetic acid and Oxo-synthesis process for detergents,
plasticizers, and alcohols. Recent market studies show that there will be a dramatic
increase in demand of CO and syngas derivatives.
Methanol is the largest consumer of synthesis gas. The reformed gas is to meet certain
requirements with regard to its composition. It is characterized by the stoichiometric
conversion factor, which differs from case to case.
Raw Materials for Synthesis Gas
Various raw materials for synthesis gas production are natural gas, refinery gases,
naphtha, fuel oil/residual heavy hydrocarbons and coal. Although coal was earlier used
for production of synthesis gas, now it has been replaced by petroleum fractions and
natural gas. Petrocoke is the emerging source for synthesis gas. Coal is again getting
importance alone or with combination of petroleum coke. Reactions in the manufacture
of synthesis gas by steam reforming and partial oxidation are shown in Table 20.17.
Various routes for synthesis gas and ammonia and methanol manufacture is shown
in Figure 20.6.

Table 20.17: Reactions in the manufacture of synthesis gas by

steam reforming and partial oxidation
Process steps Reaction Process condition
Desulfurization: C H SH + H → H S + C H Al-Co-Mo
2 5 2 2 2 6
1st stage Al-Ni-Mo
C6H5SH + H2 → H2S + C6H6
Catalyst 350–400ºC
C4H4SH + 3H2 → H2S + C4H9
CS2 + 4H2 → 2H2S + CH4
COS + H2 → H2S + CO
2nd stage CH3SC2H5 + H2 H2S + CH4 + C2H4 Zinc oxide absorbent
200–500ºC
H2S + ZnO → ZnS + H2O
Steam CnHm + 1/4(4n-m)H2O → 1/8(4n+m) CH4 + 1/8(4n-m)CO2 Nickel catalyst 800ºC
reforming two Endothermic reaction
CH4 + H2O → CO + 3H2
stages
CO + H2O → CO2 + H2
Partial CnHm + [(2n+m)/4]O2  nCO + m/2H2O Exothermic reaction
oxidation
CnHm + nH2O  nCO + (n+m/2) H2
2CO  C + CO2
CO + H2  C + H2O
378 Chemical Process Technology

Fig. 20.6: Various routes for synthesis gas and ammonia and methanol manufacture

Process Technology
Various synthesis gas production technologies are steam methane reforming, naphtha
reforming, auto-thermal reforming, oxygen secondary reforming, and partial oxidation
of heavy hydrocarbons, petroleum coke and coal.
Various steps involved in synthesis gas production through steam reforming are:
• Desulfurization of gas
• Steam reforming and compression
• Separation of CO2
Various available synthesis gas generation schemes are:
• Conventional steam reforming
• Partial oxidation
Petrochemical Industry 379

• Combined reforming
• Parallel reforming
• Gas-heated reforming

20.6.2 Methanol
Methanol was first obtained by Robert Boylein in the year 1661 through rectification of
crude wood vinegar over milk of lime and was named adiaphorous spiritus liglorum.
The term methyl was introduced in chemistry in 1835. Methanol is one of the largest
volume chemicals produced in the world. Methanol consumption can be separated
into three end-use categories—chemical feedstock, methyl fuels, and miscellaneous
uses. About 71% of the current global consumption of methanol is in the production
of formaldehyde, acetic acid, methyl methacrylate, and dimethyl terephthalate. The
global methanol industry has experienced very fundamental and structural changes
and has settled down considerably.
Demand changes in key methanol derivatives may adversely affect future demand
in case of methanol. Product profile of methanol is given in Table 20.20. Globally the
demand is expected to grow exponentially, not only caused by growing internal market
of traditional applications but accelerated by new applications such as directing blending
with gasoline, methanol to olefins (e.g. propylene) and dimethyl ether (Chemical Weekly,
November 15, 2011).
Global demand for methanol will reach 122.6 million tons by 2020. Global methanol
demand was 26.6 million tons and 44.9 million tons in 2000 and 2010 respectively
(Chemical Industry Digest, July 2012, p.29). Present capacity of methanol in India is
4.65 lakh tons. Product profile of methanol, capacity for methanol, unit-wise production
and sales of methanol and methanol consumption pattern and growth are given in
Tables 20.18 to 2021.

Table 20.18: Product profile of methanol

Product Uses
DMT/ polyethylene Polyester fiber and film, adhesives, wire coating, textile sizing,
terephthalate herbicides
Methyl methacrylate (MMA) Cast sheet, surface coating, molding resins, oil additives
MTBE Oxygenate
Mono methanolamine Naphthyl-n-methyl carbamate, monoethyl hydrazine, mono­methyla­
mine nitrate
Dimethylamine Dimethyl acetamide, dimethyl formamide, dimethyl hydrazine,
2,4-dichlorophenoxyacetic salt
Methylacetate Paint remover
Dimethylaniline Solvent, flavoring, dyes, fragrance
Acetic acid Vinyl acetate, acetic anhydride, chloroacetic acid, ethyl acetate, butyl
acetate, isopropyl acetate, acetyl chloride, acetanilide
Formaldehyde Phenolic resins, pentaerythritol, trioxane, 1,4-butanediol, formal­
dehyde, sulfoxylate, tetraoxane, resorcinol resin
Methylhalides Quaternary amines, methyl cellulose, butyl rubber, trimethanol
propene
380 Chemical Process Technology

Table 20.19: Capacity for methanol in India

Units Location Capacity (Tpa) Share (%)
Gujarat Narmada Valley Fertilizers Ltd. Gujarat 2,38,100 51.11
Deepak Fertilizers & Petrochemicals Ltd. Maharashtra 1,00,000 21.46
Rashtriya Chemicals & Fertilizers Ltd. Maharashtra 7,2,600 15.58
Assam Petrochemicals Ltd. Assam 3,3,000 7.11
National Fertilizers Ltd. Punjab 2,2,110 4.74
Total 4,65,810 100.00

Table 20.20: Unit-wise production and sales of methanol

Production sales Sales
Units
2009–10 2010–11 2009–10 2010–11
Gujarat Narmada Valley Fertilizers Ltd. 1,87,079 2,02,544 1,11,511 1,26,059
Deepak Fertilizers & Petrochemicals Ltd. 65,647 81,888 65,703 81,708
Rashtriya Chemicals & Fertilizers Ltd. 44,103 68,700 19,746 41,264
Assam Petrochemicals Ltd. 33,759 30,000 15,040 15,000
National Fertilizers Ltd. 2,669 516 131 44
Total 3,33,257 3,83,648 2,12,131 2,64,075

Table 20.21: Methanol consumption pattern and growth

Users Share (%) Growth rate (%)
Formaldehyde 48 7
Pharmaceuticals 21 8.5
Oxygenates 9 –
Acetic acid 5 4
Alkyl amines 4 9
Dimethyl sulfate 3 8
Agrochemicals 3 5
Chloromethanes 4 8
Solvents/others 3 8
Total 100 6
Source: Chemical Weekly, November 15, p.199, 2011.

Methanol and dimethyl ether are likely to be notified as transport fuel which will help
lower fuel costs in India using Israel Technology (Chemical Industry Digest, Annual
January 2018; p. 15).

Methanol Process Technology

From the early 1800s until 1920s, the distillation of wood to make wood alcohol was the
source of Methanol. The most common industrially favored method for the production of
Petrochemical Industry 381

methanol was first developed by BASF in 1923 in Germany from synthesis gas utilizing
high pressure process using zinc-chromic oxide catalyst. However, due to high capital
and compression energy costs compounded by poor catalyst activity, high-pressure
process was rendered obsolete when ICI in the year 1966 introduced a low-pressure
version of the process at 5–10 MPa and 210–270ºC, with a new copper-zinc oxide-based
catalyst of high selectivity and stability.
Process steps involved in the production of methanol are:
• Production of synthesis gas using steam reforming or partial oxidation
• Synthesis of methanol
• High-pressure process (25–30 MPa)
• Medium pressure (10–25 MPa) process
• Low-pressure process (5–10 MPa)
Figure 20.7 illustrates the production of methanol from steam reforming of natural
gas and naphtha.
The major reactions take place during methanol synthesis converter can be described
by following equilibrium reactions:
CO + 2H2 CH3OH DH298ºK= –90.8 kJ/mol

CO2 + 3H2 CH3OH + H2O DH298ºK= –49.5 kJ/mol

CO2 + H2 CO+H2O DH300ºK= 41.3 kJ/mol

The first two reactions are exothermic and proceed with reduction in volume. In order
to achieve a maximum yield of methanol and a maximum conversion of synthesis gas,
the process must be affected at low temperature and high pressure.
After cooling to ambient temperature, the synthesis gas is compressed to 5.0–10.0 MPa
and is added to the synthesis loop which comprises the following items—circulator,
converters, heat exchanger, heat recovery exchanger, cooler, and separator. The catalyst
used in methanol synthesis must be very selective toward the methanol reaction,
i.e. give a reaction rate for methanol production which is faster than that of
competing.

Fig. 20.7: Methanol from steam reforming of natural gas and naphtha
382 Chemical Process Technology

20.6.3 Formaldehyde
Some major intermediates derived from formaldehyde are chelating agents, acetal
resins, 1,4-butanediol, polyols, methylene diisocynate. It is also used for the manufacture
of wide variety of chemicals, including sealant, herbicides, fertilizers, coating, and
pharmaceuticals. Product profile of formaldehyde is given in Table 20.22.

Table 20.22: Product profile of formaldehyde

Product Uses
Formaldehyde Thermosetting resin: Phenol, urea melamine, formaldehyde resins
Hexamethylenetetramine, plastic and pharmaceuticals
1,4-Butadiol
Methylene diisocyanate
Fertilizer, disinfectant, biocide preservative, reducing agent, corrosion inhibitor
Polyaceta resin
p-Formaldehyde
Pentaerythritol (Explosive-PETN), alkyl resins

Formaldehyde is commercially available as aqueous solution with concentration

ranging from 30–56 wt.% HCHO. It is also sold in solid form as paraformaldehyde or
trioxane. The production of formaldehyde in India has been growing at a fairly constant
rate during last 10 years. There are presently about 17 units in India. Installed capacity
and production of formaldehyde during 2003–04 were 2.72 lakh tons and 1.89 lakh tons,
respectively.
Various industrial processes for manufacture of formaldehyde using silver and
iron-molybdenum catalyst are given in Table 20.23. Process diagram for manufacture
of formaldehyde using silver and iron-molybdenum catalyst is shown in Figures 20.8
and 20.9, respectively.

Table 20.23: Industrial processes for manufacture of formaldehyde

Catalyst Process licensor
Silver catalyst processes Bayer, Chemical Construction, Ciba, DuPont, IG Farben, CdFChemie
Process, BASF process, ICI Process
Iron-molybdenum catalyst Degussa Process, Formox Process, Fischer-Adler, Hiag-Lurgi,
processes IFP-CdFChimleLumus, Motedisous, Nikka Topsoe, Prolex

20.6.4 Acetic Acid (CH3COOH)

Acetic acid is one of the most widely used organic acids and finds application in the
manufacture of wide range of chemicals. Acetic acid is the largest methanol-based
chemical in terms of volume. World capacity and consumption pattern of acetic
acid is given in Table 20.24. Installed capacity of acetic acid in India is mentioned in
Table 20.25. Table 20.26 shows the market share of acetic acid in India by different
companies. Product profile of acetic acid is given in Table 20.27.
Petrochemical Industry 383

Fig. 20.8: Formaldehyde using silver catalyst

Fig. 20.9: Formaldehyde from iron molybdenum catalyst

384 Chemical Process Technology

Table 20.24: World acetic acid capacity and consumption pattern

Product Consump­- Consumption Capacity Annou- Capacity change
tion 2002 growth (%) 2002 nced capa-­­ needed by 2012–2002
(’000 tons) (’000 tons) city due after announcement
by 2012
1997– 2002– 2007– (’000 tons) (%)
(’000 tons)
2002 2007 2012
Acetic 8,302 3.9 3.4 2.5 9,559 994 1,785 19
acid
Source: Chemistry Industry News, March 2004; SRI Consulting, World Petrochemicals Program .

Table 20.25: Installed capacities of acetic acid in India

Company Installed capacity (tpa)
Indian Organics Chemicals Ltd. 15,000
Somaiya Chemicals Ltd. 15,000
Somaiya Organics 20,000
Andhra Sugars Ltd. 1,000
Ashok Organic Industries 30,000
EID Parry (I) Ltd. 10,000
Gujarat Narmada Valley Fertilizer Corp. Ltd. 50,000
Kanoria Chemicals & Industries 6,000
Laxmi Organic Ltd. 9,500
Trichy Distilleries 12,000
Vam Organics 1,15,500
Ashok Alcochem Ltd. 5,400
Dhampur Sugar Mills 7,300
Pentokey Ltd. 7,000
Polychem Ltd. 7,500
Trident Alcochem 6,000

Table 20.26: Market share of major acetic acid manufacturer

Name of the company Share (%)
Jubilant Organosys Ltd. 22
Ashok Organics Ltd. 17
IOCL 9
Gujarat Narmada Valley Fertilizer Corp. Ltd. 9
Others 43
Source: [Link]/sect/chor/[Link].
Petrochemical Industry 385

Table 20.27: Product profile of acetic acid

Product Uses
Monochloroacetic acid CMC manufacture, adhesives, thickeners for drilling muds, food
industry, pharmaceuticals, textiles, 2,4-D (insecticides)
Ethyl acetate, n-butyl Coatings, adhesives, inks and cosmetics
acetate, isopropyl acetate
Vinegar Food Preservative
Cellulose acetate Fibers, plastic film
Acetic anhydride Pharmaceuticals, intermediates, cellulose acetate
Acetanilide Pharmaceutical, dyes intermediate, Rubber accelerator, Peroxide
stabilizers
Peracetic acid Special oxidants
Terephthalic acid, DMT Polyester fiber, packaging, photographic films, magnetic tape sectors
Vinyl acetate Polyvinyl acetate, polyvinyl chloride, paints, adhesives, and coatings

20.6.5 Chloromethanes (Methyl Chloride, Methylene Dichloride,

Chloroform, Carbon Tetrachloride)
Chlorinated methanes, which include methyl chloride, methylene dichloride, chloroform
and carbon tetrachloride, are important derivatives of methane and find wide application
as solvents and as intermediate products. Product profile of chloromethane is given in
Table 20.28 (Mall, 2007).

Table 20.28: Product profile of chloromethane

Product Uses
Methyl chloride Refrigerant, butyl rubber, silicones, solvent, tetramethyl lead, intermediates
Methylene dichloride Solvent, intermediates, photographic film, degreasing solvents, aerosol,
propellants
Chloroform Chlorodifluoromethane, refrigerants, propellants, pharmaceuticals
Carbon tetrachloride Dichlorodifluoromethane, trichlorofluoromethane, solvent, fire extinguishers

Process Technology
There are two major routes for the manufacture of chloromethane (Fig. 20.10):
• Direct chlorination of methane
• Through methanol route
Direct chlorination of methane: Chlorination of methane (natural gas) is carried out
at around 400–450ºC during which following reaction takes place:
CH4 + Cl2 CH3Cl + HCl
Methyl chloride
CH3Cl + Cl2 CH2Cl2 + HCl
Methylene dichloride
CH2Cl2 + Cl2 CHCl3 + HCl
Chloroform
CHCl3 + Cl2 CCl4 + HCl
386 Chemical Process Technology

Fig. 20.10: Chloromethane from methane and methanol

20.6.6 Dimethylformamide [HCON(CH3)2]

Dimethylformamide is one of widely used solvents in the manufacture of acrylic
fiber. Because of its high dielectric constant, aprotic nature, wide liquid range and low
volatility, dissolving power, it is frequently used as solvent.
Process Technology
Dimethylformamide is made by following two processes (Fig. 20.11):
Two-step processes: Process involves carbonization of methanol to methyl formate
using basic catalyst and reaction of methyl formate with dimethylamine.
CH3OH + CO + HCOOCH3 (CH3)2NH + HCON(CH3)2 + CH3OH
Dimethylformamide
Sodium, 3.5 atm, 110–120ºC
CH2OH + CO HCOOCH3
Methoxide
HCOOCH3 + (CH3)2NH HCON(CH3)2 + CH3OH

Two-stage process

Direct one-step process from synthesis gas and ammonia

Fig. 20.11: Dimethylformamide production
Petrochemical Industry 387

20.6.7 Acetylene
It played important role during and after World War II in providing feedstock for large
number of organic chemicals when petrochemical industry was not well developed.
Acetylene’s highly reactive triple bond provided a ready “handle” for chemists to grab
onto for designing process chemistry.
Safety issues involved with handling of large volumes of acetylene and its expense
are big problem with adoption of acetylene-based processes. The process of acetylene
requires much energy and is very expensive. Acetylene is still being used for manufacture
of chemicals.
Various Routes for Acetylene
Calcium carbide route: This is the oldest method for production of acetylene and still
acetylene is produced by this process in small scale as well large scale. Calcium carbide
is produced by reacting lime with coke at temperature 2,000–2,100ºC in an electric
furnace. Two processes produce acetylene from calcium carbide: Wet process and Dry
process. Dry process is preferred as in case of calcium hydroxide, which is produced
during the process (is produced in the form of dry calcium hydrate).
CaC2 + 2H2O C2H2 + Ca(OH)2
Acetylene from cracking of hydrocarbons: Cracking of hydrocarbons such as methane,
ethane, propane, butane, ethylene, and natural gas can make acetylene.
2CH4 C2H2 + 3H2
C2 H4 C2H2 + H2
C4H10 C2H2 + C2H4 + 2H2

Product derived from acetylene: Acetylene is extremely reactive hydrocarbon and

was initially was used for the manufacture of large number of chemicals which are now
being derived from acetylene route. Product profile of acetylene is given in Figures 20.12
and 20.13 (Mall, 2007, Huang et al.).
Acetaldehyde: HC  CH + H2O CH3CHO
Acrylonitrile: HC  CH + HCN HC = CH = CH2 = CHCN

Chlorinated solvents:
HC  CH + 2Cl2 CH2Cl2CHCl2 CHCl = CCl2 + HCl
CHCl = CCl2 + Cl2 CH2Cl2CCl3 CCl2 = CCl2+ HCl

Vinyl acetate: HC  CH + CH3COOH CH2 = CHOOCCH3

Chloreprene: HC  CH + CH3COOH CH2 = CHOOCCH3

CH2 = CHOOCCH3 + Cl2 CH2 = CClCH = CH2

Vinyl chloride and vinylidene chloride:

HC  CH + HCl CH2 = CHCl
CH2 = CHCl + Cl2 CH2 ClCHCl2
CH2 ClCHCl2 CH2 = CCl2 + HCl

Vinyl fluoride: HC  CH + HF CH2=CHF

Fig. 20.12: Reactions in acetylene derived chemicals

388 Chemical Process Technology

Fig. 20.13: Product profile of acetylene

20.7 ETHYLENE DERIVATIVES: ETHYLENE OXIDE, ETHYLENE GLYCOL, ETHYLENE

DICHLORIDE AND VINYL CHLORIDE
Ethylene is one of the most versatile petrochemicals and its production has steadily
increased over the years. Ethylene is called as king of chemicals and surpasses all
organic chemicals in production and in amount sold. Ethylene is the basic building
block for petrochemicals. Product profile of ethylene is given in Table 20.29. Because
of its ready availability at low cost and high purity and reactivity, ethylene has become
one of the important raw materials for large number of petrochemicals and products.
Ethylene has replaced the earliest route of production of vinyl chloride, acetaldehyde,
vinyl acetate and other chemicals through acetylene route. Installed and production
capacity of ethylene and its derivatives is mentioned in Table 20.30. Large tonnage of
ethylene is being used for the manufacture of polyethylene, ethylene oxide, ethylene
glycol and styrene. World requirement of ethylene is given in Figure 20.14. World
Petrochemical Industry 389

Table 20.29: Product profile of ethylene

Product Uses
Polyethylene LDPE, LLDPE, HDPE Films, moldings, pipes, cable covering, netting
Ethylene oxide and ethylene glycol Antifreeze, polyester, solvents, detergent, textile,
ethanol amine
Styrene Synthetic rubber and polystyrene
Ethyl alcohol Industrial solvent and chemical intermediates
Acetaldehyde (from ethyl alcohol) Acetic acid (peracetic acid), acetic anhydride, cellulose
acetate, vinyl acetate, pyridine, butyraldehyde (ethyl
hexanol)
Olefin n-Butenes, synthetic detergent, oxo-alcohols, synthetic
lubricants
Chlorinated solvents Trichloroethylene, perchloroethylene
Ethyl chloride Tetraethyl lead, chemical intermediates
Vinyl acetate Polyvinyl acetate, polyvinyl alcohol
Vinyl chloride Polyvinyl chloride (PVC)

Table 20.30: Installed capcity and production of important

ethylene and ethylene derivatives in India
Product Installed capacity 2008–09 Production 2009–10
(thousand metric ton) (thousand metric ton)
Ethylene 2,841 2,515
Ethylene oxide 120 117
Monoethylene glycol 820 738
Acetaldehyde 238 59.2
Acetic anhydride 59 43.42
Ethanol amine 10 7.0
Ethyl acetate 132.0 103.96

Fig. 20.14: World ethylene supply/demand profile 2008 production=117.3 million metric tons
Source: Polyolefins Feedstocks and Market by Howard Rappaport CMAI, Plast., India-February, 2009.
390 Chemical Process Technology

ethylene capacity is shown in Figure 20.15. World ethylene complexes, capacity, and
top 10 producers are mentioned in Tables 20.31 to 20.33, respectively. Global ethylene
capacity growth is given in Table 20.34.

Fig. 20.15: World Ethylene Capacity (120 Million tons 2008) (Source: Petrochemical Economics:
Technology Selection in a Carbon Constrained World: [Link]
[Link]

Table 20.31: World top ethylene complexes

Company Location Capacity, TPY
1 Formosa Petrochemical Corp. Mailiao, Taiwan, China 29,35,000
2 Nova Chemicals Corp. Joffre, Alta 28,11,792
3 Arabian Petrochemical Co. Jubai, Saudi Arabia 22,50,000
4 Exxon Mobi Chemical Co. Baytown, Tex. 21,97,000
5 Chevron Philips Chemical Co. Sweeny, Tex. 18,65,000
6 Dow Chemical Co. Terneuzen, Netherlands 18,00,000
7 Ineos Olifins and Polymers Chocolate Bayou, Tex. 17,52,000
8 Equistar Chemicals LP Channelview, Tex. 17,50,000
9 Yanbu Petrochemical Co. Yanbu, Saudi Arabia 17,05,000
10 Equate Petrochemical Co. Shuaiba, Kuwait 16,50,000
Source: Oil and Gas Journal, July 4, 2011.

Table 20.32: Regional capacity breakdown

Ethylene capacity, TPY
Asia-Pacific 4,26,31,000
Eastern Europe 79,71,000
Middle East, Africa 2,33,57,000
North America 3,45,08,000
South America 50,83,500
Western Europe 2,49,04,000
Total capacity 13,84,54,500
Source: Oil and Gas Journal, July 4, 2011.
Petrochemical Industry 391

Table 20.33: Top 10 ethylene producers

Capacity, TPY
Company Sites
Of entire complexes With only company partial interests
Saudi Basic Industries Corp. 15 1,33,92,245 1,02,73,759
Dow Chemical Co. 21 1,30,44,841 1,05,29,421
Exxon Mobil Chemical Co. 19 1,25,15,000 85,50,550
Royal Dutch Shell PLC 13 93,58,385 59,46,693
Sinopec 13 75,75,000 72,75,000
Total AS 11 59,33,000 34,71,750
Chevron Philips Chemicals Co. 8 56,07,000 53,52,000
Lyondell Basell 8 52,00,000 52,00,000
National Petrochemical Co. 7 47,34,000 47,34,000
Ineos 6 46,56,000 42,86,000
Source: Oil and Gas Journal, July 4, 2011.

Table 20.34: Global ethylene capacity growth (thousand tons)

Major region 2008 Capacity 2013 Capacity 08 to ’13 Delta
Middle East/Africa 19,711 34,461 14,751
Asia Pacific 39,617 56,349 16,732
America 40,421 40,434 12
Europe 30,953 31,293 340
World (Total) 130,702 162,537 31,836

20.7.1 Ethylene Oxide (EO)

Ethylene oxide is one of the important petrochemical intermediate used for the
manufacture of large number of products; some of the major uses are in the manufacture
monoethylene glycol glycol ethers which is made by reaction of ethylne oxide and
alcohols, ethanol amines. Surfactant indutry is one of largest user of EO, both for
industrial and house hold applications. Product profile of ethylene oxide is given in
Table 20.35.

Table 20.35: Product profile of ethylene oxide

Product Uses
Ethanol amines Detergent, soap solvent, cosmetics, morpholine
Monoethylene glycol Polyester, staple fiber yarn, pet bottles, film
Diethylene glycol Coolants, pesticides, rubber compounding, plasticizer,
polyurethane, alkyl resin
Triethylene glycol Natural gas conditioning agent’s plasticizer
Polyethylene glycol Pharmaceuticals, brake fluid, cosmetics
Non-ionic surfactants, ethoxylates Textile auxiliaries, binders, dyes, pesticides, pharmaceuticals,
cosmetics
Glycol ethers Brake fluid and protective coating
392 Chemical Process Technology

Chlorohydrin Process
Cl2 + H2O HOCl + HCl

C2H4 + HOCl CH2OH – CH2Cl

CH2OH – CH2Cl + Ca (OH)2 CH2 – CH2 + CaCl2 + H2O

Direct Oxidation
   Ag, 260–290ºC
H2C = CH2 + 1/2O2 C2H4O

H2C = CH2 + 3O2 2CO2 = 2H2O; DH = –135 k.J/mol

C2H4O + 5/2O2 2CO2 + 2H2O

H2C = CH2 + 1/2O2 CH3CHO

H2C = CH2 + 2O2 HCHO

20.7.2 Mono-, Di-, and Tri-ethylene Glycols (MEG, DEG, TEG)

A major petrochemical and find application in manufacture of polyester and as antifreeze
accounts for 70% of ethylene oxide production. Ethylene oxide preheated to 195ºC. EO:
H2O ratio 10:1 to maximize MEG production by-products DEG, TEG. Figure 20.16 gives
detail manufacturing of MEG, DEG and TEG from ethylene oxide.

Fig. 20.16: MEG, DEG and TEG from ethylene oxide

20.7.3 Vinyl Chloride

Vinyl chloride is one of the important petrochemical feedstocks and finds use in
manufacture of polyvinyl chloride the second largest tonnage commercial polymer
Petrochemical Industry 393

after polyethylene. About 95% of the present vinyl chloride production worldwide is
used in polymer production or copolymer application. Another important use of vinyl
chloride is in the production of vinylidiene chloride. According to SRI consulting global
production and consumption of ethylene dichloride (EDC) in 2009 (which accounted
for 95% consumption in vinyl chloride manufacture), was about 33.7 million tons with
global capacity of about 73% in 2009.
Process Technology
The original process of manufacture of vinyl chloride was by reaction of acetylene
derived from calcium carbide with hydrochloric acid in gaseous phase in presence
of mercuric chloride catalyst at temperature around 100–180ºC. However, with the
availability of ethylene from cracker plant now vinyl chloride is made from ethylene
obtained from cracker plant.
The process of vinyl chloride manufacture takes place in two stages:
• First stage: Ethylene is reacted with chlorine in either liquid or vapor phase in
presence of ferric chloride. However, the liquid phase process is more common and
the reaction takes place at around 50–90ºC and 3–5 atm pressure.
• Second stage: Vinyl chloride is produced by pyrolysis of vaporized ethylene
dichloride in a set of tubular furnaces at temperature of about 400–500ºC.
Direct chlorination
CH2 = CH2 + Cl2 ClCH2 – CH2Cl

Ethylene chloride by direct chlorination of ethylene: The original process of

manufacture of vinyl chloride by ethylene chlorination and cracking of ethylene
dichloride had been replaced by oxychlorination process in which no hydrochloric
acid is formed as by-product. Process diagram of vinyl chloride from oxychlorination
process is shown in Figure 20.17.
The process involves production of ethylene dichloride by exothermic reaction of
ethylene, hydrochloric acid and oxygen.
Liquid phase: Fixed or fluidized bed reactor is used at 170–180ºC and 15–20 atm pressure
in presence of copper chloride.
Vapor phase reaction: The temperature and pressure are 200–220ºC and 20–50 atm
pressure.
Reactions
Vinyl chloride by chlorination:

•
Initiation: ClCH2 – CH2Cl ClCH2 – CH2 + Cl
• •
Propagation: C l + ClCH2 – CH2Cl ClCH2 – CHCl + HCl
• •
ClCH2 – CHCl CH2 = CHCl + Cl
• •
Termination: Cl + ClCH2 – CH2 CH2 = CHCl + HCl

The first stage is typical electrophilic addition of a halogen to an alkene. The second
stage is a free-radical chain reaction.
394 Chemical Process Technology

Fig. 20.17: Vinyl chloride from oxychlorination process

Oxychlorination: The original process of manufacture of vinyl chloride by ethylene

chlorination and cracking of ethylene dichloride had been replaced by oxychlorination
process in which no hydrochloric acid is formed as by-product. The process involves
production of ethylene dichloride by exothermic reaction of ethylene, hydrochloric acid,
and oxygen. Liquid phase: at about 170–180ºC in at 15–20 atm pressure in presence
of copper chloride in either fixed or fluidized bed reactor. Vapor phase reaction: the
temperature and pressure are 200–220ºC and 20–50 atm pressure.
• Direct chlorination: CH2 = CH2 + Cl2 ClCH2 – CH2Cl

• Oxychlorination: CH2 = CH2 + 2HCl + ½O2 ClCH2 – CH2Cl + H2O

• Ethylene dichloride pyrolysis: ClCH2 – CH2Cl CH2 = CHCl + HCl

• Overall reaction: 2CH2 = CH2 + Cl2 + ½O2 CH2 = CHCl + H2O

20.7.4 Vinyl Acetate

Vinyl acetate is one of the important derivatives of ethylene which is used as
intermediate for manufacture of polyvinyl alcohol, polyvinyl acetate, polyvinyl
butyral, etc.
Petrochemical Industry 395

Global end use pattern of vinyl acetate is—adhesives (23%), paints and coating
(29%), textiles (21%), plastics (17%), paper and board (10%). Consumption pattern of
vinyl acetate in India is polyvinyl acetate emulsions and resins (50%), polyvinyl alcohol
(25%), ethylene vinyl acetate (10%), others (15%).
End use pattern of vinyl acetate in India is—adhesives (35–40%), textiles (30–35%),
paints and coating (15–20%), others (10–15%). Uses of vinyl acetate is given in Table 20.36.
Process Technology
• The ethylene route has replaced the traditional process of manufacture of vinyl
acetate. The production of vinyl acetate through acetylene route, which was developed
by Wacker in 1930, involves reaction of acetylene and acetic acid in liquid phase at
60–80ºC and 1–2 atm pressure in presence of mercury salt catalyst.
H2C = CH2 + CH3COOH H3COOCHC = CH2
• Vinyl acetate from ethylene route: Vinyl acetate is made by reaction of ethylene
with acetic acid by liquid phase process or by vapor phase process in presence of
palladium and cupric chloride catalyst. In the vapor phase process, the following
reactions take place:
CH2 = CH2 + CH3COOH + PdCl2 CH2 = CHCOOCH3 + 2HCl + Pd
Pd + 2CuCl2 PdCl2 + 2CuCl

2CuCl + 2HCl + H2O2 2CuCl2 + 2H2O

Table 20.36: Uses of vinyl acetate

Polyvinyl acetate Surface coating adhesives, textile resins
Polyvinyl alcohol Textile size, grease proofing paper, vinyl
emul­sifier, thickener, viscosity regulators,
adhesives,

Vinyl acetate Acrylonitrile copolymer Acrylic fibers

Polyvinyl formate Water resistant insulation enamel
Ethylene vinyl acetate copolymers Textile and paper coating
Vinyl chloride comonomers VC-VAC, LP records, VC-VAC coating
Polyvinyl butyraldehyde Safety glass

20.7.5 Ethanol
Apart from its major use as a beverage. it is one of the most versatile chemical and basic
building blocks of the organic chemical industry. Ethanol is generally produces by
fermentation of molasses. Due to the development of petrochemical industry and availability
of ethylene, now ethylene provides another major route of formation of ethanol.
However, still molasses were used to produce ethanol in India. In India some of the
important chemical are still prepared through ethanol which were earlier prepared
through petrochemical route. Two such important complexes are Jubilant Organosys
Ltd., Gajraula (Uttar Pradesh) and Indian Glycol Ltd., Kashipur (Uttar Pradesh), where
large numbers of ethanol derivatives are manufactured through ethanol route.
Various routes for manufacture of ethanol:
• Fermentation of molasses
• Catalytic hydration of ethylene
396 Chemical Process Technology

• Ethylene esterification and hydrolysis

• Gas to bioethanol
Fermentation of Molasses
Ethyl alcohol is prepared from molasses by fermentation process utilizing yeast enzymes.
Separation of 8–10% alcohol is achieved in a series of distillation columns, as alcohol
and water at 95% concentration form azeotropic mixture.
Ethanol by Esterification and Hydrolysis
Ethylene and sulfuric acid are reacted at 80ºC and 1.5 MPa to form a mixture of ethyl
sulfates, which are then hydrolyzed to ethyl alcohol.
Ethylene and sulfuric acid are reacted in absorber from which the mixture of ethylene
sulfates thus formed is fed to hydrolyzer from which the crude alcohol and sulfuric
acid are fed to stripping section and caustic scrubbing section and finally to a series of
two distillation columns for separation of ether and alcohol.
C2H4 + H2SO4 C2H5OSO3H

2C2H4 + H2SO4 (C2H5O)2SO2

C2H5OSO3H + (C2H5O)2SO2 + 3H2O 3C2H5OH + 2H2SO4

2C2H5OH C2H5OC2H5 + H2O

Ethanol by Vapor Phase Hydration of Ethylene

An ethylene rich gas is mixed with water and heated to about 300ºC and passed on to
fixed-bed catalytic reactor where catalytic hydration of ethylene takes place.
The catalyst used is phosphoric acid deposited on silica gel. The reactor effluents are
sent to separator for separation of vapor and liquid. The gases from the separator are
cooled and scrubbed with water to recover traces of alcohol. The alcohol water mixture
is sent to a series of distillation columns where ether is separated in the light end column
and finally 95% by volume ethanol water azeotrope is separated (Fig. 20.18).

Fig. 20.18: Ethanol from catalytic recycle hydration of ethylene

Petrochemical Industry 397

Gas to Bioethanol
IOCL and Lanaza Techare collaboration are going to have process of have the first
off-gas to bioethanol unit. The process uses biocatalyst for fermentation of waste off-
gases. Ethanol produced from recycling of the refiner’s off-gas to have greenhouse
gas emissions saving. It will save about 1 million tons of CO2 per annum to produce
40 million liter per annum of ethanol. The process allows refineries to divert waste
gases from the grid, supporting the transition to fully renewable power while
recycling the carbon to liquid fuels and petrochemicals (Chemical Industry Digest,
August 2017).

20.7.6 Acetaldehyde
Product profile of acetaldehyde is shown in Table 20.37.

Table 20.37: Product profile of acetaldehyde

Product Uses
Pyridine, picoline Solvent, drugs, dyes, agricultural chemicals
Chlor-aldehydes Insecticides, fungicides, disinfectants
Acetaldol 1,3-butylene glycol (polyesters), urethane coating,humcetant,
printing ink, crotonaldehyde, n-butyl alcohol, n-butyric acid
anhydride, 2-ethyl hexanol, rubber accelerator, sorbic acid
Paraldehyde Rubber accelerator, antioxidant dye, stuff
Peracetic acid Epoxidation reaction, reagent in caprolactam, synthetic glycerols
Pentaerythritol Alkyl resin, stabilizer, plasticizers, chlorinatedpolyether resin,
intumescents
Acetic, anhydride Acetyl salicylic acid, cellulose acetate, esters
Acetic acid Cellulose acetate, vinyl acetate, chloroacetic acid, ammonium
acetate
Lactic acid Food and, beverages, lactates, adhesives, leather processing

Various Routes for Acetaldehyde

1. Dehydrogenation of ethanol

2. Oxidation of ethanol

3. Acetylene

4. Ethylene
398 Chemical Process Technology

5. Dimethylformamide

20.7.7 Acetone
Cumene process

Hydrogenation of propanol

Propylene oxidation

Oxidation of 2-propanol

Oxidation of p-di-isopropyl benzene

Fermentation

20.8 PROPYLENE, PROPYLENE OXIDE, AND ISOPROPANOL

20.8.1 Propylene
Propylene often referred as the crown prince of petrochemicals and is superficially
similar to ethylene but there are many differences in both production and uses (Hatch
and Matar, 1978). Propylene is used in many of the world’s largest and fastest growing
synthetic materials and thermoplastics. The demand of propylene has increased rapidly
during the last 20 years and primarily driven by polypropylene demand (Mall, 2007).
Product profile of propylene is given in Table 20.38.
According to SRI consulting 2010 global production and consumption of propylene
in 2009 was both approximately 71 million tons with capacity utilization of 78.5%.
Global propylene consumption is forecasted to average growth of around 5.1% per
year from 2009 to 2014 and 3.5% per year from 2014 to 2019. Consumption of refinery
grade propylene made up 9% of total consumption in 2009, chemical grade 23% and
polymer grade 68%. Refinery grade propylene is consumed mainly for production of
cumene and isopropyl alcohol. Chemical grade propylene mostly goes into oxo-alcohol,
propylene oxide, and acrylonitrile.
Petrochemical Industry 399

Table 20.38: Product profile of propylene

Product Uses
Miscellaneous chemicals 1 butanol, 2-ethyl hexanol, allyl chloride, epichlorohydrin
Polymer Polypropylene, polyacrylamide, nylon 66, acrylic sheets
Propylene oxide Polyether-polyols, glycol ethers, isopropyl amines, propylene
carbamate, surfactants
Propylene glycol Unsaturated polyester resins, food additives, cellophane, paints and
coating, plasticizers, functional fluids, antifreeze, tobacco treatment
Acrylonitrile Acrylic fiber, acrylic acid, acrylates, methyl methacrylates, adiponitrile
Isopropanol Acetone, cosmetics, solvents, pharmaceuticals, isopropyl acetate
Polyols Polyurethane and polyester

Sources of Propylene
Propylene is a by-product of steam crackers and varying number of olefins is produced
from steam crackers depending on the type of feedstock. Other sources of propylene may
be recovery of propylene from FCC light ends, propane dehydrogenation, metathesis.
Some of the major processes for production of propylene is given in Table 20.39. Typical
composition of FCC gas stream is given in Table 20.40.

Table 20.39: Propylene production technologies

Technology Process Licensor
Olefin Conversion This process involves production of propylene from ABB Lumus Global
Technology ethylene and 2-butenes in a fixed bed metathesis
reactor containing proprietary catalyst, which
promotes reaction of ethylene and 2-butene to form
propylene and simultaneously isomerizes 1-butene
to 2-butene.
Superflex Process The process uses a fluidized bed catalytic reactor Kellogg Brown &
system using proprietary catalyst which converts Root, Inc.
low value feedstock to predominantly propylene
and ethylene products. Low value light hydrocarbon
streams from ethylene plant and refineries can be
used, e.g. C4 and C5 olefin rich stream from ethylene
plants, FCC naphtha, C4 stream, thermally cracked
naphtha from Vis breakers or cokers.
Propylur Process This process produces propylene beside ethylene Lurgi Oel Gas
from low value rich feeds ranging from C4–C8 from Chemie GmbH
ethylene plant and refineries in a fixed bed reactor
using proprietary catalyst. The process offers high
selectivity towards propylene.
UOP Oleflex Process This process produces polymer grade propylene UOP LLC
from propane and the process consists of a reactor,
catalyst regeneration section and product separation
and fractionation section. The process uses platinum
catalyst (DeH-12 catalyst).
Contd...
400 Chemical Process Technology

Table 20.39: Propylene production technologies (Contd...)

Technology Process Licensor
UOP/Hydro MTO This process converts crude methanol (produced UOP LLC and
Process from synthesis gas using natural gas) to ethylene and Hydro Norway
propylene and can be operated either a maximum
ethylene or a maximum propylene production mode
using MTO-100 silicoaluminophosphate synthetic
molecular sieve-based catalyst. The process utilizes
fluidized bed reactor and regenerator.
Methanol to This process produces propylene through methanol Lurgi Oel Gas
Propylene (MTP) route using natural gas. In this process, propylene Chemie GmbH
Technology is produced in two steps: First methanol is con-
verted to dimethyl ether in reactor followed by
reaction of methanol/DME in second reactor.
Methanol can be produced from methane from
conventional method.
C4 Hydrogenation This process involves production of polymer grade Axens, Axens NA
and Meta-4 Process propylene plus an isobutylene rich stream or MTBE
by upgrading low value C4 stream pyrolysis C4
cuts or butene rich cut. The process steps involve—
butadiene and C4 acetylenes selective hydrogenation
and butadiene hydroisomerization, isobutylene
removal or MTBE production and metathesis step
for conversion of butene and ethylene to propylene.
The two main equilibrium reactions taking place are
metathesis and isomerization.
Olefin Ultra™ A new ultra-high activity ZSM-5 additive that
provides the highest activity has been developed by
Davision catalysts.
KBR’s Maxofin-3 KBR’s Maxofin process is based on fluidized bed Kellogg Brown &
technology cracking of gas oils and residue feeds using ZSM Root, Inc.
catalyst and proprietary MAXOFIN-3 catalyst
additive. The process gives 15% or higher propylene
yield from gas oil.
Sources: Pujaodo and Vora, 1990; Badoni, et al. 1996; Meyers, 1986; Dunn, et al. 1992; Venner and
Kantorowicz, 2001; Petrochemical Processes 2003; Zinger, 2003; Nee, 2003; Dharia, et al. 2004, Eng.
et al. 2004.

Table 20.40: Typical composition of FCC gas stream

Products Yield weight (%)
Dry gas (including ethylene) 12.7
Propane 6.5
Propylene 21.0
Butene 35.8
Source: Badoni, et al. 1996

Catalytic Dehydrogenation
Catalytic dehydrogenation of light paraffins is of increasing importance because of the
growing demand of olefins such as propylene and isobutene (Reasco and Haller, 1994)
Petrochemical Industry 401

and n-butenes. Propane dehydrogenation accounts for 2% of the total world propylene
production. Some of the commercial processes available for dehydrogenation of propane
and n-butane are (Badoni, et al. 1996):
• Oleflex (UOP)
• Catofin (ABB Lumus)
• FBD-4 (Snamprogetti SPA)
• Star (Phillips Petroleum Company)
Catalytic dehydrogenation takes place at high temperature (650ºC) using platinum
based or chromium-alumina or Fe, Cr/Al2O3 as catalyst. Reactor effluent treatment for
the separation of hydrogen, propylene, and propane is not simple and total investment
is high. These production units can be installed only in areas where field propane is
available at low costs.

Methanol to Propylene
This process produces propylene from natural gas via methanol by converting methanol
to dimethyl ether in adiabatic reactor using high activity, high selectivity catalyst. The
methanol, water, DME stream is then feed to series of MTP reactor where steam is
added. The product stream is first processed for removal of traces of water, CO2 and
DME, followed by further processing for yielding polymer grade propylene.

20.8.2 Propylene Oxide, Propylene Glycol, and Polyols

Propylene oxide, propylene glycols, and polyols are important derivatives of
propylene. Propylene oxide is used for the manufacture of propylene glycol and
polyols. Major consumption of propylene oxide is manufacture of polyurethane
and polyester resins. Propylene glycol find major application in the manufacture
of unsaturated polyester resins, food additives, pharmaceuticals and personal care,
tobacco humectants, cellophane, paints and coatings. Polyols major use is in the
manufacture of polyurethane.

Propylene Oxide
Processes for making propylene oxide: There are two major processes for the
manufacture of propylene oxide: Propylene chlorohydrin process and propylene
oxidation process using peroxides.
Propylene Chlorohydrin Route: The chlorohydrination process consists of formation
of propylene chlorohydrin by the reaction between hypochlorous acid and propylene.
The propylene chlorohydrin is epoxidized to propylene oxide by a 10% solution of milk
of lime or NaOH. Various steps involved are:
• Propylene hypochlorination: Propylene is reacted with aqueous chlorine resulting in the
formation of propylene chlorohydrins. Unreacted propylene is recycled.
• Neutralization: Neutralization of propylene chlorohydrins containing hydrochloric
acid which is formed during the process.
• Dehydrochlorination: Reaction of propylene chlorohydrin with milk of lime or caustic
soda to produce propylene oxide
• Purification: Distillation of crude propylene oxide for separation heavy ends
402 Chemical Process Technology

Reactions:
Cl2 + H2O HOCl + HCl

By-products formed during the reaction are 1,2-dichloropropane and chlorinated

di-isopropyl ether. Some of the disadvantages and major economic drawbacks of the
process which led to the wide acceptability of epoxidation processes are use of costly
chlorine, production of weak calcium chloride byproduct, and corrosion problem due
to chlorine handling.
Oxidation route using peroxide compounds: In this process, propylene and peracetic
acid (in ethyl acetate) which is produced by oxidation of acetaldehyde are reacted in
a series of three specially designed reactors at 50–80ºC and 90–120 MPa pressure. The
reaction products are fed to the stripper where a mixture of propylene and propylene
oxide are obtained as top product while mixture of ethyl acetate and acetic acid is
obtained as bottom product. Both mixtures are fed to two separated columns where
separation of propylene oxide, ethyl acetate, acetic acid, and heavy end takes place.
Reaction:
Peroxide from acetaldehyde

Oxidation of propylene

Propylene Glycol
Propylene glycol is made by hydrolysis of propylene oxide. The process steps involve are:
Reaction section: Hydrolysis of propylene oxide resulting in formation of mono­pro­
pylene glycols (MPG). Small amount of dipropylene glycol (DPG) and tripropylene
glycol (TPG) are also formed.
Concentration section: Concentration of glycol solution in multiple effect evaporator.
Distillation section: Separation of MPG, DIPG and TPG separated from MPG column.
n series of distillation column where MPG is separated in first column.
Polyols
Polyols are made by polymerization of propylene oxide/ethylene oxide using a pro­
prietary catalyzed chain starter. The process consists of:
Petrochemical Industry 403

• Raw material preparation: Preparation of chain starter and addition in reactor along
with EO/PO
• Reaction: Polymerization using catalyzed chain extender
• Purification: Purification of raw polyol by neutralization.

Isopropanol
Ever since its first commercial introduction in 1920 as one of the first petrochemicals,
isopropyl alcohol has found wide use as a solvent and raw material for other chemical
products like acetone, isopropyl acetate, glycerol, isopropyl and disopropyl amines,
corrosion inhibitor di-isoprpopyl ammonium nitrate, floatation agent isopropyl
xanthate, isopropyl myristates, etc. (Akiyama, 1974).

Process technology
Two major processes for isopropanol manufacture are:
• Esterification of propylene by sulfuric acid and hydrolysis
CH3 – CH = CH2 + H2SO4 (CH3)2CH – O – SO3H

(CH3)2CH – O – SO3H + H2O CH3 – CH(OH)CH3 + H2SO4

• Direct catalytic hydration of propylene (vapor phase, liquid phase and mixed phase)
CH3 – CH = CH2 + H2O CH3 – CHOH – CH3 DH298ºK = – 51 kJ/mol
Although originally isopropyl alcohol was made by esterification of propylene and
hydrolysis, problems of corrosion and a high heat requirement has led to the use of
direct hydration process.
Direct hydration of propylene: In liquid phase hydration of propylene (Tokuyama Process)
silico tungstate is used. The catalytic hydration process takes at 250–27ºC at 200 atm
pressure. Propylene conversion has been reported around 60–70%.

Butanols (N-butanol and Iso-butanol)

Various routes for making butanol are:
• Acetaldehyde route
• Hydroformylation of propylene
• Oxidation of butane
Condensation of acetaldehyde: The process involves aldolization, dehydration,
hydrogenation

Hydroformylation of propylene: Butanol is manufactured from hydrogenation of

n-butyraldehyde and iso-butyraldehyde mixture obtained by hydroformylation
reaction of propylene and synthesis gas. Hydrogenation takes place at temperature
404 Chemical Process Technology

150–200ºC and 5–10 MPa pressure using copper or nickel catalyst. The butanols from
the hydrogenation reactor go to a series of distillation columns for separation of light
effluents and n-butanol and iso-butanol. About 88% of n-butanol and 12% iso-butanol
are obtained.

Butadiene (CH2= CH – CH = CH2)

Butadiene is one of the major petrochemicals with a wide range of uses as feedstock
for production of a variety of synthetic rubbers and polymer resins, the bulk of which
are related to styrene butadiene rubber (SBR), nitrile rubber, chloroprene rubber,
polybutadiene rubber, and acrylonitrile butadiene styrene (ABS) resin. Another major
use of butadiene is in the manufacture of adiponitrile which is a raw material for the
production of nylon 66. Global demand growth for butadiene is set to accelerate.
Butadiene based synthetic rubbers are mainly used in the automotive industry. It is
also widely used for manufacturing of engineering resins.
There are four major routes for production of butadiene:
• Steam cracking of naphtha
• Catalytic dehydrogenation of butenes
• Catalytic dehydrogenation of butanes
• Dehydrogenation-dehydration of ethanol (molasses route).
2-Ethyl Hexanol
Major use of 2-ethyl hexanol is in the manufacture of di-2-ethylhexylphthalate which
is used as plasticizer for vinyl resins. Other application is in synthetic lubricants,
antioxidants and antifoams. 2-Ethyl hexanol is made either by the oxo-synthesis or from
acetaldehyde route by condensation and hydrogenation. 2-Ethyl hexanol is also used in
the manufacture of ethyl hexa acrylate. Ethyl hexaacylateprodices soft and tacky film
with excellent low temperature flexibilities. Ethylhexanol also find application cable
coating compositions, nitrocellulose lacquers, as softener in nitrile rubber compounds,
in plastic compounds for water proof agents (Nandini Chemical Journal, July 1998,
p.21, Mall 2007).
Propylene route: In first step 4n-butyraldehyde is produced along with 1-isobutyral­
dehyde. 4n-butyraldehyde is further hydrogenated to 2-ethylhexanol

Propylene Carbonate (C3H6CO3)

Propylene carbonate is prepared by reaction of propylene oxide and carbon dioxide in
presence of ion-exchange resins (Mall, 2007).
Petrochemical Industry 405

Uses: Propylene carbonate is used as special solvent. It is used in solvent extraction,

plasticizers, organic synthesis, natural gas purification, and fiber spinning solvent.
Acrylic Acid
Acrylic acid is a versatile chemical which find application in the manufacture of glacial
acrylic acid and acrylic esters (acrylates and methaacrylates), polyacrylic acid which
is used in manufacture of superabsorbent polymers, flocculants, detergents, paper
chemicals and resin. SAP is used for water retention in infants’ diaper, adult in continence
products and feminehygine products (Nandini Chemical Journal, July, 1999). Various
acrylic esters are methyl acylate, ethyl acrylate, butyl acylate, 2-ethyl hexyl acrylate.
Process technology: Various routes for making acrylic acid are:
• Acetylene route
• Ethylene oxide Route
• Ethylene Route
• Chlorination of propianic acid
• Propylene route
• Formaldehyde and acetic acid route
Amongst the above process propylene oxidation through acrolein is commonly used.
Propylene route: In this route, acrolein is made in first stage by oxidation of propylene
in presence of mixed catalysts (prepared from oxides of bismuth, potassium, cobalt, and
iron, nickel, tin, tellurium, tungsten, etc.). In the second stage, acrolein is oxidized to
acrylic acid in the presence of mixed oxides of molybdenum and vanadium at 250–280ºC
in the presence of steam.
CH2 = CH – CH3 + O2 CH2 = CH – CHO
Acrolein

20.9 AROMATIC PRODUCTION

Aromatic hydrocarbons especially benzene, toluene, xylene, ethyl benzene is major
feedstock for a large number of intermediates which are used in the production of synthetic
fibers, resins, synthetic rubber, explosives, pesticides, detergent, dyes, intermediates, etc.
Styrene, linear alkyl benzene and cumene are the major consumer of benzene.
Benzene also finds application in the manufacture of a large number of aromatic
intermediates and pesticides. As per CMAI, demand for benzene is forecast to grow at
an average annual rate of 2.8% per year through 2020 resulting in nearly 57 million tons
of demand by 2020. Originally, the aromatics were produced from coal tar distillation,
which is the by-product of destructive distillation (carbonization).
Major application of toluene is as solvent. Other uses are in the manufacture of benzoic
acid, chloro derivatives, nitrotoluenes, toluene sulfonic acid, toluene sulfonamide,
benzaldehyde, etc. Xylenes are another important aromatic. Various sources of aromatics
are mentioned in Table 20.41.
406 Chemical Process Technology

Table 20.41: Various sources of aromatics

Processes Description
Coal carbonization From coke oven plant during carbonization, light oil is obtained as by
(Coke oven plant) product which contains about 2–8 kg, 0.5–2 kg, 0.1–0.5 kg of benzene,
toluene and xylene respectively per tonne of coal.
Steam cracking of Steam cracking of naphtha and light hydrocarbon like ethane and
hydrocarbons propane produce liquid product (pyrolysis gasoline) rich in aromatics
containing about 65% aromatics about 50% of which is benzene. About
30–35% of benzene produced worldwide is from pyrolysis gasoline.
Catalytic reforming Catalytic reforming is a major conversion process, which converts
low octane naphtha to high-octane gasoline and produce aromatics
rich in BTX. Major reactions involved are dehydrogenation of
naphthalenes to aromatics, isomerisation of paraffins and naphthenes,
dehydrocyclisation of paraffins to aromatics, and hydrocracking of
paraffins.
BP-UOP cyclar process In this process, BTX is produced by dearomatization of propane and
butane. The process consists of reaction system, continuous regeneration
of catalyst, and product recovery. Catalyst is a proprietary zeolite
incorporated with a non noble metal promoter.
Dearomatization of Process consists of extraction of aromatics from high aromatic naphtha
naphtha feed without prior reforming. The process is useful for naphtha having
high aromatics.
Hydrodealkylation and Hydrodealkylation: It involves production of benzene by dealkylation
disproportionation of toluene either by catalytic or thermal process.
Catalytic process: Hydeal, Deltol
Thermal process: HAD (ARCO), THDC Gulf Oil
Disproportionation: It involves conversion of toluene into benzene
and xylenes.
This process consists of conversion of C8 stream into valuable o- and
p-xylene having isomerisation and isomer separation stage.
Mitsubishi’s forming This process uses metallosilicate zeolite catalyst to promote
process dehydrogenation of paraffins followed by oligomerization and
dehydrocyclization of paraffins followed by oligomerization.
KTI pyroforming This process uses a shape selective catalyst to convert C 2 and C3
paraffins to aromatics.
Cheveron’s aromax It is similar to conventional catalytic reforming processes and L-type
process zeolite catalyst.
Isomerization and isomer This process consists of conversion of C8 stream into valuable o- and
process p-xylene having isomerisation and isomer separation stage.
Mitsubishi’s forming This process uses a metallosilicate zeolite catalyst to promote
Process dehydrogenation of paraffins followed by oligomerization and
dehydrocyclization of paraffins followed by oligomerization.
KTI pyroforming This process uses a shape selective catalyst to convert C 2 and C3
paraffins to aromatics.
Cheveron’s aromax It is similar to conventional catalytic reforming processes and L-type
process zeolite catalyst.
Source: Mall, 2007.
Petrochemical Industry 407

Amongst the xylenes, about 80% of the production is of p-xylene. Finds application in
the manufacture of terephthalicacid/DMT.O-Xylene used in the manufacture of phthalic
anhydride and m-xylene for isohthalic acid. Typical yield of benzene, toluene, xylene
in kg per ton of coal carbonized is about 2.8, 0.5–2, and 0.1–0.5 respectively (Wiseman,
1986).

20.9.1 Catalytic Reforming

Catalytic reforming is a key conversion process in a petroleum and petrochemical
industry. The catalytic reforming gives flexibility to meet gasoline octane number
requirement. It can also make aromatics of high market value. Catalytic reforming
is a refining process that uses selected operating conditions and selected catalysts to
convert. Basic objective of catalytic reforming is:
• To produce high octave blending stock for motor fuel
• To produce high value aromatic hydro carbon such as BTX

20.9.2 Process Description

A typical catalytic reforming process includes following three sections:
• Naphtha hydrotreating
• Catalytic reforming
• Catalyst circulation and regeneration
Basic steps in catalytic reforming involve feed preparation, temperature control,
reaction in reformer and product recovery. Various types of catalytic reformer are—
semi-regeneration, non-regeneration cyclic moving bed. Two types of reformer reactors
are in use—radial flow and axial flow. Details of this has been covered in Chapter 19.
20.9.3 Reactions in Catalytic Reforming Process
Number of reactions takes place in catalytic reforming. Dehydrogenation is one of the
major reactions. Some of the major reactions are:
Dehydrogenation
Methyl Cyclohexane Toluene + H2
MCP Benzene + H2
Isomerization
n-Hexane Neohexane
Dehydrocyclization of paraffins, i-paraffins to aromatics
n-heptance Toluene + H2
Hydrocracking
BTX from Petroleum

20.9.4 Major Units of Aromatic Complex

• Heavy Naphtha pretreatment unit
• Catalytic reforming (Platformer unit, CCR unit continuous catalyst regenerator)
• Recovery plus
• Pressure swing adsorption (PSA)
• BTX separation
• Xylene fractionation unit for separation of o-xylene from m- and p-xylene
• p-xylene andm-xylene separation by crystallization, adsorption.
408 Chemical Process Technology

20.9.5 Process Steps in Aromatic Production

Figure 20.19 gives the details description of aromatics complex. The various steps
involved in aromatic production are given below:
• First step in making BTX is to distill off a suitable fraction rich in natphthenes which
serves as precursors for aromatics.
• Catalytic reforming or a team cracking to produce an aromatic gasoline.
• Preliminary treatment of this cut: fractionation and/or selective hydrogenations
essentially pyrolysis gasoline
• Solvent extraction to eliminate non-aromatic from aromatics
• Distillation to produce pure benzene and toluene and in cased reformates used alone
or blended art a pyrolysis gasoline, the following additional treatment
• Distillation aromatic C8 to yield by super fractionation ethyl benzene and o-xylene,
after passage through a separation column in a light cut and a heavy cut (splitter)
• Production of p-xylene at low temperature with a mother liquor by product rich in
m-xylene
• Isomerization/delakylation/disporoportionation of m-xylene to p-xylene
Separation of Aromatics

Fig. 20.19: Aromatics complex (Source: Mall, 2007; Courtesy: Macmillan India.)
Petrochemical Industry 409

As nonaromatics and some of the aromatics have close boiling points, various methods
used for their separation are:
• Liquid–Liquid Extraction (DEG, TEG, tetramethylene Sath NMP-EG, Monoethyle
methylforma- midamorphine, DMF)
• Distillation, extractive or azeotropic distillation.
• Adsorption
• Crystallization
Process Variables
Various process variables in the catalytic reforming for the production of aromatics are
• Feed quality and N + 2A
• Temperatures
• Space velocity
• Hydrocarbon hydrogen ration
• Presence of impurities
Effect of Feed Quality on Aromatic Yield
• Naphthenes dehydrogenate very fast and give rise to aromatics. Therefore, N + 2A is taken
as index of reforming. Higher the N + 2A, better is quality to produce high aromatics.
N = Naphthenes %    A = Aromatics %
• Lighter fraction has a poor naphthene and aromatic content are, therefore, poor feed
for reforming. Low IBP feed results in lower aromatics and H2 yield
• Heavy fractions have high naphthene and aromatic hydrocarbon content. Therefore,
good reforming feed but tendency of coke formation is high
General recommended feed ranges for production
1. Benzene = 60–90ºC fraction
2. Toluene = 90–110ºC fraction
3. Xylenes = 110–140ºC fraction
4. Octane blending stock = 90–140ºC fraction
p-Xylene
The p-xylene plant consists of five units are:
1. Pretreatment unit: This unit is used for reducing sulfur content to 5 ppm (max.) by
dehydro-desulfurization which takes place at 330–370ºC and 24 kg/cm2 pressure in
presence of cobalt molybdenum catalyst.
2. Reformer unit: To get maximum amount of C8 aromatics by reforming process (Process
similar to described earlier).
3. Fractionation unit: For separation of o-, m-, and p-xylenes from combined C8
reformate and isomerisate from isomerisation unit (after clay treatment).
4. Parex unit: This unit is for the separation of p-xylene by selective adsorption using
molecular sieve followed by desorption. Other method for separation of p-xylene is
by crystallisation process.
Isomerization: Isomerization of C8 stream from Parex unit rich in m- and o-xylene and
ethyl benzene to p-xylene, which is sent to fractionation unit for separation of high
component. The bottom of the column is recycled for further recovery of xylenes.
410 Chemical Process Technology

Aromatic Conversion Processes

Because of higher demand of benzene and p-xylene in comparison to toluene and
m-xylene, various processes are commercially available for conversion of toluene and
m-xylene to more value added products like benzene and p-xylene. Processes are
also available for conversion of paraffins into aromatics. Some of the major aromatic
conversion processes and paraffin aromatization processes are given in Tables 20.42
and 20.43.

Table 20.42: Aromatic conversion processes

Aromatic conversion process Process details
Isomerization Isomerizatin of meta-xylenes to para- and orthoxylenes
Transalkylation and disproportion Transalkylation and disproportionation of C7 and C9
Toluene disproportionation Toluene disproportionation to xylenes and benzene
Selective toluene disproportionation Selective conversion of toluene to paraxylene by dispropor­
tionation
Xyelene isomerizations Maximization of p-xylene, ethyl benzene (EB) conversion
and EB dealkylation process
Aromataziation Conversion of light hydrocarbons to benzene, toluene and
xylenes

Table 20.43: Paraffin aromatization processes

Process Licensor
Cycler UOP-BP
Aroforming IFP-Sheddon Technology Management
M-2 Forming Mobil
Z-Forming Research Association

Cyclar Process
Cyclar process inexpensive and plentiful LPG requires minimal feed pretreatment and
product purification requirements and simplicity in operation. Reaction involved in
the cycler process is shown in Figure 20.20. Process flow diagram of UOP-BP cycler
process for LPG aromatization is shown is Figure 20.21.
Feed: Propane, butane, pentanes or mixture.
Liquid product: Largely BTX essentially free from C6–C9 paraffinic and naphthalenes.
Preparation of benzene toluene and xylene charges very little with the composition
of feed.
Aromatic yield:
63.6% of feed for propane
67.5% of feed for butane
→ Very high H2 yield of 5.5–6% for feed
→ H2 purity of about 95%.
Petrochemical Industry 411

Fig. 20.20: Reactions involved in cyclar process

(Source: Hydrocarbonprocessing (Gosling, et al. 1991)

Fig. 20.21: UOP-BP cyclar process for LPG aromatization

(Source: Hydrocarbonprocessing (Gosling, et al. 1991)

20.10 AROMATICS PRODUCT PROFILE, ETHYL BENZENE AND STYRENE, CUMENE AND
PHENOL, BISPHENOL, ANILINE
Aromatics are backbone of organic chemical industries. Aromatic hydrocarbons
especially benzene, toluene, xylene (BTX), and ethyl benzene are major feedstock for
large number of intermediates which are used in the production of synthetic fibers,
resins, synthetic rubber, explosives, pesticides, detergent, dyes, intermediates, etc.
Styrene, linear alkyl benzene, and cumene are the major consumer of benzene. Product
profile of aromatics is shown in Figure 20.22.
412 Chemical Process Technology

Fig. 20.22: Product profile of aromatics

20.10.1 Ethyly Benzene and Styrene

Ethyl benzene and styrene are two important aromatics. Ethyl benzene is mainly used
for making styrene. Styrene which finds application in synthetic rubber and polymer
industry for the manufacture of SBR and polystyrene, ABS plastic.
Major route for styrene manufacture is dehydrogenation of ethyl benzene which is
manufactured by alkylation of benzene. Styrene plant consists of two major units. The
process involves:
• Production of ethylene either from molasses route or by naphtha/natural gas cracking
• Production of ethyl benzene by alkylation of benzene
• Dehydrogenation of ethyl benzene to styrene
Petrochemical Industry 413

Ethyl Benzene
Ethyl benzene is made by alkylation of benzene with ethylene. Ethylene can be produced
from either from molasses route or naphtha/gas cracker. The convention alkylation
catalysts are metal chlorides (BF3, AlCl3, etc.) and mineral acids (HF, H2SO4). However,
with development of zeolite, now the benzene alkylation I is done by using ZSM-5
catalysts using vapor-phase process (Mobil-badger Process) and liquid phase alkylation
using MCM-22 zeolite proprietary catalyst-based catalyst.
Vapor phase alkylation of benzene: The process consists of vapor phase alkylation
of benzene with ethylene using zeolite catalyst in a fixed bed catalytic distillation
technology. Alkylation and distillation take place in the alkylator. Unreacted ethylene,
and benzene vapor are condensed and fed to the finishing reactor where the remaining
alkylation is completed in the presence of a catalyst. The product stream goes to
fractionating columns where ethyl benzene is separated from the higher ethylated
benzene and heavy ends. Higher ethylated alkyl benzene is sent to the trans-alkylator
where its trans-alkylated to produce additional ethyl benzene (Petrochemical Processes
2003” Hydrocarbon processing March 1999, p.10).
Liquid phase alkylation of benzene with ethylene using MCM-22 catalyst: In this
process, alkylation of ethylene takes place in a liquid filled alkylator reactor containing
multiple fixed beds of MOBIL MCM-22 catalyst. During alkylation, ethyl benzene and
small quantity of polyethylbenzene are formed which is converted to ethyl benzene
using trans-alkylation catalyst. The product streams from alkylator and trans-alkylator
are sent to various fractionating columns for separation of product ethyl benzene,
polyethylbenzene, benzene, gases and heavy ends.
C6H6 + C2H4 C6H5CH2CH3
Styrene
Styrene is one of the most important monomers for the production of polymers, resins
and rubber. The biggest consumer of styrene monomer is polystyrene, other major
derivatives are expanded polystyrene, styrene butadiene (SB) latex, SB rubber, styrene
block co-polymers (e.g. ABS, MBS, SBS) (SNOW: an innovative technology for styrene
synthesis, hydrocarbon Asia, 2007, p.42).
Styrene is made by catalytic dehydrogenation of ethyl benzene.
C6H5CH2CH3 C6H5CH = CH2 + H2

Styrene can be also directly recovering from raw pyrolysis gasoline derived from
cracking of naphtha, gas oils Using GT styrene process.
Lumus/UOP EB one process: Styrene is made by catalytic dehydrogenation of
ethylbenzene in the presence of steam. In Lumus/UOP EB one process involves first
alkylation of benzene with ethylene followed by dehydrogenation of EB to form styrene.
The benzene and recycled benzene are preheated the liquid phase reactor containing
zeolite catalyst. The polyethylbenzene formed during alkylation is fed to another reactor
for transalkylating with benzene. Transalkylation reaction is isothermal and reversible
in distillation section. The reactor effluent from both reactions is sent to the distillation
section for separating ethyl benzene from polyethylbenzene.
C6H6 + C2H4 C6H5CH2CH3
C6H5CH2CH3 + C6H6 2C6H5CH5CH3
C6H5CH5CH3 + C6H6 C6H5CH2CH3
414 Chemical Process Technology

Ethyl benzene and recycled ethyl benzene are then dehydrogenated to styrene in
the presence of steam at high temperature (550–680ºC) under vacuum in a multistage
reactor.
C6H5CH2CH3 C6H5CH = CH2 + H2

H2 + ½O2 H2O

During dehydrogenation stages, air or oxygen is introduced to partly oxidize

the hydrogen to reheat the process gas and to remove the equilibrium constrain for
dehydrogenation reaction (HC, 1999). Reactor effluents are cooled to recover waste heat
and condensed, uncondensed gases are used as fuel. The condensed product containing
styrene is sent to distillation columns for separating styrene monomer, unconverted
ethyl benzene is recycled.
Toluene is formed during the process which is recovered.
C6H5CHCH2 + H2 C6H5CH3

C6H5CHCH2 C6H5CH3 + C

GT styrene process: Styrene can be also directly recovered from raw pyrolysis gasoline
derived from cracking of naphtha, gas oils Using GT styrene process. Raw pyrolysis
gasoline is fractionated into a heart cut C8 stream from which styrene is separated by
extractive distillation.
Innovative SNOW technology: The snow technology has been jointly developed
by Snamprogetti and Dow represents a technological and economical breakthrough
in styrene production and uses benzene and ethane as raw material which is
dehydrogenated in the same reaction for EB dehydrogenation. SNOW reactor is rise type
(SNOW: An innovative technology for styrene synthesis, Hydrocarbon Asia, 2007, p.42).

20.10.2 Phthalic Anhydride

Phthalic anhydride first became commercially important during the nineteenth century
as an intermediate for dyestuff industry. However, now phthalic anhydride is largely
used for the manufacture of plasticizers, alkyd resins, and unsaturated polyester
resins where about 95% of the phthalic anhydride production is consumed. With an
aggregate installed capacity of 267,200-tpa across India, major PAN producers include
IG Petrochemicals Ltd and Thirumalai Chemicals Ltd. Consumption pattern of PAN is
shown in Figure 20.23. List of the phthalic anhydride manufacturers in India is given
in Table 20.44.

Fig. 20.23: Consumption pattern of PAN (Source: Dutta, P. Phthalicanhydride: A Techno-

commercial Profile Part I: Indian Scenario, Chemical Weekly, Jan 1, 2008 p.209.)
Petrochemical Industry 415

Table 20.44: Phthalic anhydride manufacturers in India

Company Location Installed capacity (TPA)
I.G. Petrochemicals Ltd. Taloja, Maharashtra 120,000
Thirumalai Chemicals Ltd. Ranipet, Tamil Nadu 100,000
Asian Paints Ltd. Ankleshwar, Gujarat 25,200
Mysore Petrochemicals Ltd. Raichur, Karnataka 12,000
SI Group Ltd. Thane, Maharashtra 10,000
Total 267,200
Source: Dutta, P.” Phathalicanhydride: A Techno-commercial Profile Part I: Indian Scenario, Chemical
Weekly Jan1, 2008 p.209.

The basic raw material for the manufacture of phthalic anhydride is naphthalene and
o-xylene. Phthalic anhydride was manufactured from naphthalene. With the availability
of large amount of o-xylene as a byproduct during p-xylene production, now phthalic
anhydride is made from o-xylene. Both vapor phase and liquid phase oxidation of
o-xylene are available.
Phthalic anhydride is produced by oxidation of naphthalene in the gas phase using
vanadium pentoxide catalyst supported on silica or silicon carbide promoted with
various other metal oxides, e.g. titanium oxide (wire) in either a fixed bed multiple
reactors or fluidized bed reactor.

Production of phthalic anhydride from o-xylene is similar to naphthalene route.

Catalytic oxidation of o-xylene is done either in fixed bed catalytic reactor having multi
tube or fluidized bed reactor in the presence of vanadium pentoxide and titanium oxide
catalyst.

20.10.3 Cumene
Cumene is made by alkylkating benzene with propylene using zeolite catalyst. Following
three major processes are available
416 Chemical Process Technology

1. Catalytic distillation technology: The process uses a specially formulated zeolite

alkylation catalyst in a proprietary catalytic distillation (CD) process and a trans-
alkylator reactor using zeolite catalyst. In CD column combines both reaction and
fractionation takes place.
2. Liquid phase q-max process: In this process, cumene is produced by liquid phase
alkylation of benzene with propylene in presence of zeolite catalyst.
3. Cumene by Mobil Badger process: The process produces cumene from benzene
and any grade of propylene using a new generation of zeolite catalysts from Exxon
m Mobil. The process includes a fixed bed alkylation reactor and a fixed bed trans-
alkylation reactor and distillation section.

20.10.4 Phenol
According to SRI consulting report 2010 global production and consumption of phenol
were both around 8.0 million tons with global capacity utilization of 77%. Phenol
consumption is expected to average growth of 5.1% per year from 2009 to 2014 and
around 2.5% from 2014–19. Phenol is consumed mainly for production of bis-phenol
A and phenolic resins which accounted for 42% and 28%, respectively of total phenol
consumption in 2009.
Various routes for phenol:
• Phenol from cumene
• Phenol from benzoic acid
• Phenol from chlorobenzene
• Benzene sulfonation.
With the availability of propylene now phenol is made by cumene route with added
advantage of acetone as by product.

20.10.5 Aniline
The process of aniline manufacture involves two stages: Companies which produce
aniline is given in Table 20.45.

Table 20.45: Company-wise production of aniline

Company Years Production Sales quantity Sales value
Gujarat Narmada Valley Fertilizers Ltd. 2008–09 27,077 27,090 1,865
2009–10 33,848 33,825 2,167
2010–11 39,896 – –
Hindustan Organic Chemicals Ltd. 2009–10 5,538 5,231 309
2010–11 1,833 1,826 135
Source: Chemical Weekly January 24, p.198, 2012.

Nitrobenzene Route
• Nitration of benzene with nitric acid
• Hydrogenation of nitrobenzene to aniline
Petrochemical Industry 417

Ammonolysis of chlorobenzene

Ammonolysis of phenol

20.10.6 Benzoic Acid (C6H5COOH)

Benzoic acid is the simplest member of the aromatic carboxylic acid. Benzoic acid,
which is used in the manufacture of caprolactam, phenol, terephthalic acid and used as
mordant, is manufactured by liquid phase catalytic oxidation of toluene in presence of
cobalt acetate at 165ºC and 11.2 atm pressure. Major processing steps in the manufacture
of benzoic acid consist of:
• Catalytic liquid phase air oxidation of toluene
• Stripping of unreacted toluene and light end precursors from the benzoic acid for
recycle
• Distillation to recover benzoic acid as a pure overhead product
418 Chemical Process Technology

20.10.7 Bisphenol
Bisphenol is an important building block and its measure use is in the manufacture
of polycarbonate plastic and epoxy resins. Other uses include in flame retardants,
unsaturated polyester resin and polyacrylate, polyetherimide and polysulfone resin
(Chemical Weekly, 2008).

India and Global Demand of Bisphenol (Chemical Business, 2012)

• Demand of bisphenol in India during 2010–11 was 30,000 tons per annum
• Global installed capacity: around 5.2 million tons
• Global demand around 4.2 million tons
• Global growth rate in demand 5–6%
• Polycarbonate resins are the largest and fast-growing BPA market, consuming 60%
of the global production.

Process Technology
Various process technologies available for manufacture of bisphenol are:
• Condensation of phenol with acetone
• Condensation of phenol with alkenyl phenol
• Condensation of phenol with ethylene and acetylenes
• Condensation of phenol with alkyl benzene.

Bisphenol from Phenol and Acetone

Bisphenol is synthesized by a condensation reaction between phenol and acetone using
proprietary cation exchange resin-base catalyst (4PET) in a packed bed reactor. The
catalyst has higher acetone conversion, higher BPA selectivity and longer life. Reactor
effluents are process in series of distillation column for separation of product bisphenol,
unreacted acetone, water, phenol. Phenol and acetone are recycled. Bisphenol is purified
by crystallization where bisphenol crystals are separated from the impurities. Although
the impurities are removed with mother liquor, however, two stage crystallization can
lower the impurities captured in the crystal. Bisphenol is sent to prilling tower to get
final bisphenol in the form of spherical prill.

BIBLIOGRAPHY
1. 2-Ethyl hexanol-Indian and global scenario. Nandini Chemical Journal, July 1998, p.21, Mall 2007
2. “Acrylic acid-investment opportunity”, Nandini Chemical Journal July 1999, p.10.
3. Chte V, Singal S, Koppel P, Ravikumar R. “ Syngas fro gasification as an alternate feedstocks for
chemicals, Petrochemicals and Power’ Chemical Industry Digest, February 2016, p.70.
4. “Energy Conservation Process Industry”, Energy Conservation Department, Engineers India
Ltd., New Delhi, 1992.
5. “Petrochemical Processes 2003” Hydrocarbon Processing, 2003.
6. Akiyama S. “Direct hydration of C3H6 yields Isopropyl alcohol”, Chemical Engineering, July 9,
1973.
7. Austin GT. “Industrially significant organic chemicals part 6” Chemical engineering, May 27,
1974.
8. Badoni RP, Kumar Y, Uma Shanker, Prasada Rao TSR. Chemical Engineering World, Vol. 31,
12, December 1996, p. 105.
Petrochemical Industry 419

9. Bhatacharya D, Brijesh Kumar, Raj Gopal S. “Indian: A versatile indigenous process Technology”,
J of Petrotech July–Sep 2011, p.56.
10. Briggs BA, Simpson SO, Lemerk CA, Ward DJ. “Fluid catalytic cracker as a source of petrochemical
olefins”, Chemical Age of India, Volume 38, No. 1, 1987, p. 21.
11. Burns KG, Ciarella DJ, Rowe CT, Sigmon JL. “Chemicals increase ethylene plant efficiency”,
Hydrocarbon Processing, January 1991, p.83.
12. Chambers LE, Potter WS. “Design ethylene furnace part I, Maximum ethylene”, Hydrocarbon
Processing, January 1974, p.121.
13. Chauvel A, Lefebvre G. “Petrochemical Processes”, 1989, Volume I, Edition Technip, Paris.
14. Chauvel A, Lefebvre G. “Sources of olefinic and aromatic hydrocarbons’, Petrochemical Processes,
1985, Volume I, edition Technip, p.129.
15. Chauvel A, Lefebvre G. “Sources of Olefinic and aromatic hydrocarbons”, Petrochemical
Processes, 1985, Volume I, edition Technip, p.129.
16. Chauvel A, Lefebvre G. “Treatment of olefinic C4 and C5 cuts”, in Petrochemical Processes,
Synthesis-Gas derivatives and major hydrocarbons, Editions Technip Paris 1985, p.195.
17. Chemical Business, Annual Report 2010–11 Dept of Chemicals & Petrochemicals (Ministry of
Chemicals & Fertiliser), Govt. of India, April 2ii, p.22.
18. Chemical Business, January 2012, p.12.
19. Chemical Industry Digest, August 2010, p.5.
20. Chemical Industry Digest, July 2012, p.29.
21. Chemical Industry Digest Vol. 30, October 2017.
22. Chemical Industry Digest AuguVolume 30, August 2017, p.13.
23. Chemical Industry Digest September Volume 30,2017, p.11.
24. Chemical Industry Digest Annual January 2018, p.15.
25. Chemical Engineering World February 2011, p.71.
26. Chemical Weekly, December 27, p.198, 2011.
27. Chemical Weekly, January 1,2008, p.209.
28. Chemical Weekly, January 24, 2012, p.198.
29. Chemical Weekly, June 10, 2008, p.187.
30. Chemical Weekly, November 15, p.199, 2011.
31. Chemistry Industry News, March 2004 SRI consulting, World Petrochemicals Program
32. Convers A. “Make chemicals from C4 olefinic fractions”, Chemical Age of India,
33. Dave RR, Khurana ML. “Evaluation of Feedstocks for aromatics, olefins and surfactant Plants”,
Proceeding of National workshop in crude oil evaluation, edited by Nagpal, JM, Tata Mcgraw
Hill Publishing Company Limited, New Delhi.
34. Desai DM. “New technologies for Petrochemical’s part-1”, Chemical Business, Sept.–Oct. 4,
25, 1991.
35. Dharia D, Letzsch W, Kim H, McCue, Chapin L. “Increase light olefins production”, Hydrocarbon
Processing, April 2004, p.61.
36. Dutta P. “Phathalic anhydride: A Techno-commercial Profile Part I: Indian Scenario.
37. Eng C, Tallman MJ, Oriss R, Miller R. “Economic routes to propylene”, Hydrocarbon Asia, July/
August 2004, p.36.
38. Feigl J, Schmidt G. “Consider furnace replacement for existing olefin units”, Hydrocarbon
Processing, June 2007, p.45.
39. Ganapati M. “Aromatic technologies state of the art”, Chemical Weekly, 8 Dec. 1992, p.129.
40. Gosling CD, Wilcher FP, Sullivan L, Mountiford RA. “Process LPG to BTX products”,
Hydrocarbon Processing, December 1991, p.69.
41. Gunardson HH, Abrardo JM. “Produce CO rich synthesis gas”, Hydrocarbon Processing, Volume
66, No. 4, 1998, p.87.
420 Chemical Process Technology

42. Gupta AK. Invited lecture, AICTE Staff development programme on Hydrocarbon Engineering,
IIT Roorkee, 3–22 January, 2000.
43. Gupta AK. Invited lecture, QIP short term course on Advances in Hydrocarbon Engineering,
IIT Roorkee, 23 June-4 July, 2003.
44. Gupta AK. Invited lecture, QIP short term course on Advances of Petrochemicals, organized
QIP Center, Indian institute of Technology, Roorkee (India), 21 June-5 July, 1994.
45. Handa SK. “Feedstock choice in petrochemicals industry” Chemical Industry Digest, August
2010, p.60.
46. Howard Rappaport “Plyolefins Feedstocks & Market” CMAI. PlastIndia-Feb-2009.
47. [Link]
48. Huang Sun-Yi, Lipp DW, Farinto RS. “Acetylene derived chemicals” in KirmOthomer
encyclopedia of Chemical technology, Fifth edition volume 1 Wiley-Interscience, p.227.
49. Hydrocarbon Processing, March 1999, p.10.
50. Joshi P. “Special feature on future of oil & gas sector India” FIPI Volume 16 issue 1 Jan–March
2017.
51. Kappor S, Vaidyanatht RA, Menegaz D. “Why integrate refineries and petrochemical plants”
Hydrocarbon processing February, 2009, p.29.
52. Little DM. “Catalytic Reforming”, 1985, Penn Well Books, Tulsa, Oklahoma.
53. Mall ID. NPTEL lecture Organic Chemical technology 2013.
54. Mall ID. “Petrochemical process technology”, First edition, New Delhi, Macmillan India 2007.
55. Mall ID. “Petrochemical Process Technology”, Re (print 2015, Second edition., Laxmi Publication
2016 New Delhi.
56. Masood R. “Role of raw materials in petrochemical industry”, Chemical Industry News, July
2002, p.13.
57. Meyers RA. ‘Handbook of Petroleum Refining processes’, McGraw Hill, 1986.
58. Morgan M. “C5 hydrocarbons and derivatives new opportunity”, Chemistry and Industry 2
September, 1996, p.646.
59. Moulijan JA, Makkee M, Diepen AV. “Chemica Process Technology”, John Wiley & Sons, 2001.
60. Nee RD. “The evolution role of fluid catalytic cracking in the petrochemicals market”,
Hydrocarbon Processing, March/April 2003, p.26.
61. Oil and Gas Journal, Vol 109, issue 27, April 7,2011.
62. Petrochemical Economics - Technology Selection in a Carbon Constrained World.
63. Petrochemical Overview, SRI Consulting Chemistry Industry News, March 2004.
64. Petrochemical Processes, 2003. Hydrocarbon Processing March 2003.
65. Pujaodo PR, Vora PV. “Make C3–C4 olefins selectively”, Hydrocarbon Processing, vol.69, no.3,
March 1990, p.65.
66. Sarin AK. “Refinery and Petrochemical integration” Chemical Industry digest Feb 2016, P.49.
67. Singh S. Chemical Industry Digest September 2017, p.13.
68. SNOW: An innovative technology for styrene synthesis, hydrocarbon Asia, 2007, p.42.
69. Styrene market and Asian demand to drive global benzene markets, Chemical Weekly, November
22,2011, p.205.
70. Taraphdar T, Yadav P, Prasad MK. “Natural gas fuels the integration of refining and petro­
chemicals”, PTQ quarterly, Q3, 2012, p.39.
71. Teng J, Xie Z. “OCC process for propylene production”, Hydrocarbon Asia May/June 2006, p.26.
72. Towfighi J, Sadramdi M, Niuei A. “Simulation of furnace length”, Petrochemical Technology,
Quarterly Autumn, 2001, p.137.
73. Venner RM, Kantorowicz SI, “Metathesis: refinery and ethylene plant applications”, Petroleum
Technology QuarterlySummer, 2001, p.141.
Petrochemical Industry 421

74. Vermilion WL, Niclaes HJ. “Petrochemicals from the FCC unit”, Hydrocarbon Processing,
September 1977, p.193.
75. Wiseman P. “Petrochemicals”, 1986, Ellis Horwood Ltd, Chichester, p.33.
76. Wiseman P. “Petrochemicals”, 1986, Ellis Horwood Ltd, Chichester, p.33.
77. [Link]/sect/chor/[Link]
78. Wysiekierski AG, Fisher G, Schillmoller CM. “Control coking for olefins plant”, Hydrocarbon
Processing, January 1999, p.97.
21
Polymer, Elastomer and
Synthetic Fiber

21.1 INTRODUCTION
Use of plastics, synthetic rubber and fibers has taken enormous importance in our daily
life in various forms. Increasing population increasing cost of cotton has increased the
use of synthetic fiber in textile industry. Use of various synthetic fibers like polyester and
nylons have also increased in automobile sectors. Although polymers were accidentally
synthesized, however as more and more applications were later discovered, polymers
have penetrated into all fields of application and in volume of around 205 million tons per
annum including standard polymers, engineering resins, elastomers, duromers, fibers
and textiles, dispersions. Polyolefins (LDPE, LLDPE, HDPE, and polypropylene) are
by far the largest group of thermoplastic polymers (CMAI, 2003). Polypropylene resins
along with polyester resins (PET) are one of the fastest-growing categories of commodity
thermoplastic resins in the world. The United States and China now represent more than
15% and 22%, respectively of world polypropylene consumption. Amongst the plastics,
thermoplastic market represents approximately 10% of global chemical industry. World
polymer demand in 2010 was 280 million tons. Types of polymer and its global demand
are shown in Figure 21.1. Typical consumption of plastic by industry and as polymer
is shown in Figure 21.2. PET resins in packaging industry has revolutionized our life
especially in the forms of PET bottles for water and soft drinks.

Fig. 21.1: World total polymer demand in 2010 approx: 280 million tons
(Courtesy: CAMI Consulting, 2010)

Plastics have become one of the important commodities giving big challenge to steel
and stainless steel which is shown in Table 21.1. Plastics can be readily, efficiently and
continuously converted to various useful products like packaging films, tubes and pipes,
422
Polymer, Elastomer and Synthetic Fiber 423

tanks, cables, fibers, molded bottles, extruded sheets, polymer composites (Trivedi,
2017). Volume wise its production is more than steel comparative production (MMTA).

Fig. 21.2: Plastic consumption, according to industry and polymer

(Source: Ways to get rid of the plastic, Chemical News, October 2011, p.21.)

Table 21.1: Comparative production of steels and polymers

Materials MMTA Specific gravity range
Steel 1800 7.5–8.0
Stailess steel 450 7.8–8.0
Polymers 380 0.95–1.5

Plastic materials are lighter than metals and due to this plastic products are uses is
almost 7–8 times in volumes as compared to steel. Plastics can be reinforced with talk or
calcium carbonate or glass fibers or carbon fibers and other fillers and additives. Plastics
may be foamed to lower density (Trivedi, 2017). Some of the recycled or discarded
plastics may be recycled or may be re-polymerized. Per capita consumption of plastic in
India is low 9.7 kg as against 100 kg or more in advance countries. The plastic industry
in India is growing at 8.1% every year. Estimate indicates that production is growing
from 14 million tons per year to 30 million tons per year in 2030 (Chemical News, April
2018)
Polyolefins represent the largest segment of the global thermoplastics business at
approximately 88 million tons (about 62% of the total market in 2002). Major success
factors for polyolefins are: easy accessible, reasonable raw materials (oil and natural
gas based), low production cost by modern energy saving and non polluting processes,
resources saving products, environmentally harmless products, energetically exploitable
products after usage, broad product portfolio, and tailor made products. Various types
of polymer and their uses are illustrated in Figure 21.3.
Global consumption of polyethylene in 2009 was approximately 64 million metric
tons. Global capacity utilization was 80% in 2009, down from 82% in 2008. Polyvinyl
Chloride (PVC) is the second largest commodity thermoplastic in the world, after
424 Chemical Process Technology

the polyethylenes. According to global production and consumption of polyvinyl

chloride (PVC) in 2010 was approx. 34 million metric tons. Average global utilization of
polyethylene rates are expected remain under 80% during the next five years, gradually
increasing to the high-80s by 2019. World polyethylene per capita consumption is
targeted to grow from 9.0–11.0 kg from 2001 to 2006. High density PE (HDPE) accounted
for around 45% of global polyethylene consumption in 2009, followed by linear low
density PE (LLDPE) and low density PE (LDPE). Figure 21.4 shows the percent uses of
plastic in different fields.
Due to non-biodegradable nature of the plastics, now biodegradable plastic or
bioplastics are also getting importance. However, increased cost is major deterrent in
its use on large scale.

Fig. 21.3: Various types of polymer and their application (Source: Mall, 2007)

Global demand for polymers is estimated to increase at 5% per annum to reach 227
MMT by 2015. Polymer demand in India is expected to grow at 13–14% per year and
will account for 9% of global polymer demand by 2015. The total polymer demand in
India by 2015 is estimated to be around 22 MMT. Table 21.2 gives the detail of India
share in global polymer demand.

Table 21.2: India’s share in the global polymer demand by 2015

2004 2015
India 4% 9%
Rest of world 96% 91%
Source: Dept of Chemicals & Petrochemicals, Govt. of India, IMACS Analysis.
Polymer, Elastomer and Synthetic Fiber 425

Fig. 21.4: Uses of plastics in different fields (Source: Envis, Volume 5, Issue 2, April–Jun 2007, p.15.)

21.2 PLASTIC INDUSTRY IN INDIA

• Consumption—4.8 million tons/annum
• Over 96% (4.6 million tons) is accounted for commodity plastics
• Per capita consumption, 4.8 kg as against world average 20 kg
• Projected demand in 2010–11 was 8.5 million tons (growth rate @15%)
• Raw material prices are influenced by international demand and supply of crude oil.
Reliance polymers is one of the largest producers of polymers in the world with a
combined capacity of 4.4 million metric tons per annum across their brands Repol PP
(Polypropylene), Reliance PE (polyethylene) and rayon (PVC) and finding application
in diverse sectors packaging, agricultural, infrastructure, automobile, health care and
lifestyle resulting in better products. Reliance is also major producer of PET resins
(Table 21.3).

Table 21.3: Installed capacity and production of performance plastics 2015–16

(in thousand tons)
Performance plastics Installed capacity Production
ABS resin 128 117
Nylon 6 and nylon 6,6 28 21
Polymethyl methacrylate (PMMA) 4 1
Styrene acrylonitrile (SAN) 136 99
PET chips/polyester chips 2,199 1,453
PTFE (Teflon) 20 9
426 Chemical Process Technology

21.2.1 Classification of Polymer

Natural and synthetic polymers could be classified in several other ways, viz., organic
and inorganic; on the basis of physical properties as plastomers (plastics), elastomers
(elastic), and fibrous (fiber); on the basis of response to temperature as thermoplastics and
thermosets. Various ways of classification of polymer is given in Figure 21.5 (Mall, 2007).
Polymers or resins are generally classified in two broad categories: thermoplastic and
thermosetting. Repeated heating and cooling does not alter the chemical nature of
thermoplastic while thermosets are permanent setting resin and once solidified these
materials may not be reshaped or formed by applying heat. Thermoset plastic are
stronger than thermoplastic (Mall, 2007).

Thermoplastics
Thermoplastics are organic chain polymers that usually become soft when heated and can
be molded under pressure. Thermoplastic resin are linear or branched chain polymers
with little or no cross linking (Hatch and Mater, 1979). Various thermoplastic resins
are polyethylene, polypropylene, PVC, polyvinyl acetate, polymethyl methacrylate,
polycarbonates, and polystyrene (Table 21.4).

Thermosetting Plastics
Thermosetting plastics are a network of long chain molecules that are cross-linked which
gives the polymer a three-dimensional infusible structure. They polymerize irreversibly
under heat or pressure to form hard, rigid mass. Various thermoset resins are phenol-,
urea-, melamine-formaldehydes, polyurethane, alkyd resins, epoxy resins, etc. Various
thermoset resins are given in Table 21.5.

Table 21.4: Major thermoplastic polymers

Name Abbreviation Family Formula Melting Density
temp.
Low density LDPE Polyolefin 110 (Tm) 0.910
polyethylene
High density HDPE Polyolefin 120 (Tm) 0.950
polyethylene
Polypropylene PP Polyolefin 175 (Tm) 0.902

Polyvinyl chloride PVC Vinyl 100 (Tg) 1.35

Polyvinyl acetate PVA Vinyl

Polystyrene PS Styrenic 100 (Tg) 1.05

Contd...
Polymer, Elastomer and Synthetic Fiber 427

Table 21.4: Major thermoplastic polymers (Contd...)

Name Abbreviation Family Formula Melting Density
temp.
Acrylonitrile ABS Styrenic — — —
butadiene styrene
Acrylonitrile SAN Styrenic — — —
styrene
Polymethyl- Acrylic
methacrylate

Polyhexamethy- Nylon 66 Polyamide 265 (Tm) 1.14

lenediamide
Polycaprolactum Nylon 6 Polyamide 225 (Tm) 1.14

Polyethylenetere- PET Polyester 270 (Tm)

phthalate

Polybutylenetere- PBT Polyester 250 (Tm) 1.3

phthalate

Polycarbonates PC Polyester 190 (Tg) 1.2

Polyacetals Polyethers 181 (Tm)

Source: Hatch and Matar, 1979.

Table 21.5: Various thermoset resins

S. no. Name Family Formula
1. Polyurethane Ester-amide

2. Alkyd resins Polyester

3. Unsaturated polyesters Polyester

4. Epoxy resins Polyether

Contd...
428 Chemical Process Technology

Table 21.5: Various thermoset resins (Contd...)

S. no. Name Family Formula
5. Phenol formaldehyde Phenolic

6. Urea formaldehyde Urea

7. Melamine formaldehyde Melamine

Source: Hatch and Matar, 1980.

21.3 ELASTOMER
Rubber can be broadly classified as natural rubber and synthetic rubber. Natural rubber
is a product of the tree Heveabrasiliensis while synthetic rubber is elastomer derived from
petrochemical feedstock product. Table 21.6 shows the general and special purpose rubber.

Table 21.6: General purpose and special purpose rubber

General purpose Special purpose
• Styrene butadiene rubber (SBR) • Polychloroprene (CR)
• Styrene butadiene • Styrene isoprene rubber (SIR)
• Emulsion/solution • Acrylonitrile butadiene (NBR)
• Polybutadiene (BR) • Silicone rubbers
• Polyisoprene (PS) • Acrylic rubber
• Ethylene propylene (EP) and ethylene • Polyester urethanes
propylene diene (EPDM) • Polyether urethane elastomer
• Butyl rubber (BR) • Epichlorohydrin
• Ethylene vinyl acetate (EVA) • Polyisobutylene
• Polydialkyl siloxane (Silicon rubber)
• Vinyl pyridine butadiene rubber (PBR)
• Hypalon
• Polysulfide rubber
• Fluorocarbon rubber

21.4 SYNTHETIC FIBER

Synthetic fiber industry is playing an important role in providing one of the basic needs
of mankind. Synthetic fiber may be broadly classified as woven and non-woven fiber.
Polymer, Elastomer and Synthetic Fiber 429
Fig. 21.5: Classification of polymer
430 Chemical Process Technology

With development of petrochemical industry there has been significant growth in the
synthetic fiber industry due to availability of raw materials. Some of the important
petrochemical-based synthetic fibers are nylon 6, nylon 6,6, acrylic fiber, polyester,
polypropylene fiber, polyurethane fiber, etc. Cellulosic-based synthetic fiber especially
viscose rayon has been providing synthetic fiber before arrival of the petrochemical-
based fiber. Some of the important cellulose-based fibers are viscose rayon, acetate
rayon, cuprammonium rayon, etc.
• First manmade fiber—naturally occurring polymers from cellulose and protein—
Viscose rayon first manufactured in 1886 in England
• First true synthetic in 1935—Nylon by DuPont
• Nylon was followed by acrylic and mod acrylic fiber based on acrylonitrile in 1950.
• Polyester fiber in 1953 in India
• Viscose rayon in India started in 1950
• Acetate rayon in 1954 in India.
Installed capacity and production of synthetic rubber, polyester yarn/fiberfil, and
fiber intermediates in 2015–16 are given in Tables 21.7 to 21.9. World consumption of
non-woven man-made fiber is mentioned in Table 21.10.

Table 21.7: Installed capacity and production of synthetic rubber 2015–16 (in thousand tons)
Synthetic rubber Installed capacity Production
Styrene butadiene rubber (SBR) 271 379.13
Polybutadiene rubber (PB) 114 114
Nitrile rubber (NBR) 25 0
Ethyl vinyl acetate (EVA) 15 2
Total synthetic rubber 425 495.13
Source: Annual Report 2016–17, Department of Chemicals and Petrochemicals, Ministry of Chemicals
and Fertilizers, Government of India.

Table 21.8: Installed capacity and production of polyester yarn/fiberfil 2015–16

(in thousand tons)
Synthetic fibers Installed capacity Production
Polyester filament yarn 2,820 2,179
Polyester staple fiber 1,170 1,040
Polyester staple fiberfil 69 51
Polyester industrial yarn 22 15

Rayon grade pulp: Harihar Polyfiber, Gwalior Rayon, Travancore Rayon, Baroda Rayon,
Andhra Rayon, Shri Ram Rayon, Kesoram Rayon, South India Viscose Rayon.
Caprolactam: Gujarat State Fertilizer and Chemicals (Vadodara), Fertilizer and Chemicals
(Travancore).
DMT/purified terephthalic acid (PTA): Bombay Dying, BRPL, Reliance (Patal Ganga,
Hazira, Vadodara), IOC (Panipat).
p-Xylene: BRPCL, Reliance (Patal Ganga, Hazira, Vadodara, Jamnagar), Indian Oil
Corporation projected consumption of fiber in India.
Polymer, Elastomer and Synthetic Fiber 431

Table 21.9: Installed capacity and production of fiber intermediates 2015–16

(in thousand tons)
Fiber intermediate Installed capacity Production
Acrylonitrile 41 2
Caprolactam 120 86
Monoethylene glycol (MEG) 1,153 1,001
Purified terephthalic acid 3,753 3,432
Total fiber intermedites 5,067 4,079
Source: Annual Report 2016–17, Department of Chemicals and Petrochemicals, Ministry of Chemicals
and Fertilizers Government of India.

Table 21.10: World consumption of nonwoven man-made fibers (% of total)

Man-made fibers 1998 2000 2005 2007
Polyester 24 22.5 23.0 23
Polyamides 1.5 1.5 1.5 1.5
Acrylic fibers 1.5 2.0 3.0 3.0
Polypropylene fibers 62.0 63.0 62.7 62.7
Viscose rayon 8.0 8.0 7.0 7.0
Other synthetic fibers 3.0 3.0 2.8 2.8
Total consumption, million tons 2.4 3.3 2.5 4.0

Details of man-made fiber is shown in Figure 21.6.

Fig. 21.6: Man-made fiber and raw material (Source: Mall 2017, NPTEL 2013).
432 Chemical Process Technology

Terms Used in Synthetic Fiber Industry

• Denier: It is the measure of coarseness of a yarn and is defined as the weight in grams
of a length 9000 meters of a yarn or filament.
• Tex and Millitex: Tex is the defined as the weight in grams of 1000 meters.
• Tenacity: The tenacity or strength of rayon is expressed as grams per denier. If
a load of 250 g will just break at a denier yarn, the tenacity is said to be 2.5 g per
denier.
• Elongation at break: Elongation is an important property of a yarn. If a length of
100 cm of a yarn can be stretched 112 cm before it breaks, it is said to have elongation
at break of 12%.
• Moisture regain: Regain of a fiber is the percentage of moisture calculated on oven
dry basis.
• Staple: The chopped fiber is called staple.
• Filament yarn: Reeled filaments yarn
• Elasticity: The elasticity of a fiber is its ability to recover from strain.

21.4.1 Overview of Indian Man-made Textile Industry

• Second largest producer of cellulosic fiber/yarn
• Fifth largest producer of synthetic fibers/yarns.
• Production of synthetic fibers nearly 10 lakh MT (2009–10)
• Production of synthetic yarn about 15 lakh MT (2009–10).

Indian: Fiber Demand

• Currently All fiber demand is arround 80 lakh MT
• Cotton 43 lakh MT and polyester around 30 lakh MT
• All fiber demand to grow nearly 130 lakh MT by 2020 @5% CAGR
• PFY has grown at around 10% CAGR in last decade and is likely to sustain similar
growth rates.

Indian: Textile Growth Drivers

• Higher disposable income and changing lifestyle
• Increasing fashion awareness even in tier B and C cities
• New emerging segment of non-apparel application
• Increasing urban households and working women population
• Rapid spread of organized retail sector
• Rise in exports to traditional and new markets
• Favorable government policies like TUFS, SITP (textile parks).
Emerging scenario of man-made fiber is given in Table 21.11. Table 21.12 gives
the details of demands of man-made fiber in India. Brief details of various synthetic
fiber producing units in India is given in Table 21.13. Table 21.14 gives the details of
rising demand of polyester. Per capita consumption of cotton and man-made fiber are
mentioned in Table 21.15.
Polymer, Elastomer and Synthetic Fiber 433

Table 21.11: Emerging scenario of synthetic fiber

Year 2010 2020
Cotton 33% 29%
Polyester 48% 55%
Others 19% 16%
Source: Rakesh Mehra. Emerging trends in Man-Made Textiles, the Synthetic & Rayon Textiles Export
Promotion Council (SRTEPC), 5th Texcon Asian Textile Conference.

Table 21.12: Man-made fiber demand in India

CAGR CAGR
KT 2000 2005 2010 2015 2020
2010/2000 2020/2010
Polyester 1,381 1,672 2,844 4,591 5,513 7% 7%
Nylon 86 117 111 118 107 3% 0%
Viscose 284 271 309 334 293 1% –1%
Acrylic 111 110 96 121 110 –1% 1%
Polypropylene 42 54 64 80 76 4% 2%
Total MMF 1,904 2,224 3,424 5,244 6,099 6% 6%
All fibers 4,948 5,735 7,826 10,871 12,984 5% 5%
Source: PCI.

Table 21.13: Various synthetic fiber-producing units in India

Sl.
Name and location of industrial unit Product
no.
1 JK Synthetics, Rajasthan NFY, PFY, NTC, PSF, ASF
2 Garware Nylon, Pune NFY, PFY
3 Nirlon Synthetic Fibers and Chemicals NFY, PFY, NTC
4 Modipon, Modi Nagar, Uttar Pradesh NFY, PFY
5 Century Enka, Pune NFY, PFY
6 Baroda Rayon Corporation NFY, PFY, VFY, NTC
7 Shree Synthetics, Madhya Pradesh NFY, PFY
8 Stretch Fibers NFY
9 Petrofils Cooperative PFY
10 Chemicals and Fibers, Thane PSF
11 Ahmedabad Manufacturing and Calico Printing Company PSF
12 Swadeshi Polytex, Uttar Pradesh PSF
13 Indian Organic Chemicals, Manali, Tamil Nadu PSF
14 Bongaigaon Refinery and Petrochemicals PSF
15 Reliance Industries (formally Indian Petrochemicals ASF
Corporation, Koyali, Baroda, Gujarat)
16 Neomar Ltd. PPSF
17 Shriram Fibers, Manali, Tamil Nadu NTC
Contd...
434 Chemical Process Technology

Table 21.13: Various synthetic fiber-producing units in India (Contd...)

Sl.
Name and location of industrial unit Product
no.
18 National Rayon Corporation, Kalyan, NTC, VTC, VFY
19 Travancore Rayon, Rayanopuram, Kerala VFY
20 Century Rayon, Kalyan, VFY, VTC
21 JK Rayon, Uttar Pradesh VFY
22 Kesoram Rayon, Triveni, West VFY
23 South Indian Vescose, Tamil Nadu VFY, VSF, PNSF
24 Indian Rayon Corporation, Veraval VFY
25 Sirsilk Ltd, Kaghaznagar, Andhra Pradesh AFY, ATSF
26 Rayon, Nagda, Madhya Pradesh VSF
27 Rayon, Mavoor, Kerala VSF
28 Shriram Rayon, Rajasthan VTC
29 Harihar Poly Fibers, Harihar, Karnataka PNSF
Source: Technical EIA Guidance Manual Project Sponsored by the Ministry of Environment and
Forests.

Table 21.14: Rising demand: Domination of polyester

kg per capital
Year Market share (%)
Cotton Polyester
1960 3.3 0.0 67
1970 3.3 0.5 55
1980 3.2 1.2 48
1990 3.5 1.6 47
2000 3.3 3.2 37
2010 3.6 5.2 33

Table 21.15: Per capita consumption of cotton and man-made fiber

Year Cotton, kg per capita Man-made fiber, kg per capita
2005 1.85 2.4
2010 1.65 2.75
2015 1.51 3.3
2020 1.52 3.6

21.5 RAW MATERIALS

Plastic, elastomers and synthetic fiber production needs extremely pure raw materials
and chemicals. The most important chemicals are monomers, catalysts, and solvents.
Various raw materials for polymers, elastomers and synthetic fiber are given below:
• Ethylene, propylene, vinyl chloride, vinylpyridine styrene, isocyanate, phthalic
anhydride
Polymer, Elastomer and Synthetic Fiber 435

ƒ Butadiene, isoprene, styrene, chloroprene, ethyl vinyl estate

ƒ Vinyl esters, vinyl ethers, acrylic and methacrylic esters, vinyl ethers
ƒ Dimethylformamide for dry spining
ƒ Adipic acid, hexamethylenediamine, benzene, ammonia, caprolactam
ƒ p-xylene, dimethyterephalate, terephthalic acid, ethylene glycol
ƒ Formaldehyde, phenol, urea, melamine
• Phenol, phosgene, bisphenol A
ƒ Maleic anhydride
ƒ Cellulosoe, NaOH, acetic acid , carbon disulfide acetic anhydride, etc.
• Catalysts which are used to speed up or initiate the polymerization reaction. Common
catalysts include Zieger catalysts (titanium chloride and aluminum alkyl compounds),
chromium-containing compounds, and organic peroxides.
• Various solvents are sometimes used to dissolve or dilute the monomer or reactants.
The use of solvents facilitates polymer transport through the plant, increases heat
dissipation in the reactor, and promotes uniform mixing in the reactor.

21.6 POLYMERS
21.6.1 Polyolefins
Polyolefinsis family of polymers derived from a particular group of base materials
known as olefins, are the world’s fastest growing polymer family. Polyolefins such
as polyethylene (PE) and polypropylene (PP) are commodity plastics found in
applications varying from house hold items such as grocery bags, containers, carpets,
toys and applications, to high tech products such as engineering plastics, industrial
pipes, automotive parts, medical appliances and even prosthetic implants (Kapur,
et al, 2008). Ethylene and propylene are monomers for polyethylene and polypropylene
respectively. Global polyolefin market is likely to be 200 million tons by the year 2020. In
India, the domestic polymer industry (like global industry) is dominated by polyolefins
(polyethylene, polypropylene) (Shashi Kant and Kapur, 2011). Market coverage of
polyethylene, polypropylene is given in Table 21.16. Polystyrene is another important
polyolefin and find wide application in manufacture of all sorts of packaging material.
Styrene copolymerized with acrylonitrile resulting in SAN polymer is characterized
with high tensile strength than polystyrene. Another important styrene copolymer is
acrylonitrile butadiene styrene (ABS) plastic that finds use in engineering plastic and
is characterized with special mechanical properties.

Table 21.16: Polyethylene/polypropylene market coverage

Polymer types Grade Market coverage
HDPE Film grade Blown film with paper like quality, suitable for
counter bags, carrier bags and wrapping films
Pipe grade Pipes PE-80/100 class, drinking water and gas pipes,
waste pipes and sewer pipes their fitting, etc.
Large BM grade Universal container grade, vol. approx. 1,500 L;
heating oil storage tanks, transport containers
Small BM grade Disinfectant bottles, up to 2 L, tubes for the cosmetics,
containers from few mL up to 10 L.
Contd...
436 Chemical Process Technology

Table 21.16: Polyethylene/polypropylene market coverage (Contd...)

Polymer types Grade Market coverage
Raffia grade Stretched films and tapes for production of high
strength knitted and woven sacks/bags/nets, etc.
Injection molding For transport and stacking crates, particularly bottle
crates
LLDPE Films Garment bags, grocery sacks, liner, blends, trash
bags, cast like film diapers, etc.
Roto molding Large industrial parts used indoors, large industrial/
agri­cultural tanks, shipping drums, toys, etc.
Injection molding House wares, crates, master batches, pails, food
container, etc.
PP Homo polymer Injection molding (battery cases, crates, furniture,
house ware, luggage, sports/toys), blow molding,
sheets, Tape/Raffia, FIBC,TQPP/BOPP films (food
packaging, bottle labels, etc.), extrusion coatings, etc.
Random copolymer Thin walled injection molding, low heat seal and high
transparency films, Blow molding, packaging parts,
automotive parts, etc.
Impact copolymer Automotive parts (bumper, exterior trims, instrument
panels, interior trims), appliances, house wares, rigid
packaging, thermoforming, etc.
Source: Kapur, et al. 2008, Journal of the Petrotech Society, Mall 2006, Mall 2013.

Catalyst for Polyolefin

There are four major families of catalysts used for olefin polymerization are given below.
The main driver for change in polyolefin catalysts is requirement of improved resin
performance. Characteristics of catalyst is given in Table 21.17. Ziegler Natta catalysts
are spherical, high activity with low fines, thus leading to operational advantages and
reduced cost. Metallocene catalyst afford greater control over molecular weight, molecular
weight distribution, short-chain branching (SCB) and SCB distribution (Jensen, et al. 2008).
• Ziegler Natta catalyst
• Phillips (chrome)
• Metallocene
• Late transition metal catalyst.

Table 21.17: Characteristics of polyolefin catalyst

Type State Typical examples
Ziegler/ Heterogeneous TiCl3, TiCl4/MgCl2
Ziegler–Natta Heterogeneous VCl4, VPCl3
Phillips (chrome) Heterogeneous CrO3/SiO2
Metallocene Homogeneous Cp2ZrCl2
Heterogeneous Cp2ZrCl2/MgCl2
Late transition metalbased Homogeneous Ni, Pd, Co, Fe, with diimine, and other ligands
Source: Kapur, et al. 2008.
Polymer, Elastomer and Synthetic Fiber 437

21.6.2 Polyethylene
Polyethylene is one of the most widely used thermoplastic and its ever increasing
demand is due to availability of monomer ethylene from naphtha and gas cracker
plant. First polyethylene plant in India was based on ethylene from molasses. Some of
the other driving force for fast growth and use of polyethylene are ease of processing
the polymer, its relative low cost, resistance to chemicals and its flexibility (Hatch and
Matar, 1979). A wide variety of polyethylene varying density and characteristics for
wide range of application is available.
• Low density polyethylene (Branched) produced by high pressure
• LDPE 0.910–925 MP 105–110ºC Crystallinity 60–70%
• Medium density MDPE 0.920–940
• High density HDPE 0.941–0.959 MP 125–130ºC
• Crystallinity 75–90%
• Very few side chains. Produced by low pressure
• Linear high density to ultra high density homopolymers
• Linear low density polyethylene (LLDPE) 0.916–0.940 alpha-olefin as comonomer
density 70.941
• High molecular weight – High density PE (HMW-HDPE)

Molecular mass: 200,000–500,000

Advantage: Low cost, excellent dielectric properties, moisture resistance, very good
chemical resistance, available in food grade, processed by all thermoplastic molding.
Process Technology for Polyethylene
Several processes have been commercialized for the manufacture of polyethylene
with varying densities. Various processes for manufacture of polyethylene are given
in Table 21.18.

Table 21.18: Various polyethylene processes

Process Licensor Process Product
Innovene process BP Chemicals Polymerization in fluidized bed reac­ LDPE, HDPE
tor using Ziegler Natta catalyst or
chromium catalyst
Temperature 75–110ºC
Broster process Borealis A/S Uses gas phase low pressure reactor. Bimodal and
Ziegler Natta catalyst unimodel
Comonomer hydrogen LLDPE,
Prepolymerization in slurry loop MDPE
reac­t or and fluidized bed reactor.
Temperature 75–100ºC
Contd...
438 Chemical Process Technology

Table 21.18: Various polyethylene processes (Contd...)

Process Licensor Process Product
High pressure free Exxon Chemicals Polymerization occurs in autoclave LLDPE
radicals process Co reactors or tubular reactor
Speriline gas phase Montell Polymerization in gas phase reac­tor LLDPE,
process Technology Co using Ziglernatta catalyst HDPE
Phillips Co, LPE Phillip Petroleum Polymerization takes place in an iso­ Lineal
process Co. butene slurry using very high activity polyethylene
proprietary catalyst in loop reactor.
UNIPOL PE process Union carbide Low pressure polymerization in flui­ LLDPE to
Corp dized bed reactor at 25 kg/cm2 and HDPE
100ºC
Sclairtech process DuPont Polyethylene is produced by solution HDPE,
polymerization using ethylene gas and MDPE,
cyclohexane as solvent. Comonomer: LLDPE
butene or octane or both; Catalyst:
Ziegle Natta catalyst
Source: Hydrocarbon processing. Petrochemical Process, 2003.

UNIPOL Process
The process produces low density polyethylene and high density polyethylene using low
pressure in gas phase. Wide range of polyethylene is produced using proprietary solid
and slurry catalyst. The process produces wide range of polyethylene in a gas phase,
fluidized bed reactor using proprietary solid and slurry catalyst. Gaseous ethylene,
comonomer and catalyst are fed to fluidized bed reactor containing a fluidized bed of
growing polymer particles operating at 25 kg/cm2 and 100ºC. Polymer density is easily
controlled from 0.915 to 0.97 g/cm. Process flow diagram for polyethylene manufacture
is given in Figure 21.7.

Fig. 21.7: Fluidized-bed gas phase: PE process

Polymer, Elastomer and Synthetic Fiber 439

DuPont Sclairtech Process

A broad range of polyethylene with density varying from 0.919 to 0.9605 g/cm2 with
varying melt index can be made by this process. The process can be divided into three
major areas
• Reaction area
• Recycle/recovery area
• Extrusion and finishing
• Dowtherm vaporizer.
The process involves solution polymerization of gaseous ethylene using cyclohexane
solvent and comonomer butene or octane comonomer (incase of low density polymers).
Zigler catalyst is used to polymerize ethylene using cycloheaxane as solvent. A chain
terminator is used to control the molecular weight at the reactor outlet a catalyst
deactivator is added to terminate the reaction. The polymer is depressurized to flash
off solvent, unreacted ethylene and comonomer from the molten polyethyelene which
are separated and recovered using distillation. The polymer after stripping the residual
solvents fed to main extruder and resulting polymer pellets are dried and send to blender
for homogenizing and finally conveyed to storage silo. In the process, Dowtherm is
added as heating media. Process flow diagram for the manufacture of polyethylene by
Sclairtech process is given in Figure 21.8.

21.6.3 Polypropylene
Polypropylene is a low density semi-crystalline stereo-regular polymer which exists
in three forms—isotactic, syndiotactic, and atactic. Polypropylene was discovered
in March 1954 by Professor Giulio Natta demand of polypropylene is growing at a
much faster rate due to its strong demand. Per capita consumption of polypropylene
is given in Figure 21.9.

Process Technology for Polypropylene

Polypropylene polymerization process have undergone a number of revolutionary
changes since the production of crystalline polypropylene were commercialized in 1957

Fig. 21.8: LLDPE process by Sclairtech process

440 Chemical Process Technology

Fig. 21.9: Per capita consumption of polypropylene

(Source: Shah, A. Indian propylene markets (India Petrochem 2009).

by Motecatini in Italy and Hercules in U.S. Commercial polypropylene processes based

on low pressure processes using Ziegler–Natta catalyst that produces a product with an
isotactic content of 90% or more. Various processes for polypropylene manufacturing are
given in Table [Link] polypropylene processes are given in Figures 21.10 and 20.11.
UNIPOL process: The process produces homopolymer, random copolymer and impact
copolymer polypropylene. Polymerization takes place in a fluidized bed reactor using

Table 21.19: Polypropylene manufacturing process

Process and licensor Summary of process Product
Borstar Produced by bulk polymerization A versatile process and through the choice
Polypropyene in loop reactor followed by final of reactor combinations, homopolymer,
process gas phase a fluidized bed reactor random copolymers, heterophasic
Licensor Borealis (temp. 80–90ºC and 25–35 bar) copolymers and a very high rubber content
A/S heterophasic copolymers can be produced
Spheripol Process Homopolymer and random copo­ Process produces propylene based
Montell lymer polymerization takes place polymers including homopolymer PP,
Technology in liquid propylene in a loop random and heterophasic impact and
reactor. Heterophasic impact specialty impact copolymers
copoly­m eri­z ation is done by
adding a gas phase reactor.
Novolen Process Polymerization is conducted in Polypropylene homopolymer, ran­
Krupp Uhde one or two gas phase reactors dom copolymer and impact copo­lymer
GmbH connected in series. including metallocene PP
Union carbide gas A wide range of polypropylene is Homopolymer, random polymer and
phase UNIPOL PP made in a gas phase, fluidized bed impact copolymer polypropylene
process reactor using proprietary catalyst.
Sperizone Process Sperizone process is new A broad range of propylene based
Technology owner: proprietary gaseous technology polymer can be produced including
Basellpolyolefins based on a multi-zone circulating mono- and bimodal (medium/wide, very
concept reactor. wide MWD)
Source: Petrochemical Processes 2003, Hydrocarbon Processing, March 2003.
Polymer, Elastomer and Synthetic Fiber 441

Fig. 21.10: Polypropylene process

Fig. 21.11: Polypropylene manufacturing by Unipol process (Sources: Petrochemical processes.

Hydrocarbon Processing, March 2003, p.124.) (Courtesy: Hydrocarbon Processing)

slurry (TiCl4 supported on MgCl2 in slurry form in mineral oil. Co-catalyst TEAL,
purified propylene and ethylene incase of random PP), purified H2 and selectivity
control agent is continuously fed to the reactor. Temperature 35ºC and pressure
33 kg/cm2 are maintained in the reactor. Figure 21.11 illustrates the Unipol process for
manufacturing of polypropylene.

21.6.4 Polystyrene
Polystyrene is an important thermoplastic. Polystyrenes because of its ease of fabrication,
low specific gravity, thermal stability and low cost, find wide applications in consumer
durable goods, electronics, packaging, toys, structural foams, wall tiles, shoe soles,
blister packages, lenses, bottle caps, wire and cable sheathing, small jars, vacuum formed
refrigerator liners, containers of all kinds, transparent display boxes and automobile
interior parts. When styrene is copolymerized with acrylonitrile, the polymer styrene
442 Chemical Process Technology

acrylonitrile (SAN) resin has a higher tensile strength than polystyrene. Acrylonitrile
butadiene styrene (ABS) polymer has special mechanical properties and find application
as engineering plastics.
Styrene is produced by dehydrogenation of ethyl benzene which is made by alkylation
of benzene. Ethylbenzene by UOP EB one process is produced by liquid phase alkylation
of benzene using proprietary zeolite catalyst which can be regenerated repeatedly
thereby avoiding significant catalyst disposal problems associated with other aluminum
chloride catalyst. The process offers better product quality, better heat integration, low
investment and a more rugged and reliable catalyst system. ([Link]
aromatics/[Link])
Lumus/UOP classic SM process: In this process, styrene is made by catalytically
dehydrogenating ethylbenzene in presence of steam in multistage reactor system. The
reaction is carried out at high temperature under vacuum. The process uses an oxidative
reheat technology. Polystyrene is clear transparent resin with a wide range of melting
points and good flow properties which make it suitable for injection molding (Hatch
and Matar, 1979).
Process Technology
The two major processes for the production of polystyrene are NOVA’s Polystyrene
Technology and UOP Polystyrene Technology.
NOVA’s polystyrene technology: The process produces a complete range of general
purpose (crystal) and impact resistant polystyrene. This is based on bulk continuous
polymerization technology.
UOP polystyrene technology: This process is based on continuous bulk polymerization to
produce a wide range of general purpose polystyrene, high impact polystyrene and SAN
resin. A typical plant includes feed preparation, reactor section, de-volatilization section,
monomer recovery section, water removal, product pelletizing and bulk resin handling.

21.7 ELASTOMERS
Elastomers are used in wide variety of industrial, medical and household products and
major portion of elastomers consumption goes into tires, next largest product sector
is latex goods. There are two major types of elastomers; natural rubber a product of
tropical tree Heveabrasiliensis and synthetic rubber- a family of materials derived from
petrochemical feed stocks (Chemistry and Industry August 5, 1996, p.574). Major natural
rubber producing countries are Thailand, Indonesia, Malaysia, Africa, Latin America,
Brazil, Cambodia, Nigeria, Sri Lanka and India.
Demand for natural is estimated to be around 10.9 million tons in 2011 out of which
around 45% was from Asia. About 92% of natural rubber is produced from Asian
countries. The demand for natural rubber globally is projected to grow by 3–4% through
2013 (Chemical Weekly, Jan 17, 2012).
Synthetic rubbers have slowly replaced natural rubbers and have undergone various
developments for applications in automotives, chemical industry, energy generation,
sports, aerospace industry, etc. Styrene butadiene rubber (SBR), polybutadiene, nitrile
rubber are some of the important elastomers.
21.7.1 Historical Development
Natural and Synthetic Rubber
1525 Elastic ball reported by Mexico tribal people
Polymer, Elastomer and Synthetic Fiber 443

1735 First scientific study of rubber by Charles de la Condamine

1820 First planting of rubber in India at Travancore
1832 Rosburg factory was set up for rubber goods with non–vulcanized rubber
1845 RW Thomson invented the pneumatic tire
1902 First commercial plantation
1910 First large scale commercial production of butadiene rubber
1914–18 Methyl isoprene rubber in Germany
1930 Organic polysulfide rubber
1931 Neoprene production started
1932 First synthetic rubber plant in USSR
1933 BUNA-S made in USSR
1936 First automatic tire factory (Dunlop) in India
1963 First synthetic rubber plant in India
1976 First nitrile rubber by Synthetics Chemicals
1978 First polybutadiene plant in India by IPCL
Petro-based synthetic rubber 20% in India, 80% in developed countries.
Annual growth rate 7%.
Natural Rubber
Christopher Columbus voyage to Haiti 1496
Tree: Cau-achu Weeping wood
Priestley (1770), Rubber Rub-off
1839 Vulcanizing of rubber
1840 Henry Wickham smuggled 70,000 Herca tree seed to England
planted at London.

21.7.2 Synthetic Rubber

With the availability of petrochemical feedstocks, there has been tremendous increase in
the production of synthetic rubber. World synthetic rubber market and its production
is given in Figures 21.12 and 21.13, respectively. Synthetic rubber may be classified as
general purpose rubber, specialty rubbers, thermoplastic rubber or liquid processing
rubber (e.g. silicon rubber, liquid polysulfide rubber). Synthetic and natural rubber
consumption scenario is given in Table 21.20. Forecast of synthetic rubber and natural
rubber consumption in India is given in Table 21.21.

Capacity (2011) by region (15,965 kmta)

Fig. 21.12: World synthetic rubbers market by region

444 Chemical Process Technology

Fig. 21.13: World rubber production (Sources: International Rubber Study Group.)

Table 21.20: Synthetic and natural rubber consumption scenario

India 2005 2010 2015
Capacity 85 113 –
Consumption 233 406 613
Oversupply/(shortage) (148) (293) –
Source: IISRP (2011), TSRC Corporation.

Table 21.21: Indian consumption of synthetic rubber (SR) and natural rubber (NR) forecast
(Unit: 000’ metric ton)
2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020
NR, Tire Sector 661 680 772 783 850 897 950 1,010 1,046 1,093 1,152
NR, Non-tire Sector 283 284 295 308 329 342 358 383 397 414 447
Sub-total 944 964 1,017 1,091 1,179 1,239 1,308 1,393 1,443 1,507 1,599
SR, Tire Sector 145 143 156 164 166 178 189 210 214 221 248
SR, Non-tire Sector 261 285 342 414 452 513 570 625 636 661 687
Sub-total 406 428 498 578 618 691 759 835 850 882 935
Total of rubber 1,350 1,392 1,515 1,669 1,797 1,930 2,067 2,228 2,293 2,389 2,534
consump­­tion
Source: IRSG (December), TSRC Corporation 2011.

21.7.3 Styrene Butadiene Rubber

Styrene butadiene rubber (SBR) is the most widely used elastomer in the [Link] is
used for both tire and non-tire application. Styrene butadiene rubber known as Buna-S
was first prepared by IG Farben Industry in Germany. There has been significant
development in the process technology of styrene butadiene rubber manufacture.
Amongst the various processes, emulsion polymerization of SBR is most commonly
used. The cold emulsion polymerization process has replaced the hot polymerization
process. In India, first SBR manufacture was started by Synthetic and Chemicals, Bareilly
in 1963, however; the unit has been closed presently.
Although butadiene is recovered from cracker plant, it can be also made from ethanol
route. Styrene is made from ethyl benzene by alkylation of benzene with ethylene which
can be also recovered from FCC gases.
Polymer, Elastomer and Synthetic Fiber 445

SBR is made by emulsion polymerization at 50ºC. Initiation occurs through reaction

of potassium peroxodisulfate with n-dodecyl mercaptan. Chain propagation occurs
by the growing chain free radical of mercaptyl attaching either butadiene or styrene.
The reaction is terminated at 60–75% of completion. Unreacted butadiene and styrene
were recovered. Antioxidant is added followed by coagulation, washing and drying.
It is used as elastomer, emulsion and solution. Used in tires and tire-related product,
mechanical goods, automotive uses, adhesive, shoe products.
SBR is a hard rubber which is used for soles of shoes, tire treads and other places where
durability is important. It is a type of copolymer called a block copolymer. Its backbone
chain is made of three segments—first polystyrene, second polybutadiene and third
polystyrene. Polystyrene is tough hard plastic and this gives SBS its durability (file:/A:\
Poly (styrene-butadiene-styrene).htm). Process flow diagram of SBR manufacture is
given in Figure 21.14.

Fig. 21.14: Process flow diagram of SBR manufacture

21.7.4 Polybutadiene
Stream of steam cracker is major source of butadiene. Other routes for butadiene
manufacture are:
• Catalytic dehydrogenation of butenes
• Catalytic dehydrogenation of butane
With the availability of butadiene from cracker plant, manufacture of polybutadiene
has increased significantly in recent years.
Polybutadiene is made by free radical emulsions, alkali methyl solution and
transition metal coordination solution processes. Most processes are based on
solution process. Large volume use of polybutadiene rubber has been primarily in
blend with other polymers. Blend with SBR or natural rubber has improved crack
resistance.
It is also characterized by better resistance to heat degradation and blowouts, good
hysteresis properties, large scale use in tire tread, modification of plastics, conveyor
and V-belts, sports goods, foot wear material, 90% in tire industry.
446 Chemical Process Technology

21.7.5 Polyisobutylene (Butyl Rubber)

Polyisobutylene is gas impermeable and because of this property it is used for making
ballon. Polyisobutylene is made by polymerization of isobutylene. Isobutylene can be
recovered from C4 stream of steam cracker and FCC. Other routes for isobutylene are:
dehydrogenation of isobutene, n-butane with small amount of isoprene formed by
isomerization in gas phase using platinum catalysts.
Butyl rubber is made by slurry polymerization. The polymerization is carried out
in slurry of monomer in methyl chloride using an aluminum chloride catalyst at –100
to –90ºC. The rubber is precipitated by adding water and finally washed and dried. Butyl
rubber has unique elastomeric qualities, low rate of gas permeability, thermal stability,
good ozone and weathering resistance, vibration damping and higher coefficients of
friction, chemical and moisture resistance. Used in tubes, tire inner liner due to low
permeability of air, automotive mechanical parts, adhesives, and sealant.

21.7.6 Nitrile Rubber

Acrylonitrile butadiene copolymers are commonly known as nitrile rubber. Nitrile
rubbers are available in many grades varying in acrylonitrile content. Increase in
acrylonitrile improves resistance to fuels and oil, tensile strength and modulus,
processing behavior, heat resistance; increases abrasion resistance and hardness,
permeability resistance to gas diffusion; decreases low temperature flexibility, resilience
and elasticity, plasiticizer compability (Patel, 1991). Abroad range of properties can be
obtained from properly compounded nitrile rubber.
Nitrile rubber is made by emulsion copolymerization of butadiene and acrylonitrile
at 5ºC. The basic steps involved are polymerization, coagulation, washing and drying.
A basic polymerization recipe in addition to the monomer contains water, stabilizers,
emulsifiers, shortstop catalyst activator and electrolytes. Following polymerization
cycle material is transferred to blow down tank in which short stop and antioxidant are
added and residual monomers are recovered. Then finally, the latex is concentrated,
coagulated, washed, dewatered and finally dried. Nitrile rubber is used in seals; O-rings,
gaskets, oil field parts, diaphragm, gloves, belts, wire cable insulation, hosepipes, foot
wear shoes products, molded rubber goods.
In the polymerization process the monomer is emulsified in water, a free radical
generating catalyst is added and the mixture is agitated. After the polymerization the
material from the polymerization reactor is transferred to blow tank in which short
stop and antioxidant are added and the residual monomers are removed. The latex
formed is concentrated and coagulated into fine crumbs by addition of salt and acids.
This followed by washing, dewatering and drying. The dried crumbs are compacted
(Patel, 1991).
Acrylonitrile 18–50%, with increase in acrylonitrile resistance to oil, fuel, abrasion
and heat increases, higher tensile strength, hardness, gas impermeability.
• Low temperature resistance, resilience, plasticizer compatibility decreases require
less sulfur, more accelerators than SBR, highly oil resistant.
Application: Fuel hoses, collapsible containers. Nitrile rubber may be reinforced by
phenolic resins and PVC.
• Resistance to ozone, weathering, better gloss, bright colors, high resistance to abrasion
and oil.
Process flow diagram of manufacture of nitrile rubber is given Figure 21.15.
Polymer, Elastomer and Synthetic Fiber 447

21.7.7 Polyisoprene
Polyisoprene is one of the most well known natural elastomers derived from the sap of
the Heavea tree. However, synthetic polyisoprne is made by polymerization of isoprene.
Isoprene is recovered from the C5 fraction of naphtha cracker. Isoprene polymerization is
carried out in an inert hydrocarbon solvent (aliphatic solvents). Basic steps in manufacture
of polystyrene are—raw material preparation and purification, polymerization, catalyst
deactivation and removal, solvent recovery, polymer drying. Polymerization catalysts
are either of the coordination (Zeigler) or alkyl lithium types. Coordination catalysts
are trialkyl aluminum/titanium tetrachloride. Often polymerization short stops and
antioxidants are added. The solvent remaining is stripped off.
Polyisoprene has good uncured track, high pure gum tensile strength, high
resilience, low hysteresis, good hot tear strength. Tire market is the major consumer
of polyisoprene, a substitute of natural rubber in the tread of truck, aircraft and off the
road tires, for dipped goods, adhesive, extruded thread.

Fig. 21.15: Process flow diagram of acrylonitrile rubber (nitrile rubber) manufacture

21.7.8 Neoprene (Polychloroprene)

Chloroprene is made either via acetylene route or from butadiene. Butadiene process is
commonly used (Nadini Chemical Journal, April 1998, p.21). Acetylene route involves
dimerization of acetylene to monovinyl acetylene followed by reaction of monovinyl
acetylene with HCl.
Chloroprene from butadiene involves three steps:
• Chlorination of butadiene: Various steps involved are
• Chorination of butadiene- 1,4 dichloro 2-butene and 3,4-dichloro-1-butene
• Isomerization of 1,4 dichloro 2-butene to 3,4-dichloro 1-butene
• Dehydrochlorination of 3,4-dichloro 1-butene to chloroprene in presence of caustic
soda resulting in formation of chloroprene (CH2 = CH – CCL = CH2).
Polychloroprene is made by emulsion polymerization process using resin acid soap
emulsifier. Polymerization is carried out at 40ºC in presence of sulfur.
Uses: Adhesives, transportation industry (automotive: gaskets, V-belts, shock absorber
covers, wire jackets, molded seats; aviation: wire cable, gaskets, seats, etc. rail brake
hose, track mountings).
448 Chemical Process Technology

21.7.9 Chlorobutyl Rubber

Chlorobutyl rubber is made from isobutylene and 1–3% isoprene. Introducing a
continuous stream of chlorine gas in a hexane solution of butyl, which is prepared by
low temperature copolymerization of isobutylene, and isoprene in methyl chloride
gives chlorobutyl. Chlorobutyl rubber possesses greater vulcanization flexibility and
tubeless tires, tire side wall components, heat resistant truck inner tubes, hose pipes,
gaskets, conveyor belts, adhesive, sealants, tire curing bays, tank lining, etc.

21.7.10 Silicone Rubber (Polysiloxanes)

Silicone elastomer is made by ring opening reaction caused by action of alkali on
monomer acyclic siloxane characterized by exceptional mechanical and electrical
performance under extreme temperature condition. Used in aerospace, appliances,
electrical industry, construction industry, automotive industry, gaskets sealings, spark
plug boots, hose, rubber rolls.

21.7.11 Fluorosilicone Rubber

Fluorosilicone rubber (FSR) is characterized by excellent low temperature flexibility,
very good heat resistance, excellent aging characteristics. However, it has poor resistance
to aromatic hydrocarbon and common polar solvent.

21.7.12 Polyurethane Rubber

Polyurethane is made by reacting polyisocyanates and polyhydroxyl groups using curing
agents. Good abrasion resistance, oil and solvent resistance, oxygen ozone, temperature.
Finds wide application in solid tires for industrial trucks, seals and boots, calendar sheet,
potting and sealing of electronic components, general engineering mechanical goods,
shoe heels and soles, elastic threads, insulation, mattresses, vibration damping.

21.7.13 Ethylene/Propylene Number

Ethylene/propylene number (EPDM) is made by polymerization of ethylene, propylene,
diene using Ziegler–Natter type catalyst in combination of transition metal halides
and metal alkyls. Polymerization is carried out in a series of two or three vessels.
Adding polar material (e.g. water) stops polymerization. Unpolymerized monomers
are recovered and rubber is separated from the solvent by steam flocculation. Rubber
floc or crumbs are dewatered and dried. EPDM has outstanding resistance to heat,
ozone oxidation, weathering, and aging due to the saturated backbone, low brittle point
and glass transition temperature, low density and maintain acceptable properties at
higher filler loading. EPDM are non-tacking, used in single ply roofing, wire and cable
installations and automotive parts.

21.7.14 Ethylene Vinyl Acetate Rubber

Ethylene vinyl acetate rubber (EVA) has excellent resistance to heat, ozone and sunlight,
moderate resistance to oil and gasoline. It has poor resistance to aromatic and oxygenated
solvents, fair process ability.

21.7.15 Hypalon
Hypalon are chlorosulfonated polyethylene and are made by free radical catalyzed
reaction of chlorinated and SO with polyethylene.
Polymer, Elastomer and Synthetic Fiber 449

Hypalon is characterized by ozone resistance, light stability, heat resistance, weather

ability, resistance to deterioration by corrosive chemicals and weather ability, resistance
to deterioration by corrosive chemicals and good oil resistance, flame resistance,
toughness. It finds applications in automotive eat liner coatings, spark plug boots,
primary and ignition wire, tarpaulins, hose, conveyor belt, coated fabric.
21.7.16 Spandex
Spandex is a polyurethane elastomer which has both urea and urethane linkage and
has hard and soft blocks in its repeat structure.
21.7.17 Polysulfide Rubber
Polysulfide rubber has outstanding resistance to oil, gasoline and solvents, good
resistance to weather, ozone and sunlight, impermeability to gases and vapor. It has
poor resistance to abrasion, tear, cut growth and low tensile strength.

21.8 SYNTHETIC FIBER

Nylon 6 and nylon 6,6 are low important polyamides and find application in woven
and non-woven industries. Nylon 6 and nylon 6,6 are commonly used in textile, hosiery
and tire card industry. Polyester and acrylic fibers are other important synthetic fibers.
Apart from this polypropylene and polyurethane fibers also find application.
21.8.1 Nylon 6, Nylon 6,6, Cyclohexane, Caprolactam, Adipic Acid and
Hexamethylene Diamine
Caprolactam is monomer for nylon 6 while monomers for nylon 6,6 is nylon salt which
are made from adipic acid and hexamethylene diamine. Nylons are exceptionally
strong, elastic, abrasion resistant, lustrous, easy to wash, resistant to oil and many
chemicals, low in moisture absorbency ([Link]
htm). Characteristics of nylon 6 and nylon 6,6 are given in Table 21.22. Nylon fiber
finds application in apparel, home furnishings, tire cord, hose, conveyer and seat belts,
parachutes, racket strings, ropes tents thread, monofilament, fishing net, dental floss.
Nylon 6,6 is preferred for tire cord because of high melting point. Melt spinning process
is used for producing fiber stable and yarn.
Nylon 6 is the first synthetic fiber introduced in India starting with a modest volume
of 175 tons in 1962. Installed capacity and production of nylon filament yarn and nylon
industrial yarn is 36000 and 70000 tons and 33000, 86000 tons in 2010–11, respectively
in India.
Cyclohexane
Cyclohexane is an important chemical intermediate derived from benzene. It is used for the
manufacture of adipic acid and hexamethylene diamine for nylon 6,6 and caprolactam for
nylon 6. Ninety percent of the cyclohexane is used in the manufacture of nylon fiber and
nylon molding resin and remaining 10% of cyclohexane ends up as solvents or plasticizers.
Cyclohexane is made by catalytic hydrogenation of benzene in liquid phase or vapor phase.
Process flow diagram of manufacturing process is shown in Figure 21.16.
UOP hydrogenation process uses liquid phase hydrogenation of benzene at 200–300ºC
in presence of platinum based catalyst promoted by lithium salt at 3 MPa pressure. In
the IFP process cyclohexane is produced by liquid phase hydrogenation of benzene at
160–200ºC and 4 MPa using Raney nickel catalyst.
450 Chemical Process Technology

Fig. 21.16: Cyclohexane from benzene

Table 21.22: Characteristics of nylon 6 and nylon 6,6

Name Monomer Basic Properties of the synthetic Characteristics
of the chemicals fiber
syn­­thetic Density Moisture Melting
fiber regain point
Nylon 6 Phenol, 1.14 4.5 213– Resistant to weak
cyclohexane, 221ºC acids, decomposed
O toluene by strong mineral
acid, swelling
HN
is low. Very
Caprolactam good biological
resistance, good
resistance to heat.
Good adhesion to
rubber. Tenacity
4.3–8.3 g/denier,
elongation at
breaks 18–45%.
Nylon 6,6 Adipic acid Phenol, 1.14 4.0–4.5 230ºC Resistant to weak
HOOC – (CH2)4 – cyclohex- acid, decomposed
COOH ane, by strong mineral
Hexamethylene butadiene, acid. Chemically, it
diamine furfural is extremely stable.
H2N – (CH2)6 – NH2 Good biological
resistance.
Tenacity 8.0 g/
denier, elon­ga­tions
at break 16–20%.

Caprolactam
• Caprolactam is the principal raw material for nylon 6, a versatile material used as
fibers, industrial yarns and floor covering as well as for engineering plastics/films.
• Nylon 6 was first made in 1899 by heating 6-aminohexanoic acid but commercially
feasible synthesis from caprolactam was first discovered in 1935 by Paul Shalack.
• Global caprolactam production and demand scenario is given in Table 21.23.
Polymer, Elastomer and Synthetic Fiber 451

Table 21.23: Global caprolactam production and demand scenario

Caprolactam production (’000 tons) Caprolactam demand (’000 tons)
Year
Fibers Resins Fibers Resins
1990 2,463 499 – –
2010 2,559 1,845 2,463 (56%) 1,941 (44%)

Manufacturing caprolactam: Process of manufacturing caprolactam involves three

basic steps:
• Manufacture of cyclohexanone
• Manufacture of hydroxylamine sulfate
• Manufacture of caprolactam
Manufacture of cylohexanone: In subsequent stages cyclohexane is oxidized cobalt salt
as catalyst in multicompartment reactor at a temperature of 158–160ºC and 10 atm
pressure where the liquid flows in series from one chamber to another using. The
product stream is treated with sodium hydroxide to neutralize acids, saponify esters
and to decompose peroxides. Sodium salts which are immiscible with the main product
stream are separated in a gravity settler.
Organic phase containing cyclohexane, cyclohexanol, cyclohexanone are fed
to series of three distillation columns where these are separated. Cyclohexane is
separated as top product from the last column. Cyclohexanol separated in the last
column as bottom product is dehydrogenated to cyclohexanone in presence of zinc
carbonate and calcium carbonate catalyst at 400ºC. The unconverted cyclohexanol
and cyclohexanone after removal of light ends recycled to third distillation column
for recovery of cyclohexanone.
Manufacture of hydroxylamine sulfate: Production of hydroxylamine sulfate involves
production of ammonium carbonate by absorption of CO2 in 24% aqueous ammonium
solution. Production of nitrous oxide from mixture of NO and NO2, which is produced
by oxidation of ammonia in presence of platinum catalyst at 85ºC. Absorption of nitrous
gases from the ammonia combustion in ammonium carbonate to yield ammonium nitrite.
Manufacture of caprolactam: Manufacture of caprolactam involves production of
cyclohexanone oxime by reacting cyclohexanone with hydroxylamine sulfate in a multi-
compartment reactor. During this process ammonium sulfate is formed as byproduct.
Caprolactam and aqueous ammonium sulfate are sent to a series of extractors where
toluene is used as a solvent. Various routes of caprolactam is shown in Figure 21.17
(Nair and Lal, 1969; Taverna and Chiti, 1970; Vaidya and Gupta, 1986; Chavel and
Lefebvre, 1989, Mall, 2007). Ammonium sulfate collected from the extractor bottom is
purified, crystallized, centrifuged and dried. Caprolactam solution is concentrated in
multiple effect evaporators and finally purified. Flow diagram for the manufacture of
caprolactam is given in Figure 21.18 (Mall, 2007).

Adipic Acid
• Adipic acid is the basic raw material for the manufacture of nylon 6,6.
• World overall demand for adipic acid is growing by 3.6% during 2000–2010.
• Adipic acid is manufactured from number of starting raw materials like phenol,
cyclohexane, tetrahydrofuran, etc. Various routes for adipic acid manufacture
452 Chemical Process Technology

1. Original process:
Phenol Cyclohexanol Cyclohexanone Cyclohexanone oxime Caprolactam
2. Allied chemical phenol process:
Phenol Cyclohexanone Cyclohexanone oxime Caprolactam
3. Cyclohexane process via cyclohexanone:
Cyclohexane Cyclohexanol Cyclohexanone Cyclohexanone oxime Caprolactam
4. Toyo rayon photonitrozation:
Cyclohexane Cyclohexanone oxime Caprolactam
5. SNIA Viscosa toluene process:
Toluene Benzoic acid Cyclohexane carboxylic acid Caprolactam
6. Union carbide process via caprolactam:
Cyclohexane Cyclohexanol Cyclohexanone Caprolactone Caprolactam
7. DuPont process via nitrocyclohexane:
Cyclohexane Nitrocyclohexane Cyclohexanone oxime Caprolactam
8. Techni-chem process:
Cyclohexane Cyclohexanol Cyclohexanone Nitrocyclohexanone
Caprolactam Aminocaproic acid Nitrocaproic acid

Fig. 21.17: Various routes for caprolactam

Fig. 21.18: Manufacture of caprolactam

Various routes of adipic acid manufacturing is shown in Figure 21.19 (Vaidya and
Gupta, 1986; Chavel and Lefebvre, 1989; Saxena, 2000; Mall, 2007).
Polymer, Elastomer and Synthetic Fiber 453

Fig. 21.19: Various routes for manufacture of adipic acid

Process: Cyclohexane is oxidized by air to form cyclohexanol and cyclohexanone in

presence of cobalt naphthenate catalyst at temperature of 145–150ºC. The cyclohexanol
and cyclohexanone mixture is oxidized to adipic acid in presence of nitric acid using
ammonium metavanadate and copper scrap at 60–80ºC. The adipic acid formed is
crystallized, centrifuged and finally dried with hot air.
Hexamethylene diamine is another intermediate for the manufacture of nylon 6,6.
Hexamethylene diamine is manufactured by catalytic hydrogenation of adiponitrile in
presence of catalyst either by high pressure process (60–65 MPa) or low pressure process
(3 MPa). Catalyst in low pressure is nickel whereas in case of high pressure process
it is cobalt and copper. Process flow diagram for the manufacture of hexamethylene
diamine is given in Figure 21.20.
NC(CH2)4CN + 2H2 HN = CH(CH2)4CH = NH

Fig. 21.20: Process flow diagram for hexamethylene diamine

Nylon 6
Nylon 6 is produced from polymerization of caprolactam. Process steps involved in
production of nylon 6 involves the following steps:
• Caprolactam melting and addition of additives
• Polymerization: Batch/continuous and chips production
• Chips washing and drying
• Spinning of nylon
• Recovery section.
454 Chemical Process Technology

Caprolactam is polymerized to nylon 6 polymer by ring opening polymerization at

240–270ºC in presence of water, which opens the ring structure of the caprolactam to give
aminocaproic acid. Reacting SO2 with ammonium nitrite and ammonium carbonate which
results in production of hydroxylamine disulfonate finally hydrolysis of hydroxylamine
disulfonate at 95ºC to yield hydroxylamine sulfate and ammonium sulfate as by-product.
Process flow diagram for nylon 6 manufacturing is shown in Figure 21.21.

Fig. 21.21: Manufacture of nylon 6

Nylon 6,6
Nylon 6,6 is produced by polymerization of adipic acid and hexamethylene diamine.
Manufacturing process flow diagram for nylon 6,6 is shown in Figure 21.22.
• Production of nylon salt (hexamethylene diammonium adipate) by reaction of adipic
acid and hexamethylene diamine
• Concentration of nylon salt
• Polymerization of nylon salt in a jacketed vessel equipped with internal coils and
heated by dowtherm
• Cooling and chips production
• Spinning of nylon 6,6 chips
• Recovery section

Fig. 21.22: Process of nylon 6,6 manufacture

21.8.2 Dimethyl terephthalate (DMT) and Terephathalic Acid (TPA), Polyester,

PET Resin, PBT Resin
Global polyester production in all forms is currently around 56 million tons and may
cross 100 million in the next decade. Higher capacity addition is estimated in polyester
filament and chips segment compared to staple fibers in the next 2–3 years. Indian
textile industry has the potential to grow to US$ 220 billion by 2020 from current size of
around 80 billion. Besides, the lower per capita consumption of around 5 kg as against
global average of 11 kg indicates huge potential for expansion of fiber (Udeshi, 2012).
Table 21.24 gives the details of fiber per capita consumption.
Polymer, Elastomer and Synthetic Fiber 455

Table 21.24: Per capita fiber consumption

Kg/per capita 2000 2011
North America 35 35
Latin America 7 8
West Europe 22 24
East Europe 6 12
Africa/Middle-East 3 4
China 10 20
India 4 5
Source: PCI Udeshi, 2012.
Indian polyester production is likely to grow at a CAGR of 10–11% as against global
average of 7% and is expected to reach 10 million tons by 2020. In India, the polyester
filament and resin markets are witnessing higher growth prospects. Reliance is taking
significant expansions across the polyester chain (Udeshi, 2012). Characteristics of
polyester fibers are shown in Table 21.25.
Terephthalic acid (TPA) and dimethyl terephthalate (DMT) are major building blocks
for manufacture of polyethylene terephthalate (polyester) fibers and resins. The increase
in the PET demand in the major market fibers, film and rigid packaging has been the
primary drivers for the DMT/PTA market.

Table 21.25: Characteristics of polyester fiber

Name Properties of the synthetic
of the Basic fiber
Monomer Characteristics
synthetic chemicals Density Moisture Melting
fiber regain point
Polyester Dimethyl p-Xylene, 1.38 0.4–0.5 250ºC, Disintegrate in conc.
terephthalate methanol, Sticking H2SO4, resistant to alkali,
and purified ethylene point = disintegrate in boiling
terephthalic glycol 240ºC strong alkalies. Biological
acid (PTA) resistance is good, resis­
tance to weak acid and
alkali is good. Ironing
temperature 135ºC.
Tenacity 4.0–7.0 g/denier,
elongations at break
18–22%.

Paraxylene (P-Xylene)
PX is produced from the heart cut naphtha feed range 114–140ºC. p-Xylene plant consists
of five units: Pretreatment unit, reformer unit, fractionation unit, parex or crystallization
unit, and isomerization unit. Details of the p-xylene process is given Chapter 20.
Dimetyl Terephthalate (DMT)
Global production and consumption of DMT in 2009 was almost 2.0 million tons with
capacity utilization of 84.4. p-xylene and recycle p-toluic esters (PTE) are oxidized with
air at 140–150ºC at 6 kg/cm2 in presence of catalyst cobalt or manganese salts to form
p-toluic acid and TPA, monomethyl terephthalate (MMT). The final oxidation product
456 Chemical Process Technology

goes to the esterification column. In the esterification column the oxidation product is
esterified with methanol. Esterification takes place at 240–250ºC and 25 kg/cm2. p-Toluic
acid is esterified to p-toluic ester while TPA and MMT form DMT.

Consumption of Terephthalic Acid or Purified Terephthalic Acid

Some of the advantages of TPA over DMT are as follows (Paranjbe and Mathur, 1987):
• Per unit of polyester produced about 15% less TPA is required.
• Bulk density of TPA is 1.0 ton/m3 as compared to DMT (0.5 ton/m3). Thus transpor­
tation costs and storage requirements for TPA are significantly lower.
• TPA requires a lesser feed mole ratio of glycol to PTA of around 1.2 against 1.6 for DMT.
• DMT is fed to the transesterification process in molten form while TPA cannot be melted.
• Esterification reaction of TPA does not require any catalyst whereas the transes­
terification of DMT has to be catalyzed.
• With TPA it is simpler to maintain a constant degree of esterification. In case of
DMT, transesterification step is very sensitive to the quality of raw material, change
in mole ratio, etc.
• With TPA process, water is the byproduct whereas with DMT process methanol is
the byproduct. Therefore, more process hazards in handling methanol.
• With the TPA process, it is easier to reclaim polymer.
• Product from TPA is better with respect to thermal and hydrolytic stability.
• Product cost in case of TPA is lesser due to reduced raw material requirement,
reduced transport and handling cost.
There are two major steps:
1. Catalytic oxidation of PX to make crude terephthalic acid (CTA): This involves
oxidation, crystallization, solvent recovery, filtering, drying, etc.
2. Purification of CTA to make TPA: It involves hydrogenation, crystallization (AMCO
process), centrifuging, drying, conveying, storage, bagging, etc. or by leaching and
sublimation (Mobil process)

TPA Manufacturing Process Technology

AMCO process: Manufacture of terephthalic acid by AMCO process consists of two
steps—oxidation of p-xylene to crude terephthalic acid and purification of crude
terephthalic acid by crystallization.
1. Crude terephthalic acid:
• Oxidation section
• Crystallization section
• Separation and drying section
• Off-gases recovery section
• Solvent recovery section
• Catalyst recovery section.
2. Pure terephthalic acid:
• Feed preparation section
• Reactor section
• Crystallization section
• Separation and drying section
• PTA storage and warehouse.
Polymer, Elastomer and Synthetic Fiber 457

Oxidation of p-Xylene: p-Xylene is oxidized with air at 20 atm pressure and 200–210ºC
temperature in presence of catalyst cobalt acetate, manganese acetate and hydrobromic
acid as promoter. Reactions involved in manufacturing process is shown in Figure 21.23.
Figure 21.24 illustrates the process technology for PTA.

Fig. 21.23: Reaction involved in PTA manufacturing from p-xylene (Source: Singh, 2011).

Fig. 21.24: Process technology for purified terephthalic acid

458 Chemical Process Technology

Mobil process: In Mobil process, p-xylene is oxidized in presence of cobalt based

catalyst without using any promoter. The reaction takes place in acetic acid medium
at around 130ºC. Methyl ethyl ketone is used as activator. After cooling, washing and
centrifuging, crude TPA is sent to purification section. Detail of manufacturing process
of TPA is shown in Figure 21.25.

Fig. 21.25: Manufacturing process of TPA (Source: Ichikawa and Takeuchi, 1972.)

Here the purification of crude TPA takes place in two steps. The crude TPA is
slurried with acetic acid and charged to leaching stage. During leaching impurities like
p-carboxybenzaldehyde and cobalt catalyst are removed from the crude TPA. Crude
TPA (about 99.5% pure) is further purified by sublimation. Crude TPA from leaching
operation is dispersed in steam; hydrogen and catalyst are added to the dispersed TPA,
which is then passed through heated furnace. The purified TPA vapors after separating
impurities are condensed.
Polymer, Elastomer and Synthetic Fiber 459

Polyethylene Terephthlate (Polyester)

There are two routes for making polyester: DMT route or PTA route. However, with
availability of the pure terephthalic acid and because of its advantages over dimethyl
terephthalate, now polyester through esterification route is more commonly used.
Raw material: Terephthalic acid (TPA), ethylene glycol, dimethyl terephthalate

Dacron

Terylene DMT TPA Ethylene glycol

Process unit: Typical polyester plant consist of the following unit:

• P-xylene
• DMT unit/PTA unit
• Ethylene glycol
• Polyester manufacture
• Transesterification (in case of DMT)/esterification (in case of PTA)
• Polymerization
• Spinning
• Cutting and bailing.
Polyethylene terephthalate (PET) from DMT: PET from DMT is made by transesterification
route by reaction of dimethyl terephthalate with ethylene glycol followed by poly-
condensation. Polyester through transesterification route was more common earlier due to
non-availability of purified terephthalic acid. During transesterification, methanol obtained
as by product. Figure 21.26 describes the manufacturing process of polyester from DMT.

Fig. 21.26: Polyester from dimethyl terephthalate (DMT)

460 Chemical Process Technology

Polyester from DMT routes

Polyethylene terephthalate (PET) from TPA (PTA): PET from TPA is made by esterification
route by reaction of purified terephthalic acid (PTA) with ethylene glycol followed
by polycondensation. Figure 21.27 describes the manufacturing process of polyester
from PTA.
Polyester from PTA routes

1. Polycondensation: Temperature 270–280ºC, short polycondensation time, high

vacuum for proper degree of polycondensation. Thermal decomposition increases
with high melt temperature and higher degree of polycondensation. Thermal
instability of polyester melt influence the fiber. Decomposition lowers the viscosity
of polyester melt.
• Catalyst: Antimony trioxide
• Flasher, prepolymerizer, finisher
• Vacuum at last stage: 2 mm Hg, 285ºC.
2. Spinning: Spinning of polyester is done by melt spinning. Molten polymer passed
through spinnerate. The extruded filaments from the spinnerates are quenched and
cooled by air. The quenched filaments are passed to winding unit through finish
applicator. The spun yarn is passed to draw twisting and draw texturing unit.
Polyethylene Terephthalate (Pet) and Polybutene Terephthalate (PBT) Resin
Polyethylene terephthalate (PET) and polybutene terephthalate (PBT) are two important
saturated thermoplastics. PET apart from its major use as synthetic fiber finds application
in photographic film, videotape, computer and magnetic tapes, beverage bottles, etc.
Demand for PET packaging resin continues to grow strong and attracting new entrants
into market. PET packaging industry growth rates are driven by continued strong
demand for bottle water, the expansion of niche carbonated soft drink markets and
new packaging applications for PET.
Polymer, Elastomer and Synthetic Fiber 461

Fig. 21.27: Polyester from purified terephthalic acid

As the use of PET in packaging matures in established segments like carbonated

soft drinks and bottled water, the world PET resin market is expected to be around
17 million tons by 2010. PET packaging resin has come of age and is now a globally
traded commodity with inter regional world trade amounting to around 15% of global
consumption (Chemical News and Intelligence, [Link]).
The IntegRex™PET processsis the world’s first integrated PET process specially
designed for packaging resin. Compared to conventional PTA and PET processes,
IntegRex™technology stands out for fewer process steps, is simpler, more reliable and
462 Chemical Process Technology

more cost efficient. Polybutylene terephthalate which was introduced in 1962 and was
made available around 1971 is made by condensing terephthalic acid or dimethyl ester
with 1,4-butanediol. Polybutene terephthalate is polymerized in two stages. In first
stage bis-hydroxy butyl terephthalate (Bis-HBT) is formed through trans-esterification
of DMT with 1,4-butanediol. In second stage, Bis-HBT is polycondensed into PBT with
elimination of 1,4-butanediol. The reaction involved is:

PBT finds use as engineering material due its dimensional stability, particularly
in water and its resistance to hydrocarbon oils without showing stress cracking,
high mechanical strength and excellent electrical properties, lower water absorption.
Blends of PET and PBT are used in glass fibers reinforced grade. PBT find application
in pipe, pump hosing, impeller bearing brushing, gear wheels, and electrical parts
such as connector and fuse cases, automotive parts and toothbrush bristles. Because of
thermoplastic nature both PET and PBT may be injection or extrusion molded.

21.8.3 Acrylonitrile, Acrylic Fiber, Modified Acrylic Fiber, Polyurethane

Acrylic fibers are third largest class of synthetic fiber after polyester and nylons.
Commercial acrylic fiber was developed by DuPont in US as Orlon while modified
acrylic fiber was developed by Union carbide as Dynel. In acrylic fiber monomer is
acrylonitrile while in case of modified acrylic fiber acrylonitrile is copolymerized with
vinylidiene chloride vinyl chloride. The halogenated monomers impart flame resistance
and are suitable for home furnishing, protective coatings, sleepwear, and hospital
blankets. Characteristics of acrylic fiber and modified acrylic fiber are mentioned in
Table 21.26.

Table 21.26: Characteristics of acrylic fiber

Name Properties of the synthetic

of the Basic fiber
Monomer Characteristics
synthetic chemicals Moisture Melting
fiber Density
regain point
Acrylic Acrylonitrile Propylene, 1.17 1.5–2.5 Sticking Silk like luster, good
fiber ammonia point = resistance to weathering,
235ºC alkalies and acids, high
bulking, tensile strength
2–3 g/denier. Elongations
at break 16–21%
Modified Acryloni- Propylene, – 1.5–2.5 Sticking Good resistance to weathe­
acrylics trile, vinyl ammonia, point = ring, alkalies and acids,
chloride, ethylene 235ºC high bulking, good resis­
vinylidene tance to combustion
chloride
Polypro­- Propylene Propylene 0.85– <0.1 168– Good resistance to bacteria,
pylene 0.94 171ºC chemical and water
Polymer, Elastomer and Synthetic Fiber 463

Acrylic fibers are soft, light weight, durable, strong, high crease recovery, color
fastness to both washing and sunlight, easy care-easy laundry and low maintenance
cost, high abrasion resistance, good aesthetics-high luster, good wicking action- helps in
quick transfer of moisture and sweat resulting in quick drying, no allergic and nontoxic,
resistance to mile and insects, oils, chemicals. It is very resistant to deterioration from
sunlight exposure.
Polyurethanes are another important polymer which find application in manufacture
of flexible, high resilience foam seating; rigid foam insulation panels, microcellular foam
seals and gaskets; durable elastomeric wheels tires; automotive suspension bushings,
electrical potting compounds; high performance adhesives; surface coatings and surface
sealants; synthetic fiber ([Link]
Acrylonitrile (CH2=CH–CN)
Acrylic nitrile is one of the important monomer for manufacture of acrylic fibers;
however, earlier routes of acrylonitrile manufacture are acetylene, ethylene oxide or
acetaldehyde route and how being replaced by propylene route due to availability
of cheaper propylene from steam cracker plant. This involves ammono-oxidation of
propylene. Other uses of acrylonitrile are in the manufacture of nitrile rubber, ABS and
SAN plastics, adiponitrile and acrylamide. In addition, it is also used in the manufacture
of acrylates, intermediates for flocculants, pharmaceuticals, antioxidants, dyes and
surface active agents (Chemical Industry Digest, March 1996, p.22). Various routes of
acrylonitrile manufacturing are shown in Figure 21.28.

Acetylene Route

Ethylene Oxide Route

Acrylonitrile (CH2=CH–CN)

Acetaldehyde Route

Propylene Route

Fig. 21.28: Various routes for the manufacture of acrylonitrile

Acrylonitrile by ammoxidation of propylene: A typical acrylonitrile plant consists

of reactor section, acrylonitrile recovery section, acrylonitrile purification section and
HCN purification section. Propylene, ammonia and air are fed to fluidized bed catalytic
reactor where ammoxidation of propylene—a highly exothermic reaction occurs.
Manufacturing process technology is shown in Figure 21.29.
464 Chemical Process Technology

Process steps: Process steps are:

• Catalyst preparation: bismuth and molybdenum oxide
• Mixing of propylene, ammonia and oxygen in [Link]
• Reaction section: Macrylonitrile acetonitrile, hydrogen cyanide, unreacted mixture
of propylene, ammonia and oxygen are fed to fluidized bed reactor. Various product
from reactor are and oxygen. Reaction is highly exothermic.
• Removal of ammonia
• Absorption of absorbable component from ammonia free gas in water to separate
the non-condensable and unconverted propylene, propane, nitrogen, CO and CO2.
• Stripping of organic components and separation of HCN
• Separation of acrylonitrile and acetonitrile which are close boiling compounds. And
are separated by extractive distillation using water as solvent. A dilute solution of
acrylonitrile is separated which is recovered and concentrated
• Purification of acetonitrile
• Final purification of acrylonitrile.
Reactions: Formation of acrylonitrile occurs by the following reaction:
CH2 = CH – CH3 + O2 CH2 = CH – CHO + H2O

CH2 = CH – CHO + NH3 CH2 = CH – CH = NH + H2O

1
CH2 = CH – CH = NH + 2 O2 CH2 = CH – CN + H2O
Overall reaction:
3
CH2 = CH – CH3 + NH3 + 2 O2 CH2 = CH – CN + 3H2O; DH 515  kJ/mol
Side reactions:
2CH2 = CH – CH3 + 3NH3 + 3O2 3CH3CN + 6H2O

CH2 = CH – CH3 + 3NH3 + 3O2 3HCN + 6H2O

CH2 = CH – CH3 + 3O2 3CO + 3H2O

2CH2 = CH – CH3 + 9O2 6CO2 + 6H2O

Fig. 21.29: Process technology of acrylonitrile manufacture

Polymer, Elastomer and Synthetic Fiber 465

Acrylic Fiber Manufacture

Acrylic fibers are third largest class of synthetic fiber after polyester and nylons.
Commercial acrylic fiber was developed by DuPont in US as Orlon while modified
acrylic fiber was developed by Union carbide as Dynel.
Process technology: Manufacturing process is shown in Figure 21.30. The manufacturing
process can be broadly divided into two parts.

Fig. 21.30: Process flow diagram of manufacture of acrylic fiber

(Source: Mall, ID, Petrochemical Process Technology, 2007).

Polymerization: Polymerization includes copolymer composition, catalyst system,

polymerization reaction and monomer recovery. Major polymerization processes are
bulk polymerization, suspension polymerization, emulsion polymerization and solution
polymerization. Most of the acrylic polymers manufactured for fiber grade are made
through suspension polymerization that gives high percentage of conversion, better
product whiteness, shorter residence time and easy control of polymerization. Emulsion
polymerization is used in case of modified acrylic fiber. Inorganic compounds such as
persulfate, chlorates or hydrogen peroxide are used as radical generators.
Redox initiation is normally used in production of acrylic fiber. The most common
redox system consists of ammonium or potassium persulfate (oxidizer), sodium bisulfite
(reducing agent), and ferric or ferrous ion (catalyst) (Capone GJ, Masson, JC. Fiber
Acrylic in “Kirk-Othmer encyclopedia of Chemical Technology, fifth edition, volume
11 Willey Inter Sciences).
Spinning: Spinning includes solution/dope preparation, spinning techniques and
finishing operation including after treatment, cutting and bailing.
1. Dry spinning: In dry spinning of acrylic fiber dimethylformamide (DMF) is used. The
DMF spin dope contains the polymer in the DMF, thermal stabilizers, delustrant.
It passed through spinnerate placed at top of the solvent removal tower. The DMF
466 Chemical Process Technology

evaporated by circulating inert gas through tower at about 300–350ºC to remove the
solvent
2. Wet spinning: In wet spinning sodium thiocyanate are commonly used as solvent.
Wet spinning fiber is spun into a liquid bath containing a solvent non-solvent mixture
called coagulant. Non-solvent is usually water. The fiber emerging from spin bath
are washed and dried followed by cutting and bailing.
Polyurethane
The polyurethanes which were discovered by Otto Bayer et al. in 1937 (Riegel, 1997) are
versatile class of thermosetting polymers and offer the elasticity of rubber combined
with toughness and durability of metal. Worldwide demand for polyurethane expected
to grow at CAGR of 5.8% from 12.0 million tons in 2010 to 116.88 million tons in 2016,
with Asia pacific region accounting for over 60% of this figure, according to GBI research.
The global market value of polyurethane will rise in the coming years, with thermal
insulation becoming a key material application. According to GBI research flexible
and rigid polyurethane foams made up the bulk of the total end use segment in 2010,
accounting for 60% of the total amount (Chemical Industry Digest, July 2012, p.29).
Polyurethane is a polymer formed by combining two or more isocyanate functional
group and two or more hydroxyl groups. The alcohol and isocyanate groups combine
to form a urethane linkage. Polyurethanes are made by addition of polyols and
polyfunctional isocyanates. Commonly used isocyanates are toluene di-isocyanate
(TDI), diphenyl methane di-isocyanate (MDI), hexamethylene di-isocyanate (HDI).
Polyols may be either polyether polyols or polyester polyols. However, polyether
polyols are more commonly used. Catalysts used in polyurethane manufacture are–
aliphatic and cyclo-aliphatic tertiary amines and organic tin compounds. Typical reaction
involved by reaction of poly isocynates and poly hydroxy compounds is:
NOC – R – NCO + NHO – R’ – OH (R – NH – COO – R’ – OCO – NH)n
Diisocynate diol (linear polyurethane)

Polyurethane Foam
Poloyuretane rigid foam are characterized by good structural strength, excellent
adhesion to most substance, processing flexibility and long life. Rigid polyurethane
foams are most widely preferred insulation and find application in refrigerator,
manufacture of thermo-ware, cold sore panel, refrigerated trucks and wagons. A rigid
polyurethane foam is a cellular polymer in which the individual small cells are filled
with a gaseous blowing agent which imparts the remarkably low thermal conductivity
to these foams (Fonseca, 1993).

21.8.4 Cellulosic Fibers (Viscose Rayon and Acetate Rayon,

Cuprammonium Rayon) (Mall, 2013)
Rayon is derived from French word “rays of light” and was first sold as artificial
silk. Rayon is made from cellulose derived from naturally occurring material.
The first manufactured cellulosic fiber was invented in France in 1884; however,
first commercial production was in 1910 by Avtexfiber Inc. in USA ([Link]
[Link]/Presentation/lovelight1989-1258602-introduction-vfy/). Some
of the common rayons are viscose rayon, acetate rayon, and cup ammonium rayon.
Other rayons are cuprammonium rayon and pyroxylin rayon. Some of the natural
Polymer, Elastomer and Synthetic Fiber 467

material based are casein fiber, alginate fiber, vicara, soybean. Amongst the various
rayon, viscose rayon is most commonly commercially manufactured rayon and
that finds wide application in textile, tyre cord industry. Various types of viscose
rayons are regular rayon, high tenacity rayon, high wet modulus (HWM) rayons,
flame retardant rayon, super adsorbent rayon. Some of the major rayon producing
units in India are given in Table 21.27. Global demand of viscose fiber is 3,20,000
tons per annum.

Table 21.27: Indian capacity of viscose rayon

Name of the unit Capacity, tons
Century rayon 53,000
Kesoram rayon 17,000
Indian rayon 7,000
National rayon 13,000
Baroda rayon 4,500
Domestic demand 54,000

Properties of Viscose Rayon

Viscose rayon has a silk aesthetic with superb drape and feel and retains its rich brilliant
color. It has high moisture absorbency similar to cotton, breathable, comfortable to
wear and easily died. It is comfortable, soft to skin and has moderate dry strength
and low abrasion resistance, no static buildup, moderate resistance to acid and alkali,
excessive by flammable. Thermal properties poor and losses strength above 149ºC, chars
and decomposes at 177–244ºC. Tenacity ranges between 2.0–2.6 g/den when dry and
1.0–1.5 g/den when wet. It has poor crease recovery and crease retention in comparison
to polyester. Because of low melting point lower application in tire cord. Application
of viscose rayon is given in Table 21.28.
Various grades: Flat yarn, high tenacity, mono-filament, fibers, tow/tops, spun yarns.
Types of rayon: Regular rayon, high wet modulus rayon, high tenacity rayon, micro­
fibers, tencel rayon, lyocel, special rayon flame retardant fibers, superabsorbent rayons,
microdenier rayon fibers.

Table 21.28: Application of viscose rayon

Yarn Embroidery, chenille, cord, novelty yarns
Fabric Crepe, garardine, suiting, lace, outwear fabrics and lining of coats and outwear
Apparel Dresses, blouses, saris, jackets, lingerie, linings, millinery (hats), slacks, sport
shirts, sports-wear, suit, ties, work cloth
Domestic textiles Bead spreads, bed sheets, blankets, curtain, draperies, slip covers, table cloths,
up hosiery
Industrial textiles High tenacity rayon is used as reinforcement to mechanical rubber goods
(tires, conveyor belts, hoses) applications within aerospace, agricultural textile
industries, braided cord, tapes
Miscellaneous Sausage casing, cellophane, feminine hygiene
Source: [Link]
468 Chemical Process Technology

Raw material: Cellulose, NaOH, carbon disulfide, sulfuric acid, titanium dioxide to
de-luster the yarn, sodium sulfide, sodium sulfite, sodium hypochlorite additives.
Cellulose is obtained from rayon grade pulp or cotton linter (Table 21.29).
Rayon grade pulp: Rayon grade (also called dissolving pulp) is high cellulose content
pulp. Wood pulp is major source of rayon grade pulp. During production of rayon
grade pulp more drastic condition is used to obtain high quality dissolving pulp. During
selection of raw materials process conditions in pulping and bleaching, pulping and
bleaching chemicals and further processing of pulp special precaution is taken.

Table 21.29: Raw material for per ton of rayon fibers

Raw materials Needed per ton
Pulp 1,030 kg
NaOH 650 kg
H2SO4 960 kg

CS2 330 kg
Zinc sulfate 30 kg
Bleach chemical 50 kg
Coal 6,250 kg
Water 600 m3
Power 2,000 kg

Process steps: Details of manufacturing process of viscose rayon is given in Table 21.30.
Figure 21.31 show the process of manufacture of viscose rayon.

Table 21.30: Process details of viscose rayon manufacturing

Production of cellulose Cellulose used in the manufacture of viscose rayon is alpha cellulose.
Cellulose is obtained from pulping of wood/bamboo where special
care is taken in pulping and bleaching so that the pulp is of higher
strength with high cellulose content
Steeping This involves pulp sheets are placed in steeping compartment and
reacted with 18–20% NaOH at 20–22ºC for about 1–4 hr. Purpose
of steeping is:
• To break intermolecular bonds of the cellulose to increase
solubility of cellulose xanthate
• To convert cellulose into alkali cellulose
• To swell cellulose fiber
• To dissolve low molecular weight hemi-cellulose
Pressing This is done to remove excess liquid.
Shredding and white crumb The alkali cellulose obtained after pressing are fed to shredder at
about 28ºC for 90–120 min. This involves shredding of pressing
sheet to produce white crumb which is fluffy which allow air to
penetrate effectively.
Aging After shredding the white crumb are aged to bring down degree of
polymerization. This involves aging of crumb through exposure of
white crumb to oxygen. It helps in maintaining proper viscosity.
Contd...
Polymer, Elastomer and Synthetic Fiber 469

Table 21.30: Process details of viscose rayon manufacturing (Contd...)

Xanthation After ageing, the soda cellulose crumbs are fed into a air tight rotating
churns. The process involves treatment of white crumb with carbon
disulfide under controlled condition at 20–30ºC to form a cellulose
xanthate. This is called yellow crumb. The yellow crumb is dissolved
in caustic solution to form viscose.
Ripening, filtering and The process involves ripening of viscose by keeping for 4–5 days at
deaeration 10–18ºC which varies according to type of fiber being made. Ripeness
measured by Hotteen number. After ripening the ripen viscose is
filtered and degassing is done to remove air bubbles.
Spinning of the viscose Spinning of viscose is done by wet spinning by passing through
spinnerrate in acid bath resulting in formation of rayon filament.
Spinning bath
Sulfuric acid 10 parts
Sodium sulfate 18 parts
Glucose 2 parts
Zinc sulfate 1 part
Water 69 parts
Sodium sulfate precipitates sodium cellulose xanthate into
filament form and acid converts it into cellulose. Zinc sulfate gives
added strength. Further processing involves washing, desulfurizing,
bleaching, conditioning and drying.
Drawing and cutting Drawing is the process of stretching the rayon filament which
straighten out the fibers. The continuous yarn is cut into for
producing staple fibers.
Crimping The staple fiber is made like wool by crimper. Sarille is crimped
viscose staple having wool like fabrics.
Dyeing of viscose rayon Viscose rayon has high affinity for dye and can be dye easily with
cotton dyes.

Reactions:
470 Chemical Process Technology

Variables in spinning:
• Temperature and composition of bath • Speed of spinning
• Speed of coagulation • Stretch imparted
• Length of immersion

Fig. 21.31: Process flow diagram for viscose rayon manufacture

Polysonic Fibers (VINCEL, ZANTREL)

Polysonic fibers are new kind of viscose rayon and have uniformity, length luster and
microfibrillar structure. During the process steps are taken to maintain higher degree
of polymerization by reducing the severity of chemical processing. During the initial
stage cellulose sheets bathed in weaker caustic soda. Higher degree of polymerization
(around 500–700 against viscose rayon around 250) is achieved by precipitating the
viscose gently and slowly. The fiber is much like cotton.
Acetate Rayon
The purified cotton linters or cellulose is fed to the acetylator containing acetic anhydride,
acetic acid and conc. sulfuric acid and acetylation is carried out at 25–30ºC. The reaction
mixture called acid dope is allowed for ripening for about 10–20 hours. During reopening
conversion of acetate groups takes place. After reopening, the mixture is diluted with
water with continuous stirring. During the process flakes acetate rayon is precipitated
which is dried and send to spinning bath where dry spinning of acetate rayon takes place
by dissolving in solvent and passing through spinnerate. The solvent is evaporated by
hot air. The dope coming from the spinnerate is passed downward to feed roller and
finally to bobbin where spinning is done at higher speed.
Raw material: Purified cotton linters, wood pulp, acetic anhydride, acetic acid and
sulfuric acid.
Process steps
1. Activation with acetic acid: The process involves steeping of purified cotton in acetic
acid which makes swelling and makes cellulose more reactive
Polymer, Elastomer and Synthetic Fiber 471

2. Acetylation: The pretreated cotton with acetic acid is then acetylated with excess
acetic acid, acetic anhydride, with sulfuric acid to promote the reaction.
• One part of purified cellulose
• Three parts of acetic anhydride
• Five parts of acetic acid
• Sulfuric acid 0.1 part (as catalyst)
• Reaction exothermic
• Temperature 20ºC for the first hour
• 25–30ºC for the next 7–8 hours
Hydrolysis of triacetate: The triacetate formed is hydrolyzed to convert triacetate to
diacetate. The resultant mixture is poured in water to precipitate the cellulose acetate
DP 350–400 2.35–2.4 acetyl groups per anhydro glucose unit.
3. Spinning: Secondary acetate is dissolved in acetone, fitered, dearerated and passed
through spinerrate in hot air environment, which evaporates the solvent.
Economical production
• Low cost and availability of acetic acid and acetic anhydride
• Recovery of acetic acid
• Recovery of acetone
Process flow diagram for the manufacture of acetate rayon is given in Figure 21.32.
Properties: Tenacity 1.4 g/denser, MP 230ºC and decompose when melted, readily
soluble in acetone, methyl ethyl ketone, methyl acetate, ethyl acetone, chloroform,
ethylene chloride.
472 Chemical Process Technology

Fig. 21.32: Process flow diagram for the manufacture of acetate rayon

Cuprammonium Rayon
Cuprammonium rayon is made from reaction of Cellulose with copper salt and
ammonia. After bleaching cellulose is added in ammoniacal solution of copper sulfate
resulting in formation of cuprammonium cellulose which is spun into water and the
yarn is washed with acid to remove traces of ammonia and dried. Process flow diagram
for the manufacture of cuprammonium rayon is given in Figure 21.33.

Fig.21.33: Process flow diagram for the manufacture of cuprammonium rayon

BIBLIOGRAPHY
1. Annual Reports 2010–11, 2013–14, 2015–16, 2016–17, Dept of Chemicals & Petrochemicals
(Ministry of Chemicals and Fertilizer, Government of India).
2. Austin GT. “Cyclic Intermediates and dyes”. Shreve’s Chemical Process Industries. Fifth Edition,
McGraw Hill International editions 1984, p.772.
Polymer, Elastomer and Synthetic Fiber 473

3. Capone GJ, Masson JC. “Fiber Acrylic in Kirk-Othmerencyclopedia of Chemical technology”.

Fifth edition, Volume 11, Wiley Inter Sciences.
4. Chauvel A, Lefebvre G. “Sources of Olefinic and aromatic hydrocarbons”. Petrochemical
Processes, 1985, Volume I, edition Technip, p.129.
5. Chavel A, Lefebvre G. “Monomers for polyamide synthesis in Petrochemical Processes-2”.
Editions Technip Paris, 1989, p.233,287.
6. Chemical Industry Digest July 2012, p.29.
7. Chemical Industry Digest March 1996, p.22.
8. Chemical News and Intelligence, [Link]
9. Chemical Weekly, January 17, 2012.
10. Chemistry and Industry 5, August 1996, p.574.
11. CMAI Consulting, 2010.
12. CMAI, 2003.
13. COINDS “Comprehensive industry document Man-made Fiber Industry” Central Pollution
Control Board New Delhi, 1979–80.
14. Dept. of Chemicals and Petrochemicals, GOI, IMACS Analysis.
15. file:/A:\Poly(styrene- butadiene-styrene).htm
16. Fonseca R. “Polyurethanes”. Chemical Engineering World. Vol 28, No. 4 April, 1993.
17. Gupta BS. “Manufacture of textile fibers”. p.735 Riegel’s Handbook of Industrial Chemistry,
Ninth edition Edited by James A. Kent CBS Publishers & Distributors, Fifth edition 1997.
18. Hatch, LF, Matar, S. “From hydrocarbon to petrochemicals Part 16-thermoplastics”. Hydrocarbon
Processing, Vol.58, Sep 1979, p.175, 141.
19. [Link]
20. [Link]
21. [Link]
22. [Link]
23. Hydrocarbon processing, Petrochemical Process, 2003.
24. Ichikawa Y, Takeuchi Y. “ Compare pure TPA Processes”. Hydrocarbon Processing. Nov 1972.
25. IISRP (2011) TSRC Corporation.
26. International Rubber Study Group, 2012.
27. Jensen M, Hsain J, Myers A, Hummel A.” What is driving changes in polyolefinn catalysts and
catalyst technology? Hydrocarbon Processing. April 2008, p.81.
28. Kapur GS, Tuli DK, Malhotra RK, Kumar A. “Polyolefin materials and catalysts: An Introduction”
J of Petrotech Society, June, 2008, p.10.
29. Mall ID. “Petrochemical Process Technology”. First Edition, Macmillan 2006, Reprint 2016,
Second edition 2017. Laxmi Publication.
30. Mall ID. NPTEL Web and Video Course NPTEL, 2013.
31. Mukhopadhya R. “Recent advances in synthetic rubber and applications”. Chemical Industry
Digest, August 2011.
32. Mukhopadhya R. “Recent advances in synthetic rubber and applications”. Chemical Industry
Digest, August 2011.
33. Nadini. Chemical Journal, April 1998, p.21.
34. Nair SR, Lal IB. “Technology and applications of polyamides fibers”. Seminar or synthetic
chemical fibers in India in the coming decade, organized on IIChE North Regional Centre, New
Delhi, 28 December, 1969, p.17.
35. Paranjpe HL, Mathur BB. “Polyester raw material DMT or TPA”, Chemical Age of India, Volume
38, No. 4, 1987, p.177.
36. Patel MM. “Nitrile rubbers”, Chemical Engg. Wold vol 24, No.12, 1991, p.107
474 Chemical Process Technology

37. Rakesh Mehra. “Emerging trends in Man-Made Textiles”, the Synthetic & Rayon Textiles Export
Promotion Council (SRTEPC), 5th texcon Asian textile Conference.
38. Richardson, 1
39. Riegel, 19
40. Saxena MP. “Monomers for Synthetic Fiber”. AICTE Staff Development Programme’, Short-term
Course on Hydrocarbon Engineering, 3–22 January 2000, p.306.
41. Shah A. “Indian polypropylene markets”, Indian Petrochem 2009.
42. Shashi Kant, Kapur GS. “Polypropylene”. J of Petrotech, March, 2011, 27.
43. Singh S. “PTA manufacturing” 6th Summer School, IIPM, 10th Jun, 2011, IOC Ltd.
44. Taverna M, Chiti M, “Routes to caprolactam”, Hydrocarbon processing, November, 1970, p.140.
45. Technical EIA Guidance Manual Project Sponsored by the Ministry of Environment and Forests.
46. Trivedi P. “Plastics boon or Bust” Chemical News, October 2017, p.27.
47. Trivedi P. Hovering between the two worlds. Chemical News April 2018.
48. Udeshi RD. “Indian polyester chain-An overview” Chemical News April 2012, p.31
49. Vaidya AA, Gupta DC. “Raw materials for synthetic fibers”. Chemical Engineering World,
Volume 21, No. 3, 1986, p.35.
50. “Ways to get rid of the plastic”. Chemical News, October 2011, p.21.
51. Woodings Calvin. “Fiber regenerated cellulose”. Kirk Othmer Encylopedia of Chemical
Technology. Fifth edition, Volume 11 Wiley Inter Science, 2006, p.246.
22
Agrochemicals

22.1 INTRODUCTION
In order to meet the needs of a growing population, agricultural production and pro­
tec­tion of technology have to play a crucial role. Substantial food production is lost
due to insect, pests, weeds, rodents, nematodes and during storage. Pesticides are
now basic needs for agriculture production. Almost every country in the world uses
pesti­cides. Pesticides industry in spite of various hazards has been playing important
role in green revolution. An appreciable amount of food is lost due to insect pests,
plant pathogens, weeds, rodents, birds and in storage. Pesticides include insecticides,
fungicides, herbicides, rodenticides, nematicide at different stages of agricultural
production (Dureja, 2009).
Pesticides industry has developed substantially and has contributed significantly
towards India’s agricultural and public health. In value terms the size of Indian pesticide
industry is $3.8 billion in the year 2011. India is predominant exporter of pesticide to
USA, Europe and African countries.
Agriculture is the lynchpin of the Indian economy. Apart from fertilizers, pesticides
played important role in the green revolution during the last five decades. Indian exports
of agrochemicals have shown an impressive growth over the last five years. India is one
of the most dynamic generic pesticide manufacturers in the world with more than 60
technical grade pesticides are manufactured indigenously by 125 producers consisting
of large medium scale enterprises including about 10 multinational companies and
more than 500 pesticides formulators spread over the country (Annual Report, 2011,
Department of Chemical and Fertilizers, Government of India).
In 1948, it was first made use for malaria control and in 1949 it was first made use
for agricultural purpose. Then the indigenous production of pesticides began with the
establishment of a DDT and BHC plant in 1954. Thereafter a steady growth in production
took place with maximum growth occurring during the period 1966–1977.
The Indian pesticide industry with 85,000 metric tons (MT) of production during
financial year (FY) 07 is ranked second in Asia (behind China) and twelfth globally. In
value terms, the size of the Indian pesticide industry was estimated at ` 74 billion for
2007, including exports of ` 29 billion. Though pesticides have made us self-sufficient
in our food needs, the per hectare consumption of pesticides in India is very low.
Pesticides which include fungicides, herbicides, rodenticides, miticide, nematicide are
basically derived from various chemicals which are initially manufactured as technical
grade products and later they are converted into approved formulations (powder,
emulsions, concentrates).
475
476 Chemical Process Technology

The Indian pesticide industry is characterized by low capacity utilization. The

present total installed capacity is 146,000 tons and has low capacity utilization of <60%.
Table 22.1 shows the profile of pesticide of Indian industry. The industry suffers from
high inventory owing to seasonal and irregular demand on account of monsoons.
There is a marked difference in the consumption pattern of pesticides in India vis-a-vis
the rest of the world. Insecticides accounts for 76% of the total domestic market on the
other hand, herbicides and fungicides have a significantly higher share in the global
market. Crops like cotton wheat and rice together account for 70% of total agrochemical
consumption. The consumption of pesticide is low in comparison to other countries.
Total consumption of pesticides is given in Figure 22.1 (Agrochemical Sub-group of
Indian Chemical Councils). Profile for installed and production of major chemicals are
shown in Figure 22.2.

Table 22.1: Profile of pesticide industry in India (000’ MT)

Major groups/products Installed capacity Production
Pesticides and insecticides 2009–10 2002–03 2009–10 2010–11
DDT 6.30 2.94 3.61 3.09
Malathion 8.80 4.25 0.62 0.64
Parathion (methyl) 4.00 2.04 0.00 0.00
Dimethoate 3.20 0.76 0.96 1.12
DDVP 2.51 3.46 3.12 3.13
Quinalphos 4.00 1.77 0.99 1.01
Monocrotophos 14.00 6.52 5.74 8.60
Phosphamidon 3.90 0.84 1.00 0.03
Phorate 8.20 3.16 2.00 2.63
Ethion 5.60 1.68 0.43 0.65
Endosulfan 9.90 3.66 2.80 1.73
Fenvalerate 2.60 0.52 0.53 0.08
Cypermethrin 6.90 5.08 6.23 4.95
Anilophos 1.10 0.35 0.00 0.00
Acephate 9.20 4.84 1.083 12.84
Chlorpyriphos 9.10 6.40 2.90 3.35
Phosalone 1.00 0.44 0.00 0.00
Metasystox — 0.51 0.00 0.00
Fenthion — 0.91 0.00 0.00
Triazophos — 1.15 1.00 1.58
Lindane 0.70 0.33 0.00 0.00
Temephos 0.20 0.12 0.00 0.00
Deltamethrin 0.50 0.21 0.02 0.00
Contd...
Agrochemicals 477

Table 22.1: Profile of pesticide industry in India (000’ MT) (Contd...)

Major groups/products Installed capacity Production
Pesticides and insecticides 2009–10 2002–03 2009–10 2010–11
Alphamethrin 1.50 0.19 0.00 0.51
Captan and captafol 1.80 0.78 0.00 0.00
Ziram (thiobarbamate) 0.50 0.00 0.00 0.00
Carbendzim (bavistin) 1.50 1.26 0.19 0.26
Calixin 0.20 0.05 0.00 0.00
Mancozab 20.70 10.19 31.49 26.05
Copper oxychloride 1.50 0.24 0.00 0.00
2,4-D 1.20 0.00 0.00 0.00
Butachlor 0.50 0.24 0.24 0.09
Isoproturon 5.40 2.66 2.91 3.90
Glyphosate 2.60 0.11 1.70 2.28
Diuron 0.10 0.05 0.13 0.20
Atrazin 0.50 0.20 0.26 0.24
Fluchloralin 0.20 0.19 0.00 0.00
Zinc phosphide 0.90 0.24 0.33 0.42
Aluminum 2.30 1.99 2.16 1.80
Dicofol 0.20 0.10 0.02 0.043
Total 146.20 69.57 82.19 81.22
Source: Dubey B, Kumar A. Agrochemical Challenges and Outlook for India, Chemical News, May
2011, p.14.

Fig. 22.1: Pesticide consumption (kg/ha) (Source: Agrochemical Sub-group, ICC;

Indian Chemical Industry. 12th Five Year Plan).

Pesticide consumption is lowest (600 g/ha) in India when compared to the world
average consumption of 3000 g/ha. India is the 4th largest producer of agrochemicals
after USA, Japan and China. There are around 125 technical units, 800 formulation units
in India. Out of ` 1,80,000 crore global market, the share of global market is of ` 1,20,600
crore. Figure 22.3 shows Indian agro-chemical industry: Changing crop-wise market.
Population increasing, area decreasing, food production keeping upward trend: all are
showing in Figure 22.4. Agrochemical market: Segment-wise is shown in Table 22.2.
478 Chemical Process Technology

Fig. 22.2: Product-wise installed capacity and production of major chemicals (Source: Dubey B,
Kumar A. Agrochemical Challenges and Outlook for India, Chemical News, May 2011, p.14).

2001–02 2009–10
Fig. 22.3: Indian agro-chemical industry: Changing crop-wise market (Source: Dubey, B., Kumar,
A. “Agrochemical Challenges and outlook for India”, Chemical News, May 2011, p.14.)

Table 22.2: Agrochemical market: Segment-wise (year 2009)

Segments India (values in Cr) (2009) World (values in Cr) (2009)
Insecticides 3,301 46,575
Herbicides 1,201 95,013
Fungicides 1,198 44,712
Total 6,000 1,86,300
Source: Dubey B, Kumar A. Agrochemical Challenges and Outlook for India, Chemical News,
May 2011, p.14.
Agrochemicals 479

Fig. 22.4: Agrochemicals: A snapshot (Sources: Ministry of Agriculture, GOI; Dubey, B, Kumar, A.
Agrochemical Challenges and Outlook for India, Chemical News, May 2011, p.14.)

22.2 CLASSIFICATION AND CHARACTERISTICS OF SOME MAJOR PESTICIDES

Pesticide is any agent used to kill or control undesired insects, weeds, rodents, fungi,
bacteria, or other organisms. These are derived from various chemicals and they contain
different elements. Hence, in general any pesticide shall be classified based on the pest
they kill and based on the chemical groups they contain. Table 22.3 and Figure 22.5
show the block diagram for classification of pesticides (Mathur, 1998; Austin, 1984; Kohn
and Baker, 1997; Ramnathan and Bhate, 1996; CPCB, 2010). Apart from this, pesticides
can be basically characterized by their physical, chemical and toxicological properties.
Toxicity may be acute or chronic and it depends on type and dose of pesticide taken
and mode of intake. Table 22.4 gives the characteristics of some major pesticides (Irving
Sax,1968; Mall, et al. 2003; CPCB, 1994; Hawley, 1996; Austin, 2010).

Table 22.3: Technical grade pesticide manufacturer in India

Name of pesticides
Insecticides Acephate, BHC, chlorpyriphos, Cypermethrins, DDT, Dichlorvos, Dimethoate,
Deltamethrin, Dichloropropane and dichloropropanes, mixture (DD mixture),
Dicofol, Ethion, Endosulfan, Ethylene dibromide and carbon tetra chloride mixture,
Fenthion, Fenitrothion, Fenvalerate, Lime-sulfur, Lindane, Malathion, Methyl
parathion, Monocrotophos, Nicotine sulfate, Oxydemetonmethol, Phosphamidon,
Pyrethrum extract, Phorate, Phosalone, Quinalphos, Temephos, Triazaphos
Fungicides Aureofungin, Copper oxychloride, Copper sulfate, Carbendazim, Captafol, Ferbam,
Mancozeb, Nickel chloride, Organomercurials (MEMC and PMA), sulfur (Colloida,
wettable and dust), streptocycline, Thiram, Tridemorph, Ziram, Zineb
Rodenticides Barium carbonate, Comafuryl, Sodium cyanide, Warfarin, Zinc phosphide
Weedicides Anilophos, Butachlor, Diuron, 2,4-D, Fluchlorallin, Glyphosate, Isoproturon,
Paraquat dichloride
Plant growth Alpha naphthalene acetic acid, Chloromequat chloride.
regulants
Fumigants Aluminum phosphide, Ethylene bromide, Methyl bromide
Sources: Mathur, 1998; Austin, 1984.
480 Chemical Process Technology

Fig. 22.5: Block diagram of classification of pesticides

Table 22.4: Characteristics of some major pesticides

Pesticide Properties Characteristics
DDT Insecticide, colorless white crystal, Vomiting, numbness, partial paralysis, mild
odorless or slight aromatic odor convulsions
BP = 109ºC, TLV = 1 mg/m3 of air
Parathion Insecticide , yellowish liquid Headache, blurred vision, weakness, nausea,
BP=375ºC cramps, sweating, loss of reflexes, coma
2,4-D Herbicide, white powder, mol wt = 221 Nausea , vomiting, kidney and liver failure
Contd...
Agrochemicals 481

Table 22.4: Characteristics of some major pesticides (Contd...)

Pesticide Properties Characteristics
Carbaryl Insecticide , solid, melting point Symptoms same as parathion but to a lesser
=142ºC, TLV = 5 mg/m3 of air extent
Dieldrin Crystalline, melting point = 150ºC Headache, nausea, vomiting, general
malaise and drowsiness
BHC White crystalline powder, melting Irritation, excitation, hyperirritability, loss
point = 157ºC of equilibrium, depression
Lindane White crystalline powder, melting Acute toxicity may be excitation, hyper­
point = 157ºC, Mol wt = 290.84 irritability, and loss of equilibrium, depres­
TLV = 0.5 mg/m3 of air sion, headache, nausea, irritation of eyes,
nose and throat no chronic toxicity as such.
It emits highly toxic fumes of phosgene
when heated.
Atrazine Crystalline, soluble in water, alcohol Relatively low toxicity but a possible
and chloroform carcino­gen. It emits dangerous fumes when
strongly heated.
Guthion Crystals, slightly water soluble but Highly toxic: Toxicity is almost same as that
soluble in organic solvents, mol wt = of parathion.
317.3, MP = 74ºC
Malathion Yellow liquid, BP = 156–157ºC, slightly Toxic by ingestion and inhalation, absorbed
soluble in water, miscible with most by skin
polar organic solvents, combustible,
TLV = 10 mg/m3 of air
Copper Fungicide, bluish green powder, Toxic by ingestion and inhalation
oxychloride soluble in acids, ammonia. Insoluble
in water
Ziram Fungicide, white and odorous when Moderately toxic, strong irritant to eyes and
pure, sp gr. –1.71, MP = 246ºC, insoluble mucous membrane
in water, soluble in some solvents like
acetone and carbon disulfide
Zinc Rodenticide, dark gray gritty powder, Highly toxic by ingestion, reacts violently
phosphide sp gr. –4.55, MP >246ºC, insoluble in with oxidizing agents. Phosphine is
alcohol, soluble in acids, decomposes produced when reacted with the acids.
in water
Aldrin Insecticide , brown to white crystalline Highly toxic by ingestion and inhalation,
solid, insoluble in water, soluble in carcinogen, use restricted to non-agricultural
most organic solvents, MP = 104– application
105ºC, TLV = 0.25 mg/m3 of air
Dimethoate Insecticide, white solid, Highly toxic, a cholinesterase inhibitor,
MP = 51–52ºC, moderately soluble in restricted use
water, soluble in most organic solvents
except hydrocarbons

22.2.1 Process Technology

Pesticide manufacturing consists of the chemical synthesis of active ingredients for crop
protection, which is very often the synthesis of complex organic chemical compounds,
and subsequent formulation of these active ingredients (usually mixing and grinding
processes) (Technical EIA Guidance Manual 2010).
482 Chemical Process Technology

Major chemical reactions involved in production of technical grade pesticides

are: alkylation, carboxylation, acetylation, condensation, cyclization, dehydration,
halogenations, oxidation, sulfonation, nitration and amination. Main physical “unit
operations” include liquid/liquid extraction, liquid/liquid separation, liquid/solid
separation, gas/solid separation, distillation, crystallization, gas absorption, drying,
grinding and mixing. The pesticide industry in India falls in to three distinct categories
• Manufacture of pesticide and formulation
• Exclusively formulation
• Importers, distributors and dealers

22.2.2 Dichloro Diphenyl Trichloroethane

Dichloro diphenyl trichloethane (DDT), one of the commonly used organochlorine
pesticides, was synthesized first in 1874 and played important role in elimination of
malaria and used for agricultural purpose. However, due its persistent nature and
carcinogenic nature DDT has been banned in most of the country. DDT dissociates in
presence of moisture into DDE and DDD which are highly persistent.
DDT is mixture of two isomers p, p (1–trichloro-2,2-bis (p-chlorophenyl ethane) and
o,p (1-trichloro-2-0, chlorophenyl ethane) 2-bis (p-chlorophenyl ethane). The former is
the main constituent process steps involved in the manufacture of DDT are:
• Manufacture of mono-chlorobenzene through chlorination of benzene using iron
catalyst
• Manufacture of chloral through chlorination of ethyl alcohol
• Manufacture of DDT through condensation reaction between MCB and chloral using
oleum as condensing agent
• Recovery of by products, dil. HCl, dichlorobenzene and sulfuric acid.

22.2.3 Biopesticides
Due to growing environmental concerns and consumer inclination toward chemical-
free crops especially food crops there has been increasing use of bio-pesticides. Three
major classes of biopesticides are microbial pesticides, biochemical pesticides and plant
incorporated pesticides (http;//[Link]/wiki/Biopesticide). Biopesticides
are getting importance as they are less toxic than conventional pesticides which have
become serious threat to environment due to its increasing use. Biopesticides affect
only the target pest and closely related organisms.
Several factors such as new products, end user acceptance and acceptance of
substitutes to conventional pesticides and declining market for harmful organophosphate
insecticides, have fueled the market growth. Delivering a better alternative to manage
harmful insects, weeds and fungal plant pathogens, biopesticides are poised to witness
robust gains in coming years. The United States represents the largest region for bio-
pesticides worldwide. Europe represents the fastest growing regional market for bio-
pesticides.
With the growing acceptance of biopesticides as an efficient crop protection
alternative with ecofriendly footprint, several agricultural chemicals are leaning toward
biopesticides (Global Industry Analysts, Inc.).
Some of the important bio-pesticides are:
• Trichogramma
• Fungi (Trichoderma and Gliocladium)
Agrochemicals 483

• Baculoviruses
• Bacillus thuringiensis
• Neem.
As the organic food business is growing, demand for nontoxic pesticide for crop
protection is increasing. Use of biopesticides is being encouraged by Government of
India as part of integrated pest management program.

22.3 NEW GENERATION INSECTICIDES

Looking to environmental hazards of chemicals used as pesticides in the past, new
generation of pesticides with reduced risks to the environment and human health has
developed and are being used. These pesticides tend to be rather surgical in method
of their redicing number of insects. Some of the new generation pesticides are neo-
niconoids, spinosyns and spimosoids, indoxcarb, fiproles or phenylpyrazoles, pyrazoles,
pyridazinones, quinazolines. Seven classes of insecticides which have appearance in
recent years are methyxyacrylates, naphthoquinones, nereistoxin, nereistoxin analogs,
pyridine azomethine, pyrmidinamines, tetronic acids, clofentezine (Dureja, 2009).

22.3.1 Insect Growth Regulators

Insect growth regulators (IGRS) are compounds which alter the normal growth of
process of insects and therefore can be used to control insect populations. Some of the
IGRS are juvenile hormone-based insecticides, tebufenozide, fenoxycarb.

BIBLIOGRAPHY
1. Agrochemical Sub-group, ICC; Indian Chemical Industry. 12th Five Year Plan.
2. Annual Report 2011–2012. Department of Chemical and Fertilizers, Govt. of India.
3. Austin Georhe T. Shreve’s Chemical Process Industries. Agrichemicals Industries. 5th Edition,
McGraw Hill Publication, 1985 p.462.
4. CPCB,1994. “Wastewater management in Pesticide Industry”, Central Pollution Control board,
MOEF, New Delhi.
5. Dubey B, Kumar A. “Agrochemical challenges and outlook for India”. Chemical News, May
2011, p.14.
6. Dureja P. “The new generation Eco-friendly potent plant protection agents”. Chemical Industry
Digest, April, 2009, p.62.
7. Gessener GH. “The condensed chemical dictionary”, Galgotia Book Source Pvt. Ltd. Tenth edition
1996.
8. http;//[Link]/wiki/Biopesticide
9. Irving N Sax. “Dangerous properties of Industrial Materials, 3rd edition, Van Nostrand Einhold,
1968.
10. Kohn GK, Baker DR. “Agrochemical industry” p.1141 Riegel’s Handbook of Industrial Chemistry
Ninth edition Edited by James A. Kent CBS Publishers and Distributors, Fifth edition 1997.
11. Mall ID, Krisham Raju, Navinkumar. “Pesticide industry: Impact on Environment”. Chemical
Engineering World, Vol. 38, No.1 Jan 2003 p.116.
12. Mathur SC. “Pesticides Industry in India”. Chemical Weekly, May, 1998.
13. Ramnathan PS, Bhate PS. “Pesticides–Part II: Insecticides”. Encology volume 1, No. 2, July
1986,p.19.
14. Technical EIA Guidance Manual, Project Sponsored by the Ministry of Environment and Forests
2010.
23
Dyestuff Industry

23.1 INTRODUCTION
The dyestuff industry plays important role in the overall growth of chemical industry.
The preparation and usage of dyestuff is one the oldest forms of human activities. The
usage of natural dyestuff dates back to the bronze age. Dye flax fibers have been found
in the Republic of Georgia dated back in a prehistoric cave 36,000 BP (Balter and Make,
2009; Kavavadze, et al. 2009). Archeological evidence shows that particularly in India and
Phoenicia, dyeing have had been extensively carry out for over 5000 years. The dyes were
obtains from animal, vegetable or mineral origin with no or little processing. First synthetic
organic dye, mauveine, was discovered by William Henry Perkin in 1856 (Wikipedia).
There is also mention of dye in the Bible and other works of classical antiquity. It was
in 2600 BC when earliest written records of the use of dyestuffs were found in China.
Synthetic dyestuffs now available in several hues are amongst the oldest chemicals
produced by man (Lalbhai, 2007). Textile, carpet and garment industry is one of the largest
and most prominent sectors as major portion of the dyes are used in textile industry,
growth of the textile industry has a direct impact on the growth of dyes stuff industry.
Textile dyestuff had a worldwide market of around US$ 5.7 billion. Largest categories are
reactive and disperse dyes that accounts for about 44% of total value. Asia pacific represents
largest share and accounts for about 40% global share. At a production of 130,000 MT per
annum, Indian dyestuff industry contribute to just 7% of the world’s global production.
Installed and production capacity of dyes and dyestuffs are given in Table 23.1.
Dyes are the colored, ionizing and aromatic organic compounds which has affinity
to the substrate to which it is being applied. The dye is generally applied in an aqueous
solution which may also require a mordant for improving the fastness of the material
on which it is applied. Colors are an integral part of human perception and life. Much
before the invention of synthetic dyestuffs, natural and vegetable colors were in use in
India for centuries.. Perkins development of the first synthetic dye in 1856 led to the
birth of European dyestuffs industry and use of synthetics dyes widely extended to all
textiles substrates. The well-development textile industry in India soon started use of
synthetic dyes and depended on imported organic dyestuffs till forties. The start up of
Arlabs Ltd., in 1940, followed by other dyestuffs companies in fifties and sixties led to
the establishment of the indigenous industry. In the development phase that followed
subsequently, India slowly emerged as the supplier of dyestuffs.
Global dyestuff industry is a multi billion industry and comprises products including
dyes, pigment and intermediates ([Link] [Link]/global dyestuff-industry.
htmal) Samant, PS, Bhangae, M. Green technology in dyestuff industry. Chemical
Industry Digest, August 2014).
484
Dyestuff Industry 485

Table 23.1: Installed capacity and production of dyes and dyestuffs (000’ MT)
Major groups/products Installed capacity (2009–10) Production (2010–11)
Azo dyes 8.70 2.80
Disperse dyes 6.50 0.53
Fast color bases 0.60 0.09
Ingrain dyes 0.50 0.70
Optical whitening agents 3.40 3.04
Organic pigment colors 11.00 21.83
Pigment emulsions 6.30 5.63
Reactive dyes 7.90 2.40
Sulfur dyes (sulfur black) 3.30 8.60
Vat dyes 3.00 1.60
Solubilized vat dyes 0.10 0.04
Naphthols 3.60 0.07
Total 54.90 47.33
Sources: Annual Report 2011–2012, Department of Chemical and Fertilizers, Government of India.

23.2 DEMAND AND SUPPLY

The overall production capacity of dyestuffs is 200,000 tons per annum. With the ever
increasing standards of quality and reliability, Indian dyestuffs industry meets more
than 95% of the domestic requirement, out of which textile industry consumes nearly
60% and the remaining is shared by paper, leather and other consumer industries. As
far as pigments are concerned, the market size is 115,000 tons. Production of pigments
and major dyes is shown in Figure 23.1. The main consumer industries are textiles,
leather, paper, paints and coatings, printing inks, foods printing inks, plastics, rubber,
etc., market demand for dyes and intermediates is expected to grow at a compound
annual growth rate of 3.6% from 2013 to 2018 and reach 11 million tons by 2018.
Pigment production (total): 115,000 tons Major dyes production (total): 200,000 tons

Fig. 23.1: Production of pigments and major dyes in India (thousand tons). Source: CAMI
486 Chemical Process Technology

23.3 CLASSIFICATION OF DYES

Dyes can be classified in various ways based on origin, dyeing process, chromophores
and application.
Classification of dyes based on common application has been given in Table 23.2.
Classification of dyes based on chromophores is given in Table 23.3 (Austin,1984).
Table 23.4 shows various dyes intermediate and their structure, methods of preparation
and their uses. Process application based dyes is given in Table 23.5.

Table 23.2: Classification of dyes

Based on origin of • Natural or synthetic dyes
dyes • Organic or inorganic
Based on the dyeing Acid dyes, basic dyes, direct or substantive dyeing, vat dyes, reactive dyes,
process disperse dyes, azo dye, sulfur dyes, fluorescent brightening agent
Based on • Acridined dyes
chromophore • Anthraquinone dyes
• Aryl methane dyes
• Azo dyes
• Cyanine dyes
• Diazonium dyes
• Nitroso dyes
• Phthalocyanine dyes
• Quinoneiimine dyes (azine dyes, indamins, indophenols, oxazone,
thiazin)
• Thiazole dyes, xanthate dyes
Based on application Food, cosmetics and drug dyes, Laser dyes, leather dyes, solvent dyes,
contrast dye, carbine dyes.
Based on color index Color index recognizes 26 types of dyes by chemical classification
Source: Austin, 1985; CPCB, 2004.

Table 23.3: Chromphore: An important class of dye

Dye Chromophore
Azo dyes –N+N–

Nitro – NO2
Nitroso – NO (or = N – OH

Ethylene — —
—C=C —

Carbonyl group —
—C=O
—
Carbon nitrogen group — C = NH

– CH = N –
Carbon sulfur groups —
—C=S
— —
—C—S—S—C— —

Source: Austin, 1985.

Table 23.4: Various dyes intermediate and their structure, methods of preparation and their uses
Product Derivatives Structure Method of preparation Purpose
Benzene 4-aminobenzene Sulfanilic acid is a gray crystalline It is used to make dyes and
(sulfonic acid) solid produced from sulfonation of sulfa drugs.
aniline.

N-N-Dimethyl 1. Initially, it was prepared by Derivative of aniline DMA is a

aniline (DMA) heating aniline and iodomethane. key precursor to com­mercially
2. Industrially, it was pro­duced by important tri­aryl­methane dyes
alkylation of aniline with methanol such as malachite green and
in the presence of an acid catalyst. crystal violet
Toluene Orthochlorobenzoic 1. It may be synthesized by the As an intermediate in manu­
acid oxi­da­tion of 2-chlorotoluene with facture of drugs especially
potassium permanganate. mefenamic acid and also in
2. It can also be synthesized by diazo­ the manufacture of dyes and
tation which fol­lows Sandmeyer pigments.
reaction.
P-Nitro-benzoic acid 1. It is prepared by oxidation of As a dye intermediate, dying
4-nitro­to­luene using oxy­gen or nitric carrier, disinfectant additive,
acid as an oxi­dant. penetrating agent and pesticides
2. Alternatively it can also be pre­ a n d m a n u ­fa c t u r i n g o t h e r
pared by nitration of polystyrene compounds
fallowed by oxidation of alkyl substi­
tuent.

Dyestuff Industry
5-amino-2- p-toluene sulfonic acid, undergo It is an important inter­mediate
chlorotoluene- nitrification followed by reduction of manufac­turing red organic
4-sulfonic acid so after that filtrate hydro­chloride pigments (CI pigment red 48:2)
(C-acid) acid was crystallized into 2-amino- and some dyestuffs.
5-chloro-p-toluene sulfonic acid

487
Contd...
488
Table 23.4: Various dyes intermediate and their structure, methods of preparation and their uses (Contd...)
Product Derivatives Structure Method of preparation Purpose
α-naphthol 1. α- naphthol is manufac­tured by

Chemical Process Technology

Naphthalene Directly in making several
(1-naphthol) heating 1-nathal­ene sulfonic acid dyes and are converted into
or 1-hydroxyl- with caustic alkali or numerous dye inter­mediates,
naphthalene 2. Heating 1-naphthylamine with as well as into tanning agents,
water under pressure. antioxidants, and antiseptics
β-naphthol β-naphthol is manufactured by
2-hydroxy fusing 2-naphthalene sulfonic acid
naphthalene with caustic soda.
1-amino-8- 1-naphthylamine -4,6,8-3 acid with As azo dyes, reactive dyes and
naphthol-4, sodium carbonate solution and in organic pigments intermediates,
6-disulfonic acid three naphthylamine sodium and at mainly used in the production
(K-acid) 178–184ºC using sodium hydroxide of cationic dyes, reactive red
solution for alkali fusion K-2G other

1-amino-8- An important dye intermediate is H acid is used in the manufacture

naphthol-3, produced from naphthalene by a of a large number of azo dyes
6-disulfonic acid combination of the unit processes and pigments.
(H-acid) of sulfonation, nitration, reduction,
and hydrolysis.
1-naphthyl amine-8 Naphthylamine is an aromatic It is used directly in making
sulfonic acid (peri amine which can be obtained from several dyes and converted into
acid) nitro­n aphthalene (with iron and numerous dye intermediates, as
hydrochloric acid) or naphthol well as into tanning agents.
with sodium acetate, ammonium
chloride.
1-naphthyl amine-
6-sulfonic acid
(Cleve’s acid)

Contd...
Table 23.4: Various dyes intermediate and their structure, methods of preparation and their uses (Contd...)
Product Derivatives Structure Method of preparation Purpose
1-naphthyl amine-
7-sulfonic acid (1,
7-Cleve’s acid)

5-amino-2- p-toluene sulfonic acid, undergo It is an important intermediate

chlorotoluene- nitrification followed by reduction of manufacturing red organic
4-sulfonic acid so after that filtrate hydrochloride pigments (CI pigment red 48:2)
(C-acid) acid was crystallized into 2-amino- and some dyestuffs.
5-chloro-p-toluene sulfonic acid

2-naphthol-3,6-two It is produced from naphthalene by R-salt is an important dye inter­

sodium salt (R acid) a combination of the unit processes mediate used in the manufacture
of sulfonation, nitration, reduction, of a large number of azo dyes
and hydrolysis. and pigments.
Anthraquinone 1,4-dihydroxy 1. It is prepared by reaction of phthalic an intermediate for the synthesis
anthraquinone anhydride and 4-cholorophenol of indanthrene- and alizarin-
(quinizarin or fallowed by hydrolysis of the chlo­ derived dyes
solvent orange 86) ride. 2. It can also be prepared less
efficiently from phthalic anhydride
and hydroquinone.
1,4-diamino 1,4-Diaminoanthraquinone is An anthraquinone dye used
anthraquinone reac­ted with sodium dithionite to with disperse red 9 in colored

Dyestuff Industry
produce 1,4-diamino-2,3-dihydro­ smoke to introduce a violet
anthraquinone. color. It is also used in dyes and
marine flares.

Sources: [Link]
[Link]
[Link]

489
[Link]
490 Chemical Process Technology

Table 23.5 Process application based dyes

Acid dyes Acid dyes are water-soluble anionic dyes and insoluble in
acid bath. acid dyes are used for dying of wool, silk, nylon,
acrylic fiber, paper, leather
Basic dyes Basic dyes are water-soluble cationic dyes. Basic dyes are
mostly amino and substituted amino compounds. Basic
dyes are used for dyeing, acrylic fiber, cotton, wool, paper
Direct dyes Direct dyes are used in a neutral or slightly alkaline dye
bath without addition of mordant. Direct dyes are used for
dyeing cotton, wool, silk, paper, nylon. They are generally
azo dyes.
Disperse dyes Disperse dyes are used for dyeing for dyeing synthetic
fiber like cellulose acetate, polyesters, nylon and acrylic
fibers. These dues are applied as finely divided materials
in presence of dispersing agent.
Vat dyes Vat dyes have highly complex structures and are insoluble
in water and are used after reduction in alkaline liquor
which produces water soluble alkali salt.
Reactive dyes Reactive dyes react to form covalent bond which directly
react with the fiber and provide excellent wash resistance,
e.g. Procin MX, Cibacron F and Drimarene K
Mordant dyes Some dyes combine with metallic salt (mordant) which
improve the fastness of dye, e.g. chrome dyes. Potassium
dichromate is used as mordrant.
Azoic dyeing In azoic dyeing, colors are made on the fiber by coupling
diazotized materials while on contact with fiber. Final
color is controlled by the choice of diazoic and coupling
components.
Sulfur dyes Sulfur black dye is most commonly used. Sulfur dyes color
is produced by reacting sulfide and polysulfides with
chlorinated aromatics. It is used for cotton cloth.
Food dyes Food dyes can be direct, mordant and vat dyes and are
manufactured with high purity and precaution to meet
the required standards.

23.3.1 Gamma Acid

Gamma acid belongs to the class of hydroxyl naphthalene
monosulfonic acid is a key intermediate used as diazo and
coupling component for the manufacture of commercial
dyes belonging to the class of direct, acid, acid-modrant and
reactive dyes.

Manufacturing Process
G-salt is subjected to Bucherer reaction with liquor ammonia in presence of sodium
bisulfite in aqueous solution under pressure in an autoclave to obtain the amido G-salt.
Which then subjected to alkali fusion with excesses of caustic soda flakes then neutralized
with 40% sulfuric acid to isolate the gamma acid.
Dyestuff Industry 491

Chemical Reactions

23.3.2 Tobias Acid

Tobias acid is an important dye intermediate belonging to the class of
amino naphthalene monosulfonic acid. It is used in the manufacture
of a number of reactive, direct, acid and acid-mordant dyes.

Manufacturing Process
Oxy-tobias acid undergoes amidation by Bucherer reaction in the presence of ammonia,
ammonium sulfite and ammonium sulfate, After amidation to bias acid formed in
dissolved state as its ammonium salt, then subjected to acidification with sulfuric acid
for isolate the Tobias acid.

Chemical Reactions
492 Chemical Process Technology

23.3.3 Metanillic Acid (6-Chlorometanillic Acid)

6-Chlorometanillic acid is a key diazo-component used as an intermediate
in the manufacture of a variety of direct and acid dyes which are used
to dye cotton and wool.
Manufacturing Process
Orthonitrochlorobenzene (ONCB) is sulfonated with oleum to afford ONCB parasulfonic
acid (ONCB PSA), then reduced with iron and concentrated hydrocholoric acid at
95–100ºC in 5–6 h. The filtrate is acidified to afford the 6-chlorometanillic acid which
is centrifuged and dried.
Chemical Reactions

23.3.4 β-Naphthol
β-Naphthol is an important dye intermediate used as a coupling
component for manufacture of widely used azo dyes.
Manufacturing Process
Naphthalene is sulfonated with concentrated sulfuric acid gives naphthalene -1-sulfonic
acid. The diluted mass is neutralized with aqueous solution of sodium sulfite containing
sodium sulfate
Chemical Reaction
Dyestuff Industry 493

23.3.5 Anthraquinone-1-Sulfonic Acid (Sodium Salt)

9, 10-Anthraquinone and all its derivatives are important building block for a variety
of dyestuffs, in particular for disperse, solvent and acid dyes.

Manufacturing Process
Phthalate anhydride is treated with benzene in excess of the AlCl3 as a catalyst gives
ortho-benzoyl benzoic acid (BOB) in form of Al complex. BOB future subjected to
cyclization and sulfonation using in the presence of HgO as a catalyst to obtain
anthraquinone-1-sulfonic acid.

Anthraquinone-1-sulfonic acid (Sodium salt)

Chemical Reactions

Anthraquinone-1-sulfonic acid (Sodium salt)

494 Chemical Process Technology

23.3.6 Anthraquinone-1-Sulfonic Acid (Ammonium Salt)

Anthraquinone-1-sulfonic acid (Ammonium salt)

Manufacturing Process
Mercury is heated into 20% oleum at 80ºC for 3 hrs then anthraquinone (AQ) is heated
at 130ºC for 3 hrs to complete sulfonation of AQ after filtration the filtrate neutralize
with ammonia and after cooling 30ºC precipitate out anthraquinone-1-sulfonic acid
ammonium salt.

Chemical Reactions
H2 + H2SO4 HgSO4 + H2

23.3.7 Resorcinol
Resorcinol is a key dyestuff intermediate widely used as a coupling
component for a variety of azo dyes belonging to various classes such as
direct, acid, reactive and disperse dyes. It is also an important monomer
for the production of polymers especially polyesters. Derivatives of
resorcinol have also found use as sun screen agents and UV stabilizers.

Manufacturing Process
Benzene is sulfonated using liquid sulfur trioxide in presence of sulfuric acid and sodium
sulfate. The benzene disulfonic acid (BDSA) is converted to its disodium salt using soda
ash, which then treated sulfuric acid then resorcinol is extracted with butyl acetate.
Dyestuff Industry 495

Chemical Reaction

23.3.8 Dark Blue

Dark blue (BO) is a vat dye containing two or more keto group which has great affinity
for cellulosic fiber.

23.3.9 Violanthrone
Manufacturing Process
Naphthalene and sodium acetate with molten mixture of NaOH and KOH are added
in 1.25 hours at 185ºC then crude benzanthrone heated over 4 hours at 235ºC. The dye
which separates out is filtered off through filter press and wash well with hot water.

Chemical Reaction
496 Chemical Process Technology

BIBLIOGRAPHY
1. Annual Report 2011–2012, Department of Chemical and Fertilizers, Government of India.
2. Austin GT. “Cyclic Intermediates and dyes”. Shreve’s Chemical Process Industries. Fifth edition
Edited by George T. Austin, McGraw Hill International editions 1984,p.772.
3. Balter M. Clothes Make the (Hu) Man. Science, 325(5946):1329 and Kavavadze E, Bar-Yosef O,
Belfer-Cohen A, Boaretto E, Jakeli N, Mataskveich Z, Meshveliani T. 30000-year-old wild flax
fibres. Science 2009;325(5946):1359.
4. CPCB. “Identification of hazardous waste streams, their characterization and waste reduction
options in Dyes and dye intermediate sector”, Central Pollution Control Board MOEF, New
Delhi, August, 2004.
5. [Link]
6. [Link]
7. [Link]
8. [Link]
9. [Link]
10. James AK. Reigel’s Handbook of Industrial Chemistry. 9th Edition, CBS Publishers, 1997.
11. Kavavadze, et al. 2009.
12. Lalbhai SS. “Indian dyestuffs Industry opportunities and challenges in a Global Environment”.
Chemical Industry Digest, Annual-January 2007, p.14.
13. Wikipedia, the free encyclopedia [Link]
24
Paint, Varnish, and Lacquers

24.1 INTRODUCTION
Paint has been used for about 30,000 years and ancient painting haven found in the
walls of caves in France (Van De Mark, et al. 2005) (Van De Mark MR, Sandefur KD,
Durham KA. “Paints” in Kirk-Othmer Encyclopedia of Chemical Technology, Fifth
edition, Volume 18, Wiley-Interscience 2020). Ancient paintings also show the use of
paint. Paint and coatings provide two primary functions: decorative and protection,
which are of considerable economic importance. About 45% of the coatings produced
worldwide are used to decorate and protect new construction as well as maintain existing
structures including residential homes and apartments, public buildings, plants and
factories. Another 40% are used to decorate and or protect industrial products (http://
[Link]/products/chemical/planning/ceh/[Link]).
Decorative paints segment consist of enamels, distempers, emulsion and cement paint.
Industrial paints are automotive paints, general industrial paints, high performance
coatings, powder coatings and marine paints. Paints and coating sector may be divided
into two major sectors: industrial and decorative. Paint and coating industry has
grown steadily and production and consumption has been increasing during last few
decades. Increase in demand of industrial paints and coating show the economic growth
rate of a country. Fast growth in automobile sectors and people choice for different
shade in decorative sector has changed the requirement of paints of different shade
and quality. Large scale corrosion with varying raw material and products has also
increase the requirement of paints and coating. The boom in automotive production and
infrastructural development has also opened high potential for paint industry. Some
of the driving forces for fast growth of paint industries are: fast industrialization and
urbanization resulting in vast infrastructural development, fast growth of automotive
sector, and availability of raw materials.
Demand of paints and coating has been increased both in the domestic and industrial
sectors due to fast urbanization and industrialization. Environmental and corrosion
control has been also the driving force for development of paint and coating industry
during recent years. Demand for paints come from two broad areas: decorative and
industrial. Decorative paints accounts for major share of paint industry. Industrial paints
are used in infrastructure as well as in large scale manufacture of consumable goods,
automobiles, furniture machinery, and equipments.
A welcome development in the paint industry is use of environmentally friendly
powder technology, free from solvents and unaffected by rising price of oil or emission
of VOC (Patwardhan, 2002).
497
498 Chemical Process Technology

24.2 PROFILE OF PAINT INDUSTRY

During the past decade the global paint and coating demands grew steadily with an
average rate of 5.4% annually. Sales amount reached to 41.75 million tons with sale
value of 127.3 billion till 2013. ([Link]
ten%20Paints%20Companies%20(2013).
Demand of paints and coatings in Asia region has been faster than another region.
Asia accounts nearly for 50% of global consumption. World’s top 10 paint brands are
given in Table 24.1.

Table 24.1: World’s top 10 paint brands in 2013

Sl. no. Name of company
1 AkzoNobel (NL): [Link] $15.053 billion
2 PPG Industries (US): [Link] $14.924 billion
3 Sherwin-Williams (US): [Link] $9.85 billion
4 DuPont (US): [Link] $5.76 billion
5 Base (DE): [Link] $5.187 billion
6 Valspar (US): [Link] $4.165 billion
7 Diamond Paint (US): [Link] $3.968 billion
8 Sacal (UK): [Link] $3.881 billion
9 Nippon Paint $3.026 billion
10 RPM Inc. $3.022 billion
Source: [Link]

The Indian paint industry started in 1902 with the establishment of Shalimar Paints
in Kolkata. Since then the industry has grown and its application has increased in both
industrial and domestic sector for decorative purposed. Now the Indian paint industry
is globalized and all the leading companies are in India (“The paint industry”, Chemical
Industry Digest Annual–January 2002, p.107). The growth of Indian paint market is
driven by rapid industrialization, emergence of middle class, increase in disposable
incomes, growing infrastructures, increase in tendency to spend extravagantly and
growing youmg population leading to lavish styles ([Link]
com/in/pressreleases/india-paint-industry-outlook-2018-1054324). The Indian paint
industry is expected to grow 12–13% annually over the next five years from 28 billion in
FY2013 to around Rs 500 billion by Fy 2018 ([Link]
it/sector-info/paint/Paints-sector-analysis-Report…). Although oil bound paint was
used extensively in early stages; however, shift from oil-based paints to water-based
paints. In recent years, high growth of interior and exterior paints has been seen due
to increasing awareness of people regarding benefits of a paint for long life and good
look. Major Indian paint industries are given in Table 24.2.

Table 24.2: Major Indian Paint Industry

• Asian Paints • Berger Paints • Garware Paints • Goa Paints
• Goodlass Nerolac Paints • Jenson and Nicholson • Addison Paints • Metro Paint Industries
• Snowcem India Ltd. • ICI-India • Mercury Paints • Hoyle’s Paints
Paint, Varnish, and Lacquers 499

24.3 RAW MATERIAL FOR PAINT INDUSTRY

Some of the major raw materials for paint industry are pigments, resins, solvent, titanium
oxide, phthalic anhydride, pentaerythritol additive, etc. Although raw material for
decorative, architectural and and general purpose industrial paints are available in India;
however, automotive paints need specialty pigments and other coloring ingredients
that exhibit long-term weathering properties meeting the stringent Florida exposure
test (Bhharuka, 2003).
Resins are polymer compounds which may be natural or synthetic. Some of the natural
resins are copals or resins derived from pine tree and rosin. Some of the important
synthetic resin used in paint industry are: alkyl resin phenol and, urea formaldehyde
resins, acrylic resins, amino resins, siliconized alkyd resin, polyurethane fluropolymers,
cellosic derivatives, etc.
Some of the important pigments are silica, bayrites, lithophone, white lead, zinc
oxide, antimony oxide, titanium dioxide (anatase), and titanium oxide (rutile).
The pigments may be inorganic pigments are organic pigments. Some of the important
organic pigments are phthalocyanine blue, hansa yellow, phthanalcyanide green,
toluene red, azo pigments of various shades (Marphatia R. “Advances in surface coating
industry—pigments”, Chemical Industry News, May 2010).

24.4 GLOSSARY OF TERMS

Glossary of terms in paint is given in Table 24.3.

Table 24.3: Glossary of terms in paint industry

Paint Paints are coating generally opaque containing resin, a solvent, additives, pigment
and sometimes a diluents. Paints are finally divided pigments dispersed in liquid
composed of resin, binder and a volatile matter. The ingredients of most formulations
in conventional paints are: resin, pigment, solvent or thinners and additives.
Oil paint Oil paints are used for painting all surfaces exposed to the weather and varying
temperature changes and can be applied to metal or wood surfaced. It may be exterior
or interior oil paint. Oil paint contains drying oil, oil varnish or oil modified resin.
Water paint Water paint consists of whiting, glue and coloring. Calcimine is commonly used
for interior walls and ceilings. Water paints used widely because it is cheaper than
the oil paint.
Varnish Varnishes are an un-pigmented colloidal dispersion or solution of synthetic or natural
resins in oils or thinners. Varnishes are used as a protective and decorative coatings.
Pigment Pigments are the coloring material which provides different shades to the paint
or distemper. The pigments give opacity color durability, chemical resistance and
protection. Pigments may be inorganic or organic. Some of the commonly used
pigments are titanium dioxide, barium meta-carbonate, barium sulfate, carbon black,
chromium oxide, iron oxide, lead carbonate, strontium chromate, tuscan red, zinc
oxide, zinc phosphate and zinc sulfide.
Binders Binder is the actual film forming component and consists of resins and is the solid
ingredient which hold the pigment in suspension. It holds the paint in dry film and
cause it adheres to the surface and influences various important properties like
glossy-potential, exterior durability, flexibility and toughness.
Contd...
500 Chemical Process Technology

Table 24.3: Glossary of terms in paint industry (Contd...)

Enamel Enamel is varnish containing pigments, generally glossy and is used for interior
exterior applications. Enamel paints are oil based and glossy.
Extenders Extenders are used in paint to increase surface coverage, reduce cost, achieve
durability. These are used to modify the gloss level of paints.
Paint thinner Paint thinners used as thinner and are mineral sprit.
Gloss paint Gloss is the lusture shininess of paints and coatings. Gloss paints are oil based and
include resin to give them a hard wearing quality. Various types of gloss paints are
liquid glass, satin wood gloss, eggshell, polyurethane gloss, silthane, etc.
Galvanizing A processing of applying a thin coating of zinc to iron or steel for preventing rusting.
Lackquer Lackquer is very fast drying clear coating finish usually made from nitrocellulose
and is highly inflammable.
Primer Primer are first coat of paint which are used to provide adequate adhesion to new
surfaces. Primers may be oil- or water-based. Various types of primers are Durolite
wood primer, Prilomite cement primer, etc.
Binder or Binders are the solid ingredients in a coating consisting of resins, such as epoxy,
vehicle acrylic, vinyl acrylics, polyurethane, polyesters melamine vinyl-acrylic which hold
the pigment particles in suspension and attach them to the surface. It is the actual
film forming component of paint and imparts adhesion, binds the pigments and
influences gloss, exterior durability, flexibility and toughness.
Fire retar­dant Fire retardant paint contains additive to provide fire resistance.
paint
Bitumen Bitumen is used for waterproof coating. Bitumen paints are made by melting bitumen
paint and thinning of the melted bitumen to achieve the required consistency.
Distempers Distempers are water-based paint
Additives Paint also contains some additives which improve the surface tension, flow properties
appearance, pigment stability, UV stabilizers, etc.

24.5 GENERAL MANUFACTURING PROCESS OF PAINTS AND RESINS

Steps involved in formulation and production of various paints are preassembly and
premix, pigment grinding and milling product finishing/blending, and product filling/
packaging.
In general, the process of paint manufacture involves weighing of pigments grinding
and milling, dispersion of the pigments in an appropriate resin vehicles, mixing of the
milled pigments in mixer with thinners, drying agents . Thinners and drying agents are
used to adjust consistency, viscosity, color and drying time. Screening and filtration are
used to remove the un-dispersed pigments, centrifuging, and finally packing. Various
equipments used for dispersing are high speed dispersers, ball or pebble mill, roller
mill, roller-stator mill, etc.

24.5.1 Synthetic resins

Some of the important synthetic resins used in paint industry are epoxy resins, alkyd
resins, acrylic resins urethane resins, urea, melamine formaldehyde resins, polyurethane
resins, cellulose derivatives like nitro-cellulose, cellulose acetate, polyvinyl acetate
resins, vinyl resins, styrene resins, silicon resins, etc.
Paint, Varnish, and Lacquers 501

24.5.2 Alkyd Resin and Modified Alkyd Resin

Alkyd resins are classified as long oil, medium oil, short oil based on the basis of amount
of unsaturated oil used. Modified alkyd resins are basically a graft modification on the
alkyd backbone structure with enhanced coating properties. Some of the important
modified alkyd resins are silicon, urethane, styrene epoxy and acrylic modified alkyds
(Van De Mark, et al. 2005).
Process of Alkyd Resin Manufacture
Alkyd resins are made by condensation and polymerization of oil with a branching
polyol. The oligmerized material is usually dissolved in mineral sprits or an aromatic
solvent. Various oil used are soybean, linseed, tung, canola, sunflower, etc.
Raw material for Alkyd Resins
1. Oils: They are triglyceride of mixed fatty acids.
Chemical structure of oil:

  Main oil used in paint industry are dehydrated castor oil (DCO), soybean oil,
linseed oil, coconut oil, cotton seed oil, etc.
2. Polyols: Main polyols are neopentyl glycol, glycerin, trimethyl propanol,
pentaenthrytol, sorbitol, etc.
3. Polybasic acids: Functionality more than one suitable for polymerization:
• Phthalic anhydride
• Hexa hydrophthalic anhydride
Reaction Mechanism of Alkyd Resin
Alkyd resin reaction takes place in two stages: Monoglyceride formation and
esterification reaction.
1. Monoglyceride formation: Triglyceride of mixed fatty acid reacts with polyols at
high temperature in presence of catalyst and converted in a monoglyceride:
Oil + polyols Monoglyceride
2. Esterification reaction: Polymerization takes place with water removal by the reaction
between monoglyceride and acid group.
Acrylic Resin Manufacturing
Acrylic resins are either thermoplastic or thermosetting.
Thermoplastic polymer: Thermoplastic types are long chain polymers with high
molecular weight and they form film without any external chemical reaction.
Thermoplastic films are harden by solvent evaporation.
502 Chemical Process Technology

Thermosetting polymer: The thermosetting type of acrylic is a shorter chain polymer

containing reactive groups, which can be cured by the application of heat in usually
by reaction with another chemical to form a cross-linked film.
Raw Materials
Principal raw materials are catalysts, monomers, and solvents.
• Catalysts:
1. AIBN,
2. Benzoyal peroxide (C6H5COO)3
• Monomers: Monomers used in acrylic resins: resins are methyl styrene, acrylonitrile,
methyl metha acrylate, butyl methacrylate, methyl acrylate, ethyl acrylate
• Amino resins: Amino resins used in paint manufacture are made by reaction of
Phenol— Urea and Malamine—formaldehyde and butanol.
Reaction mechanism of amino resins: Reaction takes place in two stages:
• Methyl derivative formation: In first stage of run one mole of melamine react with max
6 mole of formaldehyde and form hexamethylol derivative of melamine (Addition
reaction).
• Methylol group reacts with hydroxyl group of butanol in slightly acidic atmosphere.
Water is generated and polymerization takes place.
• Cathodic electrodeposition (CED) resins: CED resins are basically epoxy resin
modified with amines, urethane and polyamides. These resins are water soluble.

24.6 DECORATIVE LIQUID PAINTS

Various ingredients of decorative liquid paints are pigment, bider, solvent, and Driers
additives. Various grades of products are enamels, primers, varnishes, stainers, and
intermediates. Both organic and inorganic pigments are used. Pigments provide color
and reinforce the binders. Some of the additives used are dispersing agent, wetting
agent, anti-floating agent, anti-settling agent and anti-skinning agent.
Coatings
Two major types of coatings are used: Latex type and alkyd resin based. Latex type
coatingsacrylic, vinyls and styrene based resins, copolymers and are water borne. Alkyd
and modified alkyd based resin, which are oil borne.
Coating Technology
Various types of coating technology have been used in the past. However, there
has been considerable development in the coating technology to provide improved
coating performance at lower cost and with cleaner environment. Some of the
conventional coating technologies are anode coating, metal cladding, electroplating
chemical conversion coating. Some of the new coating technologies are (Marphatis,
2001):
1. Improved low solids solvent based systems
2. High solid system reactive plural component catalyzed systems:
• Powder coating
• Radiation cured coatings
• Water-based electrodeposition coatings.
Paint, Varnish, and Lacquers 503

BIBLIOGRAPHY
1. Bhharuka. “Industrial Paints and Coatings: Bright and Luminous”. Chemical Industry Digest
Annual-January 2003, p.100.
2. [Link]
3. http:[Link]/products/chemical/planning/ceh/[Link]
4. Marphatis R. “Coatings industry: A Rosy picture”. Chemical Industry Digest Annual 2001 p.98.
5. Patwardhan V. “The paint industry”. Chemical Industry Digest Annual-January 2002, p.107.
6. Van De Mark MR, Sandefur KD, Durham KA . “Paints” in Kirk Othmer Encyclopedia of chemical
technology. Fifth edition, Volume 18, Wiley-Interscience 2020.
25
Pharmaceutical Industry

25.1 INTRODUCTION
Pharmaceuticals are the drug-containing compounds. Chemical process industries
are playing important role in development of pharmaceutical industry by providing
base chemicals for manufacture of active pharmaceutical ingredients and other
raw materials like solvents. Pharmaceutical industry has played important role in
increasing the life span of human beings by providing basic and lifesaving drugs. Due
to the developments of various drugs and preventive measures through continuous
R&D, it has been possible to control many of the diseases like malaria, tuberculosis,
typhoid, diabetes, blood pressure, asthma and many viral diseases. Development of
antibiotics, penicillin, insulin, liver extract, and tranquilizer has been the milestone
in the development of pharmaceutical industry. Pharmaceutical industry is largely
driven by scientific discovery and developments in conjunctions with toxicological
and clinical experience (Tait D, Chapter 79: Pharmaceutical Industry Encyclopedia
of occupational health and safety). A wide variety of drugs are being manufactured
to cure different diseases which include antibacterial, antiamebic, anticoagulants,
NSAIDs, anti-inflammatory, analgesic, antidiabetic, antifungal, cardiovascular,
lipid-lowering agents, anti-malarial combi-kits, neuropsychotropics, antiallergics,
antiobesity, antiulcer, cerebral activators, enzyme preparation, irons and vitamins.
The pharma industry will play a key role driving in India to become 5 trillion dollar
economy (Chemical News, August 2018, p.62).

25.2 PROFILE OF PHARMACEUTICAL INDUSTRY

As per Business World, Indian pharmaceutical has grown leaps and bound and has
emerged as world top third largest producer of drugs in terms of volume. One to keep
in mind that India has been imported by its own people (AnsumanTripthihttp://
[Link]/article/India-emerges-As-Top-five- Pharmaceuticals-Of-The-
World/05-2018-148349/). With an estimated turnover in 2013 of nearly 31 trillion and
annual growth rate of around 5% the global pharmaceutical industry has been growing
profitably over last couple of years. IMS estimates that global spending on medicines
will touch $1.3 trillion by 2018 (Nair, MD. The Indian Pharmaceutical Industry in the
global context: Emerging perspectives, Chemical Industry Digest Annual January, 2015).
According to IBEF June 2019, Indian pharmaceutical industry is the largest provider of
generic drugs globally and India supplies over 50% of vaccines. Presently over 80% of
antiviral drugs to combat acquired immunodeficiency syndrome (AIDS).
504
Pharmaceutical Industry 505

According to IMS, healthcare information worldwide sales of generic drugs will

almost double between US$ 400 billion to US$430 billion by 2016 while sales of
branded patent protection will change little growing only by about 3–8% to around
US$ 615 billion and US$ 645 billion. US and Europe together account for 53% of global
pharma market (Chemical Industry Digest Annual-Jan 2013, p.159). Global pharma
market growth rate is given in Table 25.1.

Table 25.1: Global pharma market growth rate

Year Market in billion US$ Growth rate (%)
2004 620 7.9
2005 664 7.2
2006 710 6.9
2007 756 6.4
2008 801 4.9
Source: Annual Report 2011–12, Department of Pharmaceuticals,
Ministry of Chemicals and Fertilizers, Government of India.

India‘s first pharmaceutical industry, Bengal Chemicals and Pharmaceuticals, was

started in 1930 in West Bengal. Indian pharmaceutical industry has made significant
growth and has penetrated the global market. During last four decades, the Indian
Industry has established itself as major force in global scene and today it is the 3rd
largest producer of drugs in the volume terms and the 10th largest in value terms. Indian
generic pharmaceuticals is penetrating markets across the world. India is among the
ten top global pharma markets. With turnover of about US$ 22 billion in 2011–12, the
Indian pharma industry is growing at about 12% annually. Exports are expected to cross
US$ 16 billion by 2013–14 (Drugs and Pharma, Chemical Industry Digest, Annual-Jan
2013). Top 10 global generic players rank company are Teva, Sandoz, Mylan/Merck
GX, Watson Andrx, Barr, Actavis, Ratiopharm, Stada, Ranbaxy, and Perrigo.
Indian pharmaceutical industry is highly fragmented with 300 large and about 15,000
odd small and medium size companies. The industry makes active pharmaceutical
ingredients (API) as well as formulations. There are over 60,000 formulations in the
market covering almost every therapeutic segment. About 77% units make formulation
while about 235 make API (Drugs and Pharma, Chemical Industry Digest, Annual-
Jan 2013).The annual turnover of pharmacutical industry is estimated to be about
219755 crores during the financial year 2017. The share of export of bulk drugs, drug
intermediates and drug formulations, biologicals is Rs crores for the year 2016–17
(Annual Report 2017–18, Department of Pharmaceuticals, Ministry of Chemicals and
Fertilizers, Government of India).
Top pharmaceutical industries in India are Sun Pharma, Dr Ready’s Lab, Cipla,
Lupin, Ranbaxy, Glaxo Smith, Cadila Health, Glenmark, Pharma Gel, etc.
A major challenge to the Indian pharma industry is from China due to large scale
imports of low cost intermediates for active pharmaceutical ingredients and active
pharmaceutical ingredients. Approximately ` 800 crore of Chinese API and inter­mediates
for API are being consumed by the Indian pharma industry. Indian pharma market is
predominantly a branded generics market with share of branded generics 90% and other
drugs 10% (Drugs and Pharma, Chemical Industry Digest, Annual-Jan 2013).
506 Chemical Process Technology

According to IMS, healthcare information provider worldwide sales of generics will

almost double between US$ 400 billion and US$ 430 by 2016. US and Europe together
accounts for 53% of the global pharma market. The most emerging markets include
China, Brazil, Russia and India (Annual Report 2014–15, Department of Pharmaceuticals,
Ministry of Chemicals and Fertilizers, Government of India).
The net sales of the drugs and pharmaceuticals industry registered a growth of
12.71% in the year 2013–14 (Table 25.2). The country is almost self-sufficient in case
of formulations. The imports are being made on quality and economic consideration.
Manufacturers of drugs and pharmaceuticals are free to produce any drug approved
by drug control authorities.

Table 25.2: Import and export of medicine and pharmaceuticals products (` in crores)
Years Import Export
2011–12 14,287.66 544,906.73
2012–13 16,965.09 602,016.70
2013–14 17,944.05 690,236.77
Source: [Link]

The global sales of medicines reached $ 942 billion in 2011. Total world market size
of pharmaceuticals industry in 2011, US$ 1000 billion. which is expected to reach and
1.5 trillion by 2020. Indian pharmaceutical industry has grown from a mere 0.30 billion
in 1980 to $12 billion in 2012.
Branded generics dominate the market. The process of drugs is very low in India
due to intense competition, while India is 10th globally, it is 3rd in terms of volume of
drugs produced.
India’ top Pharmaceutical industries are CIPLA, Dr Reddy’s Lab, Lupin, Ranbaxy,
Piramal Health care, Orchid chemicals, Wockhardt, Glaxo, Welcome, Fulford,
Biocon Ltd., Matrix, Alembic, Torrent Pharmaceuticals, Stanch pharmaceuticals.
There are five central public sector undertakings. Value of import of medicinal and
pharmaceutical products was ` 2,865 crore 3.18% growth in 2003–04 and ` 10,937
crore 9.82% growth while value of Drugs and pharmaceuticals and fine chemicals in
2003–04 was ` 15,213 growth 18% and ` 47,5551 crore 12.0% growth (Annual report
2011–12, Department of Pharmaceuticals, Ministry of Chemicals and Fertilizers,
Government of India). Geographical distribution of Pharma companies in India is
given in Table 25.3.
By 2020 India is likely to be among top three pharmaceutical markets. The increase
in the size of middle class households coupled with the improvement in medical
infrastructure will influence growth of pharmaceutical sector. Indian pharmaceutical
market witnessed growth at a compound annual growth of 5.64% during 2011–2016
with the market increasing from 20.95 billion dollars in 2011 to 27.57 billion dollars in
2016 (Chemical News, August 2018 p.62). According to IBEF, Indian pharmaceutical
industry was valued at US$ 33 billion in 2017 and exports of Indian pharmaceutical to
the US will get boost as branded drugs worth US$ 55 billion will become off patented
during 2017–19.
Pharmaceutical Industry 507

Table 25.3: Geographical distribution of pharma companies in India

Number of manufacturing units
S. no. State Total
Formulation Bulk drugs
1 Maharashtra 1,928 1,211 3,139
2 Gujarat 1,129 397 1,526
3 West Bengal 694 62 756
4 Andhra Pradesh 528 199 727
5 Tamil Nadu 472 98 570
6 Others 3,423 422 3,845
10,563
Source: Annual Report 2011–12, Department of Pharmaceuticals, Ministry of Chemicals and
Fertilizers, Government of India.

The Pharma sector imports raw materials like chemicals intermediates and active
pharmaceuticals ingredients (APIs). Imports accounts for 38% of the overall raw material
cost. Import of drugs and pharmaceuticals is regulated as per the Foreign Trade Policy
of Government of India. Import of some drugs and drug intermediates are restricted
under current foreign trade policy.
Some of the major challenges for Indian pharma industry are price control of
drugs, high investment in R&D sector, strict quality control to meet the international
standards, infrastructural development, regulatory reforms imposed time to time, strict
environmental norms, competitive international market.
In view of technological growth, improved instrumentations and capabilities in drug
research, low production cost of bulk drugs and formulations, India has the potential to
increase its stakes in the global arena and take on global leadership role in many areas
(Nair 2015).
Exports of medicinal and pharmaceutical products for the years between 2013–14
and 2016–17 is given in Table 25.4.

Table 25.4: Exports of medicinal and pharmaceutical products

Years Exports (` in crore)
2013–14 90,356.00
2014–15 94,350.00
2015–16 1,10,522.77
2016–17 1,12,915.48
Source: Annual Report 2017–18, Department of Pharmaceuticals, Ministry of
Chemicals and Fertilizers, Government of India.

Today India is the 3rd major producer of drugs in terms of volume and 13th in terms
of value production. Indian companies export drugs to over 150 countries (Nair, 2020).
In 2018, UP government announced it will set up six Pharma Parks in the state.
508 Chemical Process Technology

25.3 COMMONLY USED TERMS IN PHARMACEUTICAL INDUSTRY

25.3.1 Active pharmaceutical Ingredient

According to WHO, API is substance used in a finished pharmaceutical product,
intended to furnish pharmacological activity or to otherwise have direct effect in the
diagnosis, cure mitigation, treatment or prevention of disease or to have direct effect
in restoring, correcting, modifying physiological functions in human beings. API can
be a mixture of several substances.
Biologic and Biosimilars
Biologic medicine is a large molecule typically derived from living cells and used in the
treatment, diagnosis or prevention of disease. Today’s biologic medicines have made
a significant difference to the lives of patients with serious illnesses. ([Link]
[Link]/pdfs/misc/Biologics_and_Biosimilars_Overview.pdf)
Biologic: A biopharmaceutical, also known as a biologic medical product or more
simply as a biologic or biological, is any medicinal product manufactured in or extracted..
Biosimilars: Also known as follow-on biologics are biologic medical products whose
active drug substance is made by a living organism or derived from a living organism
by means of recombinant DNA or controlled gene expression methods, sharp rise in
expenses like raw materials, power and fuel, manpower, etc.
Branded Drug
Branded drugs are drugs marketed under a proprietary, trademark protected name.
Diagnostic Agents
Diagnostic agents assist the diagnosis of disease and disorder.
Drug
Drugs a substance used to in the diagnosis, cure, mitigation, treatment or prevention
of diseases.
Drug Development
It involves discovery of a new drug to the market, include many steps before obtaining
regulatory approval to market. The major steps involve preclinical research and clinical
trial on human.
Generic Drug
Generic drugs contain identical amount of same active agents as the brand name of
the product.
Excipients
Pharmaceutical excipients are basically everything other than the active pharmaceutical
ingredient. Ideally, excipients should be inert; however, recent reports of adverse
reactions have suggested otherwise ([Link]
magazine/34/4/112/4).
Formulation
Pharmaceutical formulation is the process in which different chemical substances,
including the active drug are combined to produce a final medicinal product.
Pharmaceutical Industry 509

Tablet
A tablet is a pharmaceutical dosage form. It comprises a mixture of active substances
and excipients.
Sources:
[Link]
([Link]
[Link]
industry-terminology
[Link]/documents/[Link]

25.4 STRUCTURE OF PHARMACEUTICAL INDUSTRY

The pharmaceutical industry involves manufacture of active pharmaceutical Ingredient
(API) from raw materials and formulations. Drugs are sold as syrup, injection, tablets
and capsules. Drug is composed of two components; API which is the main ingredient
and excipient which more or less inert. Substance added to a drug to give suitable
consistency or form to the drug.
The product manufactured by pharmaceutical industry may be broadly classified
into two broad groups:
• Manufacture of API
• Formulation
• Tableting
1. API manufacture: API are manufactured from raw materials which include chemicals,
power, fuel, steam water. Some of the major APIs are diazepam, propanol-HCL,
triamterene-hydrochlorothiazide, acetaminophen codeine phosphate, ibuprofen,
digoxin, ampiciline, amoxicillin, erythomycine, cephalexin, erythromycin, isosorbide,
nevirapine, etc. venlafaxine, diltiazem, carbidopa, zemfibrozil, etc.
2. Formulation: Formulation are specific dosage or combination of bulk drugs. Formu­
lation can be categorized as chronic therapy segment: cardiovascular, neurological,
antidiabetes, oncology or acute therapy segment: Anti-infective, gastro­intestinal,
respi­ratory, analgesics, vitamins/neutraceuticals ([Link]/reports/isri/
pharmaceuticals). Formulation may be solid dosage formulations (capsules, tablets for
immediate release or extended release), semi-solid formulations for oral administration
(syrups, suspensions), sterile liquid dosage formulations (ophthalmic, oral, nasal),
injectables drugs (intravenous, and intramuscular, subcutaneous injectables), lyophilized
formulations, and typical formulations (creams, gels) (Dalton Pharma services).
3. Tableting: Tableting is a complex multistage process and involves dispensing, sizing,
mixing, filling of die mold to give proper shape, compression, dusting.
25.4.1 Manufacture of API
Most of the API are made by synthesis of chemicals. The chemicals used in AP
manufacture are extremely pure. After the process of synthesis, chemicals are converted
to final products by successive chemical reaction to produce the product with unique
physical and pharmacological properties.
Pharmaceutical industry involves a complex and multistep processing to produce
final products. A large number of unit processes are use in manufacture of API. Various
unit process used are oxidation, sulfonation dehydration, halogenations condensation
and crystallization, carboxylation and acetylation, alkylation, amination, chlorination.
510 Chemical Process Technology

Major unit operations used in manufacture of drugs are distillation, mixing, drying,
evaporation, crystallization, condensation, filtration, grinding, extraction, absorption
and adsorption. During synthesis wide variety of raw materials with reactive corrosive
and flammable nature with varying reaction temperature and pressures are involved.
The design and choice of reaction vessel is very important to have proper heating/
cooling, material of construction of reactors. Synthesis of some of important chemicals
used in manufacture of API is given in Table 25.5.

Table 25.5: Some of important chemicals used in manufacture of API

Name Chemicals Process Uses
Acetylsalicylic acid Salicylic acid and Reaction of salicylic acid Used for making aspirin.
acetic anhydride. and acetic anhydride in It is used for mild pain
Salicylic acid is made bact reactor followed by
from phenol, sodium crystallization, drying of
hydroxide and the crystal
sulfuric acid Salicylic acid+
Acetic anhydride+
Acetylsalicylic acid +
Acetic acid
Asprin
Acetaminophene p-Aminopkhenol, It is made by reaction It used as analgesic and
acetic acid, acetic of p-aminophenol with antipyretic
anhydride a mixture od acetic acid
and acetic anhydride
Tripelennamine Thionyl chloride It is made by series of
(SOCl2) and toluene reaction.
Dimethylaminoethanol First step: reaction of
2-aminopyridine, thioyl chloride and
benzal­dehyde, formic toluene, dimethyla­mino­
acid, caustic soda ethanol to form 2-chloro-
N,N-diphenul amine
hydrochloride
Second step: Reaction
of bezaldehude and
formic acid to formic
acid to form 2-benzyl
aminopyridine
Third step: reaction of
2-chloro-N,N-diphenyl
amine hydrochloride.
With toluene and
sodium. Hydroxide to
form 2-chloroethyl-N,N
diethylamine
Fourth step: reaction of
sodium amid, toluene
and 2-chloroethyl-N,N
diethylamine
Contd...
Pharmaceutical Industry 511

Table 25.5: Some of important chemicals used in manufacture of API (Contd...)

Name Chemicals Process Uses
Cimetidine Guanidine, amino-thio It is made by reaction of It is used as an antiulcer
compound guanidine, amino-thio medication
compound in presence
of methyl cyanide
Barbital Chloroacetic acid, Barbital is use in series of
benzene, NaOH, reaction
sodium etrhylate
(C2H5Na), urea
(C2H5Cl)
Codeine and Morphine Made by reaction of Used as sedative and
codeine phosphate Phenyltrymethyl­ morphine with codeine analgesic drug
ammonium
hydroxide, potassium
ethylate
Diazepamvalium p-chlomethy­- Diazepam is made by It is used as antianxiety
laniline, benzyl a series of complex drug tranquilizer
chloride and reactions. In first step
hydroxyl amine, benzophenoneoxime
chloroacetyl is made by reaction of
chloride, sodium p-chlomethylaniline,
hydroxide benzyl chloride.
Benzophenoneoxime
reacted with
chloroacetyl chloride,
in presence of NaOH to
form diazepam
Piperazine citrate Ethylene diabromide It is made by cyclization It is used as anthel­
and ammonia of ethylene diabromide mintic. Use for
with alcoholic ammonia treatment of infections
due to pin worms and
round worms.
Thamine 1,6-amino-5-
(hydrochloride bromethyl-2
vitamin B1) methylpyrimidine
hydrobromide and
5-hydroethyl-4
methylthiazole
Riboflavin 1,3,4-xylidine,
(vitamin B2) d-ribose, aniline and
alloxan
Isoniazid 4-methylpyridine It is made by oxidation Tuberculostatic anti­
of 4-methylpyridine in bacterial agents
series of reaction
Nicotinic and Beta picoline, 2-methyl-
nicotinamide 5-ethylpyridine
Contd...
512 Chemical Process Technology

Table 25.5: Some of important chemicals used in manufacture of API (Contd...)

Name Chemicals Process Uses
Azithromycin Azithromycin is a acid Azithromycin is an
stable antibiotic. It is anti­­biotic used to treat
available as generic many different types
medicine of infections caused by
bacteria.
Oflaxin Ofloxacin is a synthetic Used in acute bacterial
antibiotic of the fluoro­ infection. Most com­
quinolone drug class monly used to treat infec­
tions of the lung, urinary
tract, and skin.
Neopride It consist of levosulfide
which is substituted
benzamide derivative
Ornidazole It is made by reaction
between2-methyl
nitroimidazole and
epychlorohydrin
Metronidazole It is an antibiotic
and antiprotozoal
medication.
Amoxicilin Amoxicillin is an
antibiotic
Diphenhydramine Diphenhydramine is
generic drug

25.4.2 Role of Pharmaceutical Industry and Paradigm Shift in Drug Discovery

It is well known that the pharmaceutical industry is playing important role for discovery,
development and marketing of effective drugs for plethora disease of affecting millions
of worlds population and can playing important role in terms of medicine in treating of
the bacterial, protozoal, fungal or viral and other diseases. Modern technologies such
as artificial intelligence, genome sequencing, electronic data capture and telemedicine
have the capability to develop predictive and preventive medicines as opposed to today’
therapeutic approaches and genetic screening (Nair, 2020).

25.5 RAW MATERIAL FOR PHARMACEUTICAL INDUSTRY

Pharmaceutical raw materials are essential to producing pharmaceutical drugs and include
active pharmaceutical ingredients (API), also known as bulk active, are pharmaceutically
active, having the desired pharmacological effects on the body. The raw material may
be derived from natural or synthetic. Recently, many of the raw materials previously
derived from natural sources are being produced synthetically because of economic
reason. Pharmaceutical raw materials are manufactured using different types of acids,
alcohols, esters, phenones, pyridines, etc. Pharmaceutical industries uses wide variety
of raw materials to prepare different types of pharmaceutical products such as tablets,
capsules, injections, ointments, creams, lotions, inhalers, emulsions and suspensions:
Pharmaceutical Industry 513

Amitriptyline HCl aerosil, aerosil, atenolol, butylated hydroxytoluene (BHT), atenolol,

betamethasone calcium carbonate oyster, calcium gluconate, calcium lactate, cetirizine
citric acid dihydrochloride, dexamethasone, glycerine, dextrose monoanhydrous, liquid
glucose diphenhydramine HCl, fluconazole, furosemide, loratadine, methyl paraben,
propyl paraben, propylene glycol, sodium benzoate, sodium saccharin, sorbitol, sodium
saccharin, talcum powder (As filler and base), xanthan gum, thiourea liquid paraffin,
petroleum jelly, anthranilic acid, 2 chloroethyl amine HCl, diethyl amino ethyl chloride
HCl, dimethyl amino ethyl chloride HCl, hypophosphites, chlorides, magnesium
carbonate, and potassium nitrate. Inspection and testing of raw materials used in
manufacture of API is an important step in the pharmaceutical industry to have correct
raw material meeting the quality specifications to ensure best final product is of best
quality and minimizing the waste, material costs. Quality controls for raw materials
and active ingredients comprise identity, purity and content testing following the
regulations of the pharmacopoeia.
Raw material analysis includes huge variety of chemical analysis from the very
simple using basic equipment to complex methods and use of sophisticated instruments.
Analysis of various raw materials to pharmacopeia specifications include identification,
assay and purity, related substances, heavy metals, sulfates, ash.
Various solvents used in pharmaceutical industry are acetone, acetontrile, amyl
alcohol and acetate, aniline, benzene, chlorobenzene, chloroform, cyclohexane, dimethyl
amine, dichlobenzene, ethanol, ethanol, etrhyl acetate, formaldehyde, ethylene glycol,
formamide, furfural, n-heptane, n-hexane, isopropanol and isopropyl acetate, methylene
chloride, merthylformate, toluene, xylenes, N,N-dimetrhylformamide, dimethyl
sulfoxide, etc.
Overall the future of Indian pharmaceutical is bright except recent China factor
which is likely to increase the cost of many final products due to raw material cost.
However, India can improve her dominance in the world and can become in the top
three pharmaceutical hubs to meet the $5 trillion economy.

BIBLIOGRAPHY
1. Annual Report 2011–12, 2014–15, 2017–18, Department of Pharmaceuticals, Ministry of Chemicals
and Fertilizers, Government of India.
2. Ansuman Tritpathi. [Link]
Pharmaceuticals-Of-The-World/05-2018-148349/
3. Chemical Industry Digest, Annual-Jan 2013, p.159.
4. [Link]
terminology/
5. [Link]
6. [Link]
7. Tait D. Chapter 79-Pharmacutical Industry Encylopedia of occupational health and safety.
8. [Link]/documents/[Link]
9. Nair MD. “Indian Pharmaceutical Industry–Opportunity and Challenges in the New Decade”,
Chemical Industry Digest, Annual-Jan. 2020, p.51.
26
Corrosion and Material of
Construction in Chemical Industries

26.1 INTRODUCTION
Corrosion is a global phenomenon occurring in chemical, pulp and paper industry,
oil and gas industry, petroleum and petrochemical industries and fertilizer plants and
metallurgical industries. Corrosion promotes safety, integrity and dependability of
industrial assets. Corrosion costs the world billions of dollars annually (Raghva Chari,
2019a). It is recognized as one of the most serious problems damaging the economic
growth of both developed as well as developing countries. Resulting losses each year
are in hundreds of billion dollars. The global corrosion costs is estimated to be roughly
US$2.2 trillion annually which is over 3% of the world GDP (Ramkrishanan, 2013).
India also losses a staggering figure of over US$45 billion per year due to corrosion
(Ramkrishanan, 2013). The loss in the US is an estimated $300 billion a year. India
is losing ` 80,000 crores per annum on account of corrosion in various sectors. US is
losing more than $276 billion on account of corrosion (Economics Times Sep. 30, 2007).
As per Times of India, in India it is ` 1.25 lakh crore (Times of India, Oct. 2, 2007). The
figure could be 10 times more, because many things go unaccounted. Corrosion is like
a cancer cell that often slowly develops for many years and remains undetected and
when observed it is too late to mend the damage caused by it. Every year the chemical
industries suffer huge loss which is estimated to the tune of 4000 crores. Environmental
concern due to release of pollutants to air, soil or water caused by corrosion leaks are
also becoming high consequence events ([Link]).
Corrosion is a very complex phenomenon. There is no single solution to minimize
corrosion. Knowledge of the mechanism of corrosion, factors causing corrosion, variables
affecting corrosion as well as compatibility of the conditions of the environment
by proper choice of material of construction and good design for greater corrosion
protection and corrosion monitoring are of great importance for corrosion control.
Preventive measures are important steps in corrosion control.

26.1.1 Major Areas of Concerns in Chemical Process Industries

1. Petroleum and petrochemical: Oil and gas exploration and production, petroleum
refining, gas and liquid transmission pipe lines, gas distribution, hazardous material
transport, naphthenic acids, sulfur compounds ammonia, carbon monoxide, carbon
dioxide, oxygen, chlorides, cyanides, hydrogen, hydrochloric acid, sulfuric acid, nitric
acid, phenols, and various organic chemicals.
2. Fertilizer industries: Nitric acid, sulfuric acid phosphoric acid, fluorine, ammonia,
ammonium carbamate, acid mist, high temperature aqueous carbon dioxide, etc.
514
Corrosion and Material of Construction in Chemical Industries 515

3. Caustic, chlorine, soda ash and paper: Aqueous carbon dioxide, chlorine, hydrochloric
acid, sodium chloride, slime, etc.
4. Chemical industries: Ammonia, carbon monoxide, carbon dioxide, oxygen, chlorides,
cyanides, hydrogen, chlorine, hydrochloric acid, sulfuric acid, nitric acid, mixed
acid, phenols, organic vapor, high temperature and pressure, acid mist, moisture,
pyridine and picoline, bis-phenol, organic acid, etc.
26.1.2 Fundamentals of Corrosion
Corrosion is the destruction or deterioration of material metal or nonmetal because
of its interaction with its environment and is derived from the Latin word corrode
which means “to gnaw to pieces”. Corrosion thins entire or locally metal structure and
equipments and make them unsafe and unfit for further use (Raghva Chari, 2019). In
paper industry corrosion also contaminates the quality of paper.
Deterioration of the material is caused by chemical or electrochemical reaction with
the environment whereas destruction is mainly because of mechanical wear or abrasion.
Corrosion is also some times called extractive metallurgy in reverse.
26.1.3 Theory of Corrosion
Mechanism of corrosion has been explained on the basis of free energy, thermodynamics,
reaction kinetics and extractive metallurgy (Fontana, 1987). Corrosion occurs in metals,
because most of the metals are not in their natural state until they return to the ore form
in which they are found. Corrosion in the plastic occurs because different environments
can affect the bonds between the organic molecules making up plastic. The free energy
changes determine whether a corrosion reaction will start spontaneously.
26.1.4 Classification of Corrosion
Corrosion of the equipment takes place because of environment condition and fluid
used in the equipment. Classification of the corrosion is given in Table 26.1.

Table 26.1 Classification of corrosion

Based on mechanism of Chemical corrosion—uniform or non-uniform
corrosion process Electrochemical corrosion—galvanic corrosion or bimetallic
corrosion, galvanic microcell within a metal, differential aeration
cells, uniform corrosion, crevice corrosion, deposit corrosion,
water line corrosion.
Based on nature of corrosion Corrosion can be wet or dry. A liquid moisture is necessary for
the wet corrosion while dry corrosion usually involves reaction
with high temperature gases.
Atmospheric, marine, underground corrosion, biological
corrosion, high temperature corrosion, hydrogen cracking, hot
sulfide corrosion, metal salt corrosion, carburizing.
Based on corrosion deterioration General corrosion, localized corrosion, intergranular corrosion.
Based on mechanical factors Stress corrosion cracking, fatigue, cavitations

26.1.5 Forms of Corrosion

Corrosion may be uniform and localized which may be macroscopic or microscopic.
Various forms of corrosion are uniform corrosion, pitting corrosion, crevice corrosion,
galvanic corrosion, stress corrosion, cracking corrosion, intergranular corrosion,
516 Chemical Process Technology

dealloying or selective corrosion, caustic embrittlement corrosion, fatigue, under deposit

attack, film form or under film corrosion, high temperature corrosion, microbiological
corrosion, stray current corrosion, erosion corrosion, and fretting corrosion. Brief
descriptions of various types of corrosion are given in Table 26.2.

Table 26.2: Types of corrosion and brief descriptions

Types of corrosion Descriptions
Uniform corrosion This is a surface phenomenon and occurs through uniform attack of all
surfaces of the metal exposed to acidic, alkaline, humid or moisture laden
environment and is normally characterized by a chemical or electrochemical
reaction. Uniform corrosion can be prevented or reduced by proper material
of construction, use of inhibitors, surface coating and cathodic protection.
Galvanic corrosion This type of corrosion occurs when two dissimilar metals are brought into
contact in a corrosive or conductive solution resulting corrosion of the metal
which is less noble. This type of corrosion can be prevented by selection of
combination of metals as close as possible, by insulating two dissimilar metals,
applying coating, addition of inhibitors and cathodic protection, etc.
Pitting corrosion Pitting is a localized form of corrosion and is characterized by surface cavities
which can have different shapes. The process of pitting is slow process and
results in homogeneity on the metal surface, local loss of passivity, mechanical/
chemical rupture of protective oxide film. Pitting is accelerated by more acidic
or higher temperature conditions. Prevention can be done by proper selection
of material for construction (using metals showing fewer tendencies to pitting)
and addition of inhibitors.
Crevice corrosion Intensive localized attack in crevices which exists at lap joints, bolts, rivets,
gaskets. Prevention can be done by proper design and operating procedures.
Stress corrosion SCC is caused by the simultaneous presence of tensile stress, a specific corrosive
cracking (SCC) environment. Chloride SCC and sulfide SCC are two forms of SCC. In SCC,
stressed regions undergo localized attack resulting in hairline cracks. Suitable
environment, tensile strength, a sensitive metal, appropriate temperature and
pH are important conditions necessary for stress corrosion cracking. Stress
corrosion cracking can be prevented or reduced by lowering stress, eliminating
the critical environmental species, changing the alloy, applying cathodic
protection, adding inhibitors, coating and shot penning.
Caustic This is a form of corrosion occurring in metals in contact with caustic under
embrittlement certain condition by an alkaline environment. The cracks result from the
combined action of tensile stress and corrosion.
Hydrogen damage Hydrogen blistering, hydrogen embrittlement, decarburization, and hydrogen
attack are various forms of hydrogen damage. Hydrogen blistering is caused by
the diffusion of atomic or nascent hydrogen in the crystal lattice and collection
in fissures or cavity. Hydrogen embrittlement is caused by penetration of atomic
or nascent hydrogen through the metal structure, resulting in loss of ductility.
Carburization and hydrogen attack occur at high temperature. Decarburization
is the removal of carbon from steel by moist hydrogen and high temperature.
Corrosion fatigue This is due to tendency of metals and alloys to fracture under repeated cyclic
stressing. Fatigue life which is number of cycles needed for failure, is dependent
on the stress level. Corrosion fatigue is the cracking of metals resulting from
combined action of a corrosive environment and repeated or alternate stress.
Corrosion fatigue can be prevented or reduced by eliminating or reducing the
stress by use of inhibitors and by use of coating.
Contd...
Corrosion and Material of Construction in Chemical Industries 517

Table 26.2: Types of corrosion and brief descriptions (Contd...)

Types of corrosion Descriptions
Exfoliation Exfoliation is a severe form of intergranular corrosion. It occurs mostly
in heavily rolled or extruded products where the grains are flattened and
elongated in the direction of hot working.
Intergranular This is a localized form of attack occurring at grain or adjacent to grain
corrosion boundaries with little or no attack on grain boundaries themselves resulting
in loss of strength and ductility.
High temperature Selective oxidation of chromium when exposed to low oxygen atmosphere at
corrosion high temperature. Some of the other form of high temperature corrosion may
be oxidation-reduction, sulfidation, carburization and nitriding.
De-alloying or Selective removal of one constituent of a metal from the alloy, e.g.
selective on corro­ dezincification, graphitization.
sion
Stray current A form of attack caused by electrical currents.
corrosion
Filiform of corro­ This is a form of corrosion initiated electrolytically due to presence of moisture,
sion or underfilm oxygen and corrosive ions and results in form of fine trenches under paint,
corrosion enameled or lacquered surfaces.
Microbiological Deterioration of a metal by caused directly or indirectly as a result of the activity
corrosion of living organism. Living organisms as a result of their influence on anodic
and cathodic reactions develops a corrosive condition. This type of corrosion
is commonly used in water storage tanks pipe lines and in integral fuel tanks.
This can be prevented or substantially reduced by use of biocides.
Erosion corrosion Deterioration or attack on metal by contact with high velocity liquids resulting
in pitting type of corrosion and is characterized in appearance by grooves,
gullies, waves, rounded holes and valleys. Resistance to erosion and corrosion
both play a part in providing erosion corrosion resistance. Hardness is
considered to be a measure of material’s erosion resistance.
Prevention can be accomplished by reducing velocity, using material with
better resistance to erosion, proper design and coatings. The second generation
duplex alloys, with their relatively highly abrasive solid resistances, provide
very good erosion resistance protection.
Cavitation Cavitation is the formation of growth and collapse of bubbles or cavities in a
liquid. This is corrosion of material removed by the formation and collapse of
vapor bubbles in a liquid near a metal surface. Various forms of cavitation are
traveling cavitation, fixed cavitation, vortex cavitation, vibratory cavitation.
Fretting corrosion It is a form of wear or damage of material occurring at contact between materials
under load subjected to vibration and slip. Fretting destroys the dimensional
accuracy of closely fitted parts and increases the susceptibility to fatigue failure.
Sources: Fontana, 1987; Schweitzer, 1998; Shreir, 1976; Uhlig, 1963; Chawla and Gupta, 1996; Mall,
1988, Mall, 2007, Das, 1998, Raja Gopalan, 1998, Govinda Ram, 1998; Rayner, 1994; Charkabarty,
2013; Raghvan Chari, 2019.

26.1.6 Factors Affecting Corrosion

Various factors affecting corrosion are mentioned in Table 26.3.
518 Chemical Process Technology

Table 26.3: Factors affecting corrosion

Environmental factors Effect of oxygen and oxidizer, velocity, temperature
Factors pertaining to metals Place of metals in the electromotive force series, purity of metals,
physical state of metals, inclusions, oxide surface behavior of metals
Factors pertaining to oxidizing medium
Atmospheric corrosion Primarily due to moisture, but is accelerated by contaminants such
as sulfur compounds, chlorine, sodium chloride, carbon dioxide,
oxides of nitrogen, temperature, pressure, pH, velocity, concentration,
impurities
Corrosion of metal in Oxidizing and reducing conditions. temperature, pH, velocity,
immersed liquids concentration, presence of impurities
External factors Differential aeration/agitation, effect of light, presence of colloids,
presence of bacteria, presence of cathodic metals, existence of stray
current, existence of stresses
Biological condition Biological condition leading to microbial corrosion, common in paper
industry
Source: Fontana, 1987.

26.1.7 Corrosion Cells

Principal kinds of corrosion cells are classified according to the sources of the driving
voltage. These are (Fontana, 1987; [Link]): bimetallic cells, concentration cell,
oxygen concentration (differential aeration cells), stress cells, temperature cells.
• Bimetallic cells: In bimetallic cell two different metals are coupled; sometime one
electrode may be nonmetal such as mill scale, graphite or an oxide film.
• Concentration cell: Concentration cell exist when , two electrodes of the same metal
lie in electrolytes of different composition or concentration.
• Oxygen concentration (differential aeration cells): In differential, aeration cell there
is difference in the amount of oxygen reaching the surfaces of the two electrodes.
• Stress cells: In stress cells, metal under stress is coupled to unstressed metal in a
uniform electrolyte.
• Temperature cells: Temperature cell is developed when one electrode is at a higher
temperature than the other.

26.1.8 Basic Methods of Combating Corrosion for External Pipe Corrosion

• Substitution of another material for the metal attacked
• Modification of the environment
• Separation of the metal from the environment: Protective coating cathode protection.
• Cathodic protection: Combining coating with cathodic protection makes the best
method for protecting a pipeline.

26.1.9 Corrosion Monitoring

Corrosion monitoring which involves the direct application of corrosion measurement
techniques to industrial plants and structures for the purpose of diagnosis or corrosion
control. It is a very important aspects of corrosion prevention and control. The most
important corrosion monitoring methods are: coupon method, electric resistance
method, potential measurements, polarization resistance method, impedance method
Corrosion and Material of Construction in Chemical Industries 519

and hydrogen permeation method. Destruction techniques such as, ultrasonic, eddy
current and radiography have also been used for monitoring corrosion. In coupon
method, weighed specimens are exposed to the environment for a specified period and
the loss of metal is measured. Various ways of expressing corrosion are weight loss,
milli gram per square, decimeter per day, inches per year, mils per year. Best expression
for corrosion rate is in mils penetration per year (mpy). Relative corrosion resistance
between mpy and mm per year is shown in Table 26.4.
mpy = 534 w/(DAT)
W = weight loss
D = density of specimen
A = area of specimen
T = exposure time
1 mpy = 0.0254 mm/yr = 25.4 m/yr = 2.90 nm/hr

Table 26.4: Relative corrosion resistance

Parameter mpy mm/yr
Outstanding <1 <0.020.
Excellent 1–5 0.02–0.1
Good 5–20 0.1–0.5
Fair 20–25 0.5–1
Poor 50–200 1–5
Unacceptable 200+ 5+

26.1.10 Commonly Used Terms in Corrosion

• Anode: The electrodes which loss electrons. Oxidation occurs at anode.
• Cathode: The electrode which gains electrons. Reduction occurs at the cathode.
• Anion and cation: In electrolyte anions move to anode while cation moves to cathode.
• Polarization: Polarization is the change in electrode potential in either direction, from
equilibrium electrode potential of electrode under ideal condition.
• Passivity: Passivity refers to loss of chemical reactivity experienced by certain metals
and alloys under particular environmental condition

26.2 CORROSION IN PROCESS INDUSTRY

Various problems in process industry is discussed below.

26.2.1 Corrosion in Fertilizer Industry

Corrosion problem in fertilizer plant both nitrogenous and phosphatic fertilizer plants
are very serious as they are using wide variety of raw materials which are corrosive in
nature. The various processes in the fertilizer plants are also generating large number
of products gaseous and liquid which are corrosive in nature. High temperature and
high pressure is also involved in many processes. Corrosion in ammonia synthesis
and urea synthesis offer the greatest problem because of the high temperature, pres­-
sure and corrosive materials like ammonium carbamate, CO2. Development of modified
steels for furnace and boiler tubes, catalyst baskets, corrosion resistant solution for CO2
520 Chemical Process Technology

removal. Hydrogen embrittlement is an important problem in reformed gads pipelines.

In the CO2 removal system stress corrosion cracking (SCC) is a major problem which
is caused by the combined effects of tensile stress and corrosion. Improved process
equipments and modified practices, use of corrosion inhibitors have resulted in reduced
corrosion problem in fertilizer plants and enhance the reliability and safety in plants
(Nair, 2011). Various corrosives used in fertilizer plants are given in Table 26.5. Important
engineering materials used in phosphoric acid and phosphatic fertilizer plants are given in
Tables 26.6. Material of construction in sulfuric acid plant is given Table 26.7.

Table 26.5: Various corrosives used in fertilizer plants

Plants Corrosives Remarks
A Ammonia plant
Desulfurization Sulfur and organic sulfur com­ H 2 S, carbonyl sulfide are highly
po­unds, chloride, H2S, carbonyl corrosive.
sulfide
Steam reforming High temperature CO2, CO, H2, Oxidation, carburization over heat­
and partial sulfide, chloride ing due to flame impingement, stress
oxidation corrosion cracking, sulfidation, thermal
cycling and castrophic oxi­d ation,
hydrogen embrittlement are some of
the problem.
CO shift corrosion Hot CO, CO2, H2, gases, sulfide, Lower alloy steel with ICr-0.5 Mo is
conversion steam condensate, carbonic acid used.
CO2 removal Hot aqueous CO2 solution potas­ Stress corrosion cracking is measure
sium carbonate, MEA, CO 2 problem Carbon steel shell with SS
product of MEA degradation 304 ring packing or SS 316 give better
service. Ferrite and duplex (austenitic/
ferritic) type of stainless steel show
marked resistance to SCC.
Waste heat Waste heat recovery system Corrosion in the tube containing
recovery handles flue gases from corrosive water if not properly treated
reformer and partial oxidation and high temperature and flue gases on
process for generation of stea outside. Presence of sulfur in the flue
gases also poses corrosion problem.
Various materials grades of SA 213,
ASTM a 312, ASTM A335 and ASTM
A 351 provide useful service.
Methanation and CO, CO2, H2 and condensed Plain carbon or low alloys steels, SS 304
nitrogen wash water for wire mesh and grating
Centrifugal High pressure and Temperature Stainless steel 400 series
compressors is involved.
Ammonia High temp. and high pressure, Nickel and nickel base alloy exhibit
synthesis hydrogen, atomic nitrogen and high resistance. Nitriding effect is
ammonia results in decarburi­ more pronounced in low alloy steels
zation, nitriding, hydrogen em­ above 450ºC. Austenitic steel with high
brit­tle­ment Ni content offers considerably more
resistance.
Contd...
Corrosion and Material of Construction in Chemical Industries 521

Table 26.5: Various corrosives used in fertilizer plants (Contd...)

Plants Corrosives Remarks
Ammonia storage Stress corrosion cracking in Carbon steel grades such as BS315,
carbon steel transport and BS1511–213, ASTm A516 are convention
storage tank for anhydrous material of construction.
ammonia has been reported
B Urea synthesis NH3, CO2, ammonium SS 3021, silver titanium, zirconium
carbamate lining
Carbonate Carbonate, CO2, NH3 Ammonium carbamate highly corrosive
decomposers HP
and LP
HP and LP CO2, NH3, carbamate
absorber
Concentration, CO2, NH3, urea
crystallization
prilling
C Phosphoric Rock phosphates, sulfuric acid, Highly corrosive atmosphere
acid plant (wet fluorine, hydrofluoro- silicic acid
phosphoric acid)
D Sulfuric acid plant Molten sulfur, SO2 and SO3 acid
mist, sulfuric acid, oleum
E Super phosphate Sulfuric acid, phosphoric Moist phosphate, gases and fumes
and triple super acid, rock phosphate, fluorine, highly corrosive
phosphate hydrofluorosilisic acid fumes
F Nitric acid plant Ammonia, nitric acid, sulfuric Stabilized stainless steel high chrome
acid alloy commonly used for nitric acid,
absorption tower
G Ammonium Sulfuric acid, fluorine free Free sulfuric acid (1–5%) in
sulfate plant phosphoric acid CO2 and ammonium sulfate causes serious
carbonate solution corrosion problem. Rubber lined
vessel up to temp 60ºC Ni-Cr-Fe alloy
(Inconel monel), hastelloy
H Ammonium Nitric acid SS 430 (over 15% Cr and low carbon
nitrate and commonly used)
calcium
ammonium nitrate

Table 26.6: Material of construction for wet phosphoric acid and phosphatic fertilizer plant
Equipment Material of construction Remarks
Ground rock phosphate bin Concrete
Ground rock elevator and screw Carbon steel
conveyor
MS with butyl rubber, carbon
brick lining
Contd...
522 Chemical Process Technology

Table 26.6: Material of construction for wet phosphoric acid and phosphatic fertilizer plant (Contd...)
Equipment Material of construction Remarks
Premixer MS with butyl rubber lining and Poor resistance of Ni–Cr alloy
carbon brick lining corrosion problem with MS
Rubber lined agitation is also
reported. Higher chloride in
some raw material detrimental.
Digesters or reactor agitators MS rubber lined, FiV9, Hastelloy
C SS317
Slurry and acid pump HV9,9 Carptener 20 CD 4 AC4
Inc () toy alloy 825. JESSOP-700
Hastelloy C-276, molded rubber
impeller with rubber lined
casing, CAsA-700rWorthite
Filter and filter cloth Stainless steel (SS3162) fitter
clot: polypropylene: vacuum
box UDELHOM-U9042 Filter
pan Carpenter 20, SS 317
Concentration section Concentration pump Hastelloy Corrosion of rubber lined bodies
C impeller with A-955 casings and impeller has been reported
NAP-Alloy-3 Calandria-Karbate
tubes Evaporator bodies-MS
rubber lined or carbon brick
lined, Calandria tube Karbate
Phsophoric acid storage MS. rubber lined lead lined or Acid proof bricks not found
reinforced polyester suitable Corrosion of exhaust
fan and SS 316 L impeller and
MS rubber lined casting has
been reported
Handling of exhaust gases FRP duct with inner reinforce­
ment acrylic fiber
Heat exchanger tube Tantalum tube rubber lined,
Durimet 20 for handling,
fluosilicic acid solutions from
the scrubber
Fluorine scrubber Dry fluorine non-corrosive to
metals and alloy

Table 26.7: Material of construction in sulfuric acid plant

Equipment Material of construction Remarks
Sulfur melter and handling Concrete tank with acid proof Elemental sulfur in open yard
brick lining with stool cast iron con­tains free acid, 1500–1700
or aluminum for the heating ppm and causes corrosion
tube problem. Neutralization with
lime and ammonia to bring
down acidity below 50 ppm
gave satisfactory result.
Contd...
Corrosion and Material of Construction in Chemical Industries 523

Table 26.7: Material of construction in sulfuric acid plant (Contd...)

Equipment Material of construction Remarks
Sulfur filter Molten sulfur Casing: cast Iron,
impeller end values stainless
alloy (FA 20) SS 316 Cast
Iron duct Carbon stool tube
covered with ferrules of SS310S
embedded with refractory
Hot gas duct Mild steell shell with corrosion
resisting aluminum painting or
aluminum metalizing mild steel
Waste heat boiler Localized eliminated corrosion
duo to condensation of gases
Hot gas filter
Convertor Corrosion of convertor shell by
hot spray aluminum metalizing
treatment or painting with high
temperature silicone rosin based
aluminum paint.
Absorbers Brick lined towers packed with
ranching rings or steel tank
equipped with steel coils with
SS demister for acid mist control
Duriron heat exchanger
Acid coolers
Concentration acid pumps cold FA-20 Durimet–20 Alloy 20
acid hot acid (93–90% conc. acids, Teflon
lined plug valves (60% conc.
acid), Dow 250 plug valves or
Dow 251 diaphragm valve for
conc. hollow 55%
Valves for sulfuric acid services

26.2.2 Corrosion in Pulp and Paper Industries

Pulp and paper industry is one of the highly polluting industries and uses wide variety
of corrosive raw materials and produces pollutants which are highly toxic and corrosive.
Some of the major corrosive materials being used and produced in paper industries
are chlorine, chlorine dioxide, sodium sulfide, sulfamic acid, calcium hypochlorite,
alum, sulfuric acid, smelt, fine sand particles, presence of moisture in chlorine. Various
corrosive materials used in pulp and paper industry are given in Table 26.8.

Table 26.8: Various corrosive materials in pulp and paper industry

Chipper and digester Dust causing erosion. NaOH, Na2S, H2S, thiosulfate, high temperature,
sulfamic acid
Washing screening Sand and other foreign material, excessive foam build up in black
liquor tanks
Contd...
524 Chemical Process Technology

Table 26.8: Various corrosive materials in pulp and paper industry (Contd...)
Bleaching Chlorine chlorinated organics hypochlorite, chlorine dioxide, SO2,
sodium hydrosulfite, sulfonic acid
Paper machine stock Thiosulfate, sodium sulfate, slime sand alum
preparation
Recovery section NaOH, Na2S, H2S, SO2, SO3, thiosulfate, NOx, CO2, dissolves oxygen
High temperature, dust deposit
Power plant SO2, Dissolved oxygen NOx hardness
Caustic chlorine plant Chlorine hypochlorite HCl
Chipper and digester Dust causing erosion. NaOH, Na2S, H2S, thiosulfate, high temperature,
sulfamic acid
Washing screening Sand and other foreign material, excessive foam build up in black
liquor tanks
Bleaching Chlorine chlorinated organics hypochlorite, chlorine dioxide, SO2,
sodium hydrosulfite, sulfomic acid
Paper machine stock Thiosulfate, sodium sulfate, slime sand alum
preparation
Recovery section NaOH, Na2S, H2S, SO2, SO3, thiosulfate, NOx, CO2, Dissolves Oxygen
High temperature, dust deposit
Power plant SO2, Dissolved oxygen NOx hardness
Caustic chlorine plant Chlorine hypochlorite HCl

26.2.3 Corrosion in Petroleum and Petrochemical Industries

Corrosion in hydrocarbon industry starting from upstream processing of crude oil
during drilling and processing to further downstream processing in petroleum refining
and petrochemical production is one of the serious problems incurring huge loss.
The complexity of the problem is increasing due to processing of opportunity crude
containing higher sulfur and high TAN. Presence of sulfur and naphthenic acid causes
corrosion problem at various stages of oil gas processing, and petrochemical production
causes corrosion and refineries and petrochemical complexes are investing huge amount
of money in upgrading materials of construction. Corrosion in pipelines, storage vessels,
pumps, valves, heat exchangers, condensers and structures, etc. are cause of major
concern in petroleum industries due to the presence of chloride, organic and inorganic
sulfur compounds, naphthenic acids and moisture (which are always present in crude
oil and natural gas), elevated temperature, high pressures, temperature cycling during
normal operation, startup and shut down (Mall, 2007, 2015). Corrosion problems in
refinery and petrochemical complexes compounded because of use of high temperature
and pressure at various stages of operation. In refining and petrochemical industries,
it is necessary to guard against carburizing, nitriding, oxidation, sulfidation, hydrogen
attack, intergranular corrosion and stress corrosion cracking of stainless steels and other
high alloys (Chawla and Gupta, 1996). Stress corrosion is a common phenomenon in
petroleum and petrochemical complexes. Stress corrosion occurs when certain metals
are exposed under a tensile stress to specific environments and failure can occur rapidly
without warning (Setterlund, 1991). Corrosion in oil and gas drilling, production and
petroleum refineries is shown in Table 26.9.
Corrosion and Material of Construction in Chemical Industries 525

Table 26.9: Corrosion in oil and gas drilling, production and petroleum refineries
Corrosion in oil Corrosion in oil and gas production is one of the serious problems and
and gas drilling resulting in huge loss in form of corrosion. Major corrosions cost come in
and production the form of either premature deterioration or failure resulting maintenance,
repair replacement of damaged equipment and pipelines, cost of corrosion
inhibitors, protective coatings of offshore structure, vessels, and cathodic
protection of pipe lines. Major corrosives are CO2, H2S, moisture, chloride,
sediments, organic acids, salts and microorganisms.
Gas and oil Corrosion in pipeline carrying crude oil and natural gas has been also cause of
pipeline corrosion major concern in petroleum and petrochemical industries resulting in loss of
million dollars all over the world. Large amount of natural gas and crude oil
and petroleum products are being transported through pipe lines. Corrosion
in pipeline can be either internal or external.
Crude desalting Crude oil containing bottom sediments, salts, water which is treated for
and distillation removal of salts. The effluent water high amount of dissolved salts which is at
about 150ºC and there is always risk of stress corrosion cracking and pitting.
Corrosion in crude oil distillation units represents significant portion of
refining costs as a result of lost production, inefficient operation and high
maintenance and corrosion control chemicals costs (Batra, 1993). Chlorides,
sulfur compounds, naphthenic acid are the major corrosives.
FCC corrosion Some of the majors for corrosion prevention and control in crude oil desalting,
caustic injection, neutralization of crude and vacuum column overhead vapors
and condensed water, water washing in crude column overheads and use of
corrosion inhibitors (Batra, 1993). Apart from ammonia, cyanide, hydrogen
sulfide, some CO2, chloride and organic acids may be also present.
Amine absorber Corrosion and cracking in gas processing systems using amines is very
corrosion common phenomenon and corrosive conditions in gas treating system can
result from poor design and operating practices. Corrosivity of steel in amine
absorber is related to the specific amine chemicals used along with specific
operating conditions, i.e. temperature, velocity, amine and gas loading (Kane
and Cayard, 1995).

Sulfide Corrosion
Organic sulfur compounds such as, mercaptans, polysulfides, thiophenes as well as
elemental sulfur are present in all crude in various concentrations and can cause heavy
corrosion at even lower temperature, but are especially aggressive in the refining and
petrochemical operations above 260–280ºC (Mall, 2007; Mall, 2015). Typically sulfur
contents in crude oils are in the range of 0.5–2.5 wt.% but it can be as high as 4% (Batra,
et al. 1993). Mercaptans and organic sulfides comprise the majority of sulfur species.
H2S is most active corrosive sulfur compound. H2S can corrode steel below the dew
point of water. H2S is absorbed into water where it dissociates and reacts with iron
according to following mechanism (Batra, et al. 1993).
H2S  H+ + HS–
++ –
Fe + HS  (FeSH)+
(FeSH)+ + HS–  HSFeSH

Naphthenic Acid Corrosion

Presence of naphthenic acid corrosion (NAC) is one of the major problems in refineries
and petrochemical operation. Presence of naphthenic acid is also increasing with use
526 Chemical Process Technology

of opportunity crude containing higher TAN. The corrosive action of organic acid is
complicated because as rule these acids are not handled in isolation but rather as process
mixtures with inorganic acids, organic solvent and salts as well in combination with
other organic acid (Schillmoller, 1997). Crude oils with TAN higher than 0.5 and cuts
with a TAN higher than 1 potentially corrosive between the temperature 450–750ºF.
Velocity and more importantly wall shear stress is main parameter affecting NAC
([Link] The corrosion of the naphthenic acids begins
at 225–250ºC and increases with higher temperatures until about 320ºC. Corrosion is
reduced at higher temperatures (Danllov, 1981).
Organic acids may be present in crude oils, naphthenic or saturated ring acids.
Although naphthenic acid corrosion is major source of corrosion in atmospheric and
vacuum distillation units, other units naphthenic acid corrosion occurs are:
• Furnace coils usually at exit
• Transfer pipe
• Vacuum columns
• Site stream cooler
• Pumps.
At higher temperature, naphthenic acid may increase the severity of the sulfide
corrosion. Presumably these organic acids disrupt sulfide film thereby promoting sulfide
corrosion on alloys that would normally be resistant to this attack (Kane and Cayard,
1995). Naphthenic acid corrosion and chloride corrosion are affected by presence of
hydrogen sulfide. Naphthenic acid corrosion is worse for low H2S concentrations.
There are four options for managing corrosion: upgrading material of construction,
blending high TAN crudes with low TAN crudes, process control, use of inhibitors
(Nagi–Hanspal, et al. 2013).
CO2 Corrosion
Although CO2 in natural gas stream is not corrosive if the gas is moisture free; however,
in the presence of water, CO2 reacts to form carbonic acid. CO2 corrosion is directly
related to the partial pressure of CO2. General rules of thumb relating the CO2 partial
pressure to corrosion are: (i) low corrosion rates with CO2 partial pressure below
7 psia, (ii) possible high corrosion rates with a CO2 partial pressure between 7–15 psia,
(iii) high corrosion rates of CO2 partial pressure above 15 psia, and (iv) CO2 corrosion
is directly related to gas temperature (Kresse, 1987).
Dissolved CO2 in water or aqueous solution causes severe corrosion of pipeline steel
and process equipments used in the extraction, production and transportation of oil
and gas in the petroleum industry (Das and Khanna, 2004).
CO2 is not corrosive if gas is clean and dry; however, in the presence of water CO2
reacts to form carbonic acid:
CO2 + H2O H2CO3

The corrosion rate of iron increases rapidly in an acidic atmosphere. Iron reacts with
the carbonic acid to form iron carbonate.
2Fe++ + H2CO3 Fe2CO3 + 2H+

CO2 corrosion is directly related to the partial pressure of CO2 and increases with
increase in partial pressure of CO2. CO2 corrosion is also directly related to the gas
temperature. Higher the gas temperature greater is the CO2 corrosion rate.
Corrosion and Material of Construction in Chemical Industries 527

Internal corrosion can be controlled by removing one of the active ingredients, water
and air or by adding an interior material which will make the steel inactive (Lyons,
2004). Dehydration is an effective system for controlling internal pipe corrosion. Another
method commonly used for control of internal corrosion of pipelines is the use of
inhibitory materials.

Stress Corrosion Cracking

Some of the causes of stress corrosion cracking are environmental factors: aqueous
medium, chloride, carbonate, bicarbonate, ammonia, NaOH, acids, H2S, sea water, nitrate
solution; metallurgical factors: average chemical composition, percentage orientation of
grains, composition and distribution of precipitates, dislocation, interactions, progress
of phase transformation.

Corrosion due to Moisture/Water

In the crude oil, handling the presence of water is the major cause of corrosion. A film
of liquid water adheres to the pipeline surface and oxygen is available from dissolved
air in the product. The solubility of air in products varies but some oxygen is always
present ([Link]). There are wide varieties of experiences with corrosion in
pipelines carrying crude oil. Most of crude oils contain oil-well brine which is an
excellent electrolyte to promote corrosion. Some oils are paraffinic in nature and deposit
a protective layer of paraffin on the pipe wall.
Amount of sediment and water should be controlled. Most cross country pipelines
have sufficient flow velocity to keep a moderate amount of sediment under suspension.
Low velocity gathering lines may give a great deal of trouble especially when they are
collecting sour crudes. Chloride, sulfur compounds, naphthenic acids, O2, CO2 and H2
are the main corrosive components of crude oil and natural gas (Mall 2007, 2015).

Chloride Corrosion and Chlorine Corrosion

Chloride corrosion is another problem in petroleum and petrochemical industry.
Chloride corrosion is caused by hydrogen chloride which is formed from hydrolysis of
chloride salts present in crude oil. The majority of chloride salts present are magnesium,
calcium and sodium salts. Sodium chloride is thermally and hydrolytically stable to
about 428ºC and it does not contribute significantly to the hydrogen chloride. However,
hydrolysis of calcium chloride and magnesium chloride is significant and it begins
at temperatures above 121ºC and accelerates at temperatures above 177–215ºC (Athar,
2002).

High Temperature Corrosion

High temperature corrosion is another type of corrosion which is common in various
stages of operation especially in steam cracking, reformer, reactors, distillation column,
fluid catalytic cracking units, furnaces, heat exchangers and condensers operating at
high temperature. Some of the constituents like carbon, hydrogen, nitrogen, halogens,
sulfur, ash and molten ash can work separately or synergistically to increase the severity
of corrosion by a number of degradation mechanism like carburization, hydrogen attack,
nitriding, hot ash and salt corrosion. Carburization can occur when metals are exposed
to carbon monoxide, methane, ethane or other hydrocarbons at elevated temperature
(Tillack and Guthrie, 1999; Kane and Cayard, 1995).
528 Chemical Process Technology

Steam and Water Line Corrosion

Corrosion of steam and condensate line is also serious problem in petrochemical and
industries. The two major causes of corrosion in steam and condensate line-oxygen
which results in pitting and a low pH, which give rise to generalized thinning of piping.
Formation of low pH condensate is due to carbonic acid which is formed by reaction of
CO2 with condensed steam. CO2 formation takes place due to break down of bicarbonate
and carbonates. Deposit and corrosion occur throughout the entire steam generating
system. Boiler tubes with the highest heat transfer are the common location for deposit
of contaminants from feed water and returning condensate (Huchler, 1998).
Cooling water corrosion is also common in petroleum and petrochemical complex
as huge amount of cooling water are used at various stages of operation in chemical
and petrochemical industries. Cooling water both once through and recirculation is
responsible for both corrosion and scaling of piping and exchangers. Crude refining
operation in the coastal area forces additional problem of seawater corrosion, pitting,
uniform corrosion, stress corrosion cracking, and tuberculation. Important factors
which influence corrosion in cooling water system are dissolved oxygen, temperature,
velocity, pH and dissolved solids.
Corrosion in Steam Crackers
Corrosion steam cracker plant is major challenge to the petrochemical complexes due
to carbon build up, increase in temperature and build up of chromium, iron and nickel
in the coke during operation because of high temperature and carburistion.
Corrosion in Storage Tanks
Corrosion of storage tank components—the roof, shell, bottom plates and foundation
may occurs due to atmospheric corrosion, underside corrosion due to electrochemical
process. Unlike atmospheric corrosion of visible equipment parts and accessories,
undesirable corrosion often remains hidden and unnoticed until leaks develop (Habiby
et al., 2003). Electrochemical corrosion occurs at the bottom of tanks due to anodic and
cathodic reactions.

26.3 CORROSION PREVENTION AND CONTROL

Although corrosion is unavoidable, however, its scope and severity can be minimized.
Some of the basic approaches for corrosion control are (Mall 2015):
• Selecting corrosion resistant material of construction
• Use of corrosion inhibitor
• Isolating the material from the corrosive atmosphere
• Coating and linings
• Altering the environment through process changes
• Employing electrochemical control-cathodic and anodic protection
• Designing and fabrication to minimize localized corrosion
• Corrosion monitoring.
Metallurgy choices have expanded significantly for process equipment and pumps
used for handling difficult corrosive fluids (Rayner, 1994). Material selection and
corrosion control requirements should be based on specified design life. Material
selection should be based on anticipated corrosion or material degradation rate,
material availability, fabricability, maintainability, maintenance cost and availability of
spare parts (Narain, 2000). The principal selection criteria for material of construction
Corrosion and Material of Construction in Chemical Industries 529

in petroleum industries are mechanical properties, corrosion resistance, stability of

properties, sensitization, fabricability, availability, cost, effective service life, (Brown,
1997). Large number of materials available to meet today’s corrosion needs, the selected
material may be metal, alloy, plastic, elastomeric, ceramic or combination of two or
more metals (Mall, 2015). Important engineering materials used in phosphoric acid
and phosphatic fertilizer plant for pumps, valves, heat exchangers, etc. are given in
Table 26.10. Material of construction in sulfuric acid plant is given in Table 26.7.
Established heat resistant alloys for refining/petrochemical applications are given in
Tables 26.11 to 26.13.

Table 26.10: Important engineering materials used in phosphoric acid and

phosphatic fertilizer plant for pumps, valves , heat exchangers, etc.
CD-4MCU: Cr 24.5–26.5%, Ni 4.75–6.0%, Cu 2.75– JESSOP: Cr 21%, Ni 25%, Mo 4.5%,
3.25%, Mo 1.75–2.25%, Si 1.00 Max, Mn 1.0 Max., Mn 1.7%,
C 0.045 Max., P 0.04%, Max, S 0.045 Max Iron balance Si 0.5%. Cd 0.3%, C 0.03%
Hastelloy alloy C-276: Cr 14.5–16.5% %, Mn 1.0%, Cooper FA 20 Cr 20%, Ni 29%, Mo 3–5%,
Fe 4.7%, S 0.03%, Si 0.0%, Co 2.5%, Mo 15–17%, P 0.03%, Si 1 %, Cu 4%
W 3– 4.5%, V 0.35%, C 0.02
Incoloy Alloy-825: Ni 41.8%, C 0.3%, Mn 0.5%, Fe 30%, Durimet 20: Cr 20%, Ni 29%, Mo 2%, Si 1%,
S 0.02% Si 0.2%, Cu 2.; 2%, Cr 21.5%, Al 0.1%, T 0.9%, Cu 3%, C 0.07% (Max.)
Mo 3.0%
In CA-A-700: Cr 22–25%, Ni 19–22%, Mo 1.75%–2.75%, Carpenter 20: Cr 20%, Ni 29%, Mo 2%,
MN 2%, Si 1.5%, C 0.01% Cu 3%, C 0.007%
Worthite: Cr 20%, Ni 24%, Mo 3%, Si 3.25%, Alloyco 20: Cr 21 %, Ni 28–30%, Mo 2–3%,
Cu 1.75%, C 0.007% Maxm Si 1.5% cu 4%
HV-9: Cr 21–23%, Ni 25–27%, Mo 4–6%,
Mn 2.5%, Si1.0%, P 0.04%, S 0.01% Ti 0.25%,
C 0.05%

Table 26.11: Established heat resistant alloys for refining/petrochemical applications

Alloy Cr Ni Fe Co C Si Mn Al Other
304H 19 9 Balance (Bal) – 0.07 0.75 – – Mo 2.5
316H 17 12 Bal – 0.07 0.75 2 – Ti × C + N
321H 18 10.5 Bal – 0.07 0.75 2 – Nb8 × C
347H 18 10.5 Bal – 0.07 0.75 2 – –
309H 23 13.5 Bal – 0.07 0.75 2 – –
310H 25 20.5 Bal – 0.07 0.75 2 – –
85H 19 15 Bal – 0.20 3.5 0.8 1 –
253MA 21 11 Bal – 0.08 1.7 0.6 – N O.17, Ce 0.04
330 19 35 Bal – 0.05 1.2 1.5 – –
800H 20 31 48 – 0.08 0.3 0.8 0.3 Ti 0.3
600 16 76 7 – 0.04 0.2 0.2 – –
601 23 61 14 – 0.04 0.2 0.2 – –
617 22 52 2 12 0.06 0.5 0.5 1.2 Mo 9, Ti 0.5
625 22 61 2 – 0.05 – 0.2 – Mo 9, Nb 3.6
Courtesy: Chemical Engg. Progress (CEP, Feb 1999, p.59 and Nickel Development Institute, Toronoto,
Canada)
530 Chemical Process Technology

Table 26.12: Newer heat resistant wrought alloys for refining/petrochemical application
Alloy Cr Ni Fe Co C Si Ti Al Other
803 27 34 Balance – 0.08 0.3 0.4 0.4 –
(Bal)
HK4M 25 25 Bal 0.25 0.75 0.4 0.4 – B 0.004
HPM 25 38 Bal 0.15 1.7 0.4 – – Mo 2, Zr 0.05,
B 0.01
HR120 25 37 Bal 1 0.05 0.6 0.1 0.1 W 2, Mo 2, Nb
7, B 0.004, N 0.2
HR160 28 37 2 29 0.05 2.7 0.45 – –
AC66 27 32 41 – 0.05 – – – Nb 0.8, Ce 0.06
617LCF 22 52 1.5 12.5 0.08 0.2 0.3 1.2 Mo 9
45TM 27 47 23 – 0.08 2.7 – – N 0.08, Re 0.10
602CA 25 63 9.5 – 0.18 – 0.15 2 Y 0.8, Zr 0.07
Courtesy: Chemical Engg. Progress (CEP, Feb 1999, p.59 and Nickel Development Institute, Toronoto,
Canada)

Table 26.13A: Other heat resistant wrought alloys for refining/petrochemical application (group I)

Alloy Cr Ni Mo C Si Mn Fe Other
SS 304 18–20 8–10.5 – 0.08 1.0 2.0 Bal
SS 304L 18–20 8–12 2–3 0.03 1.0 2.0 Bal
316 16–18 10–14 2–3 0.08 1.0 2.0 Bal
316L 16–18 10–14 3–4 0.03 1.0 2.0 Bal
317 18–20 11–15 3–4 0.08 1.0 2.0 Bal
317L 18–20 11–15 5.5–7.5 0.03 1.0 2.0 Bal
Hastelloy G 21–23 Balance 5.5–7.5 0.05 0.4 1–2.0 18–20 (Cbd–Tc)
(Bal) 2.18,
Co–2.07
W–0.79 4–
Hastelloy 14.5–16.5 Bal 15–17 0.021 0.1 0.5 4–7 7 Co-1.13,
C-276 V-0.2, W-3:49
Incoloy 825 19.5–23.5 Bal 2.5–3.5 0.05 0.3 0.3 28–29
Aresta 20 18 6.1 0.02 0.5 0.5 Bal Cu 1.5–30
254SMO Ti 0.6–1.2
Carpenter 20 19–21 32–38 2.0–3.0 0.07 1.0 20 Bal Cu 3.4, Cb +
Cb-3 Ta 0.83
Carpenter 20 24 Bal 5.6 0.02 0.3 0.3 31 Cu 3.3,
Mo 6 Cb+Ta 0.05
Contd...
Corrosion and Material of Construction in Chemical Industries 531

Table 26.13B: Other heat resistant wrought alloys for refining/petrochemical application (group II)
SS 304 0.08 8–12 18–20
SS 304L 0.03 8–12 18–20
SS 316 0.08 10–14 16–18 2.3
SS 316L 0.03 10–14 16–18 2.3
SS 316 T1 0.08 9–12 17–19 5.0
Incoloy 800 0.10 32–5 21.00 0.38 0.38
HK 40 0.35–0.45 20 25

26.3.1 Corrosion Inhibitors

Corrosion of the metallic surfaces can be reduced or controlled by use of corrosion
inhibitors which form protective film on the surface of the metal. Various types of
corrosion inhibitors are passivating inhibitors, organic inhibitors and precipitation
inhibitors. Various types of corrosion inhibitors are given in Table 26.14.

Table 26.14: Various types of corrosion inhibitors

System Medium Corrosion inhibitor Remarks
Steam and Water, CO Oxygen scavenger: inorganic sul­fite, Addition of catalyst to the
2
condensate hydrazine, carbohydazine, hydro­ hydra­zine mixture ensures
line quinone, and ascorbic acid. completion of the oxygen
Neutralizing type amines: morpho­ scavenging and metal passi­
line, diethylamino-ethanol, cyclo­ vating reactions. Filming
hexylamine, ammonia. amine react with carbo­nic
acid in condensate to form
neutral amine salts thus
raising the pH
Cooling Dissolved Filming type amine: Octadecyla­ B i o c i d e s a r e u s e d f o r
water oxygen, mine, ethyloxylated soya amine, removal of undesirable
hardness, diadodecylamine, and tridode­ formation of biological film
chloride, sulfate, cylamine.
etc. Addition of sodium silicate, chro­­
mates, polysulfide, sodium molyb­
date. Use of biocides (Oxidi­zing and
non-oxidizing).
Oxidizing: Chlorine, ClO2, calcium
hypochlorite).
Non oxidizing: isothiozolines, dime­
thyl bisthiocyanate
Sources: Fontana, 1987; Schweitzer, 1998; Shreir, 1976; Uhlig, 1963; Chawla and Gupta, 1996;
Muralidharan, et al. 1997; Mall, 2007, 2015. Thermex ([Link]
[Link]?levelno=2&divid=3&pageno=1&objecti.)

26.3.2 Design Consideration

Poor design of equipment/instruments, poor fabrication of joints/piping/equipment
and due to lack of precautions to be employed to reduce environmental damage can
result in the corrosion failure of equipments. Corrosion can be controlled or minimized
532 Chemical Process Technology

to a greater extent by good design which can be obtained by considering surface

conditions, smoothness of surface, cleanliness of surface, dissimilar material control,
elimination of crevices, proper design of supports, by providing adequate drainage,
avoiding electrical contact between dissimilar metals, avoiding sharp bends in piping
system, providing thicker structures to take care of impingement effects, by properly
considering the relevant codes and standards, by properly designing against excessive
vibration, selecting plant site upwind from other polluting industries, by avoiding vapor
spaces, uneven and stress distributions from control of metal surface temperature,
environment, stress, by welding procedure, eliminating or minimizing the presence
of impurities, reducing velocity of fluid, by providing easy access to the structure
for periodic inspection, maintenance and replacement of damage parts, eliminating
shielding area, etc. (Mall, 2015).

26.3.3 Coating and Lining

Apart from selection of proper material of construction, sometimes surface treatments
like coating, cladding, heat treatment, diffusion treatment and surface finish are also
helpful in reducing corrosion by isolating the material from the corrosive environment.
Corrosion prevention by coating can be achieved by barrier protection, inhibition
protection, sacrificial protection (Ramkrishanan, 2013). Various types of coating may
be either metallic or inorganic coatings like ceramic, glass. Commonly used organic
coatings are oil base, alkyd, chlorinated rubber, coal tar epoxy, catalyzed epoxy, silicone
aluminum, vinyl, urethane, etc.

26.3.4 Cathodic Protection and Anodic Protection

Cathodic protection has been very common in petroleum and petrochemical industry,
especially in case of pipelines, storage tanks and steel structure exposed to soil. Cathodic
protection is done either by an external power supply or by appropriate galvanic
coupling. Anodic protection is based on the formation of a protective film on metals
by externally applied current.

26.3.5 Corrosion in Inline Instrument

Corrosion in Inline instrument is very common problem in process industries. All forms
of corrosion discussed earlier occur in instruments and responsible for their failure.
Various corrosives listed earlier include chlorine, hydrogen sulfide, steam, CO2, dust,
slime, etc. Various affected area in inline instruments are valves, smaller diameter
pipeline flow meters. Various corrosion mitigation in the industry are use of proper
material of construction, use of inhibitors and protective coating , adequate corrosion
monitoring and inspection (Das and Rawat, 2019).

26.3.6 Corrosion Monitoring

Corrosion monitoring is one of the important aspects of overall corrosion prevention
and control as it helps in the diagnosis and corrosion control. Corrosion monitoring has
been found to improve output, increase of life of plant, improve product quality and
reduce capital and operating cost. It helps in monitoring effectiveness of solutions to the
problem in providing information for solution of specific corrosion problem and helps in
assessing the behavior of new materials and helps in reducing downtime. It helps in the
safe operation of any equipment. Significant benefits of a corrosion monitoring program
Corrosion and Material of Construction in Chemical Industries 533

are: improved safety, reduced down time, early warning before costly serious damages
sets in, reduced maintenance cost, reduced pollution and contamination risks, longer
intervals between scheduled maintenance, reduced operating costs and life extension
(Khanna, 2006). Various methods used for corrosion monitoring have been already
discussed. Non-destructive testing play role important role in role in industry and save
million of dollars annually (Raghuchari, 2019) Various methods used in industry for
non-destructive testing corrosion monitoring are visual inspection, magnetic particle
testing, eddy current testing. Visual inspection is very important in industry which tells
that more expensive non destructive testing is required or not (Raghuchari 2019). 3D
printing adds new dimension to process equipment. This is technique which promises
faster and cheaper parts production as well as more sophisticated designs (Otewell, 2019).

BIBLIOGRAPHY
1. Agarwal DC. “Defy corrosion with recent nickel alloys”, Chemical Engg. Progress, January
1999, p.62.
2. Batra B, Borchert CA, Lewis KR, Smith AR. “Design Process equipment for corrosion Control”
Chemical Engineering Progress, May 1993.
3. Bennion D. “Hazards Associated with the Use of Austenitic Stainless steel in Process Plant”,
Advances in Petrochemical Technology, The Institutional Chemical Engineers Symposium,
Series no. 50, 1977.
4. Bertness TA, Chilingarian GV. “Corrosion in drilling operations” in “Drilling and drilling fluids”
by Chilingarian, GV, Vorabutr, P. Elsevier Scientific Publishing Company. 1981, p.559.
5. Brown RS. “Select alloys for severely corrosive environment”, Chemical Engg. Progress, March
1997, p.74.
6. Charkrabarty C.”Corrosion of metals”, Chemical News, February, 2013, p.31.
7. Chawla SL, Gupta RK. “Material selection for corrosion Control”, ASTM International, Materials
park OH 44073, 1996.
8. Christman TK, Beavers JA. “Cause of stress corrosion cracking in pipe”, Oil & Gas Journal,
January 5, 1987, p.40.
9. Danllov B. “ Examples of corrosion control”, Hydrocarbon Processing, February 1981, p.95.
10. Das GS, Khanna AS. “Corrosion behaviour of pipeline steel in CO2 environment”, Trans India
Inst. Met. 37, June 2004, p.277.
11. Das S, Rawat A.”Corrosion in Inline Instruments” Chemical Industry Digest, April 2019 p.61.
12. DuPart MS, Bacon TR, Edwards DJ. “Understanding corrosion in alkanolamine gas treating
plants”, Hydrocarbon Processing, April, 1993, p.75.
13. Finzel WA. “Use of low VOC coatings”, Chemical Engineering Progress, November 1991, p.50.
14. Fontana MG. “Corrosion Engineering”, Third edition, 1987, McGraw Hill Book Company.
15. Habiby F, Imtiaz RR, Mutairi AH. ”Reduce underside corrosion in above ground storage tanks”,
Hydrocarbon Processing, January, 2003, p.59.
16. Hibner EL, Fende DS. “Conquer chloride and alloy cost”, Chemical Engineering Progress, April
1999, p.63.
17. Hanratty T. “ Corrosion under insulation is a hidden problem”, Hydrocarbon Processing, March,
2013 p. 51.
18. Huchler LA. “Select the best boiler water chemical treatment programme”, Chemical Engineering
Progress, August 1998, p.45.
19. Kane RD, Cayard, MS. “Improve corrosion control in refining process”, Hydrocarbon Processing,
November 1995, p.129.
534 Chemical Process Technology

20. Kane RD, Cayard MS. “Select materials for high temperature”, Chemical Engineering Progress,
March 1995, p.83.
21. Khanna AS. “Corrosion monitoring and control methods for chemical process industry”. Chemical
industry digest October 2006, p.49.
22. Kresse TJ. “CO2 removal reduces pipeline corrosion at two storage tank”, Oil & Gas Journal,
October 12, 1987, p.77.
23. Lack J, Harrell, B. “Reduce salt corrosion with stronger base amines”. Hydrocarbon Processing,
September, 2013, p.67.
24. Little BJ, Ray, RI, Wanye, PA. “Tame microbiologically influenced corrosion”, Chemical
Engineering Progress, September 1998, p.51.
25. McNab AJ, Treseder RS. “Materials requirement for gas treating process”, Material Performance,
Vol 10, No.1, 1971.
26. McConkey SE. “Fusion bonded epoxy pipe coatings are economical, practical”, Oil & Gas Journal,
July 19, 1982, p.148.
27. Mogul MG. “Reduce Corrosion in Amine Gas Absorption Columns”, Hydrocarbon Processing,
October 1999, p.47.
28. Muralidharan S, Venkatachari G, Rengaswamy NS. “Inhibitors & Chemical Treatments for Cooling
Water Systems”, Chemical Industry Digest-SPl Issue-Maintenance, Coating & Corrosion, May,
p.87.
29. Nagi-Hanspal Subramaniyam M, Shah P. “ corrosion control with high acid crudes” Petroeum
technology Q3 2013, p.115.
30. NairSukumaran MP. “Mega Ammonia plants material selection and combating corrosion”,
Chemical Industry Digest, Sep 2011, p.55.
31. Narain S. “Material Science and Corrosion Control”, Hydrocarbon Processing, October 2000,
p.76.
32. Otwell S. ”3D printing adds new dimension to process equipment”. Chemical Industry Digest,
February 2019, p.64.
33. Payne B. “Minimise corrosion while maximizing distillate”, Petroleum technology quarterly, Q3,
2012, p.75.
34. Picciotti M, Picciotti, F. “Selecting corrosion resistant materials”. Chemical engineering progress,
2006, p.45.
35. Punj A. “Pipe coating selection”, Chemical Engineering World, vol. 28, no. 10, October 1993.
36. Ramakrisnan B. “Preventing corrosion through coatings”, Chemical Engineering World December
2013, p.52.
37. Rayner RE. “Better metallurgy or process equipment”, Hydrocarbon Processing, 1994, p.53.
38. Raghva Chari S. “Metals corrosion, corrosion control and corrosion prevention”, Chemical
Industry Digest, February 2019, p.47.
39. Raghva Chari S. “Metals corrosion, corrosion control and corrosion prevention”, Chemical
Industry Digest, December 2019, p.63.
40. Richert JP, Bbadasarian, AJ, Shagay, CA. “Stress corrosion cracking of carbon steel in amine
system”, NACE Material Performance, January 1988, p.9.
41. Schillmoller CM. “Control organic acid corrosion with these metals and alloys”, Chemical
Engineering Progress, February 1997, p.66.
42. Schllimoller CM. Vanden Bruck “Furnace alloys update”, Hydrocarbon Processing, December
1984, p.55.
43. Schweitzer PA. “Encyclopedia of corrosion technology”, Marcel Dekker, 1998.
44. Setterlund RB. “Selecting process piping materials”, Hydrocarbon processing, August 1991, p.93.
45. Setterlund RB. “Preheat piping failures”, Hydrocarbon Processing, October 1997, p.47.
46. Singh G, Samdal OR. “Internal coating justified by operating costs”, Oil & Gas Journal, April 4,
1988, p.50.
Corrosion and Material of Construction in Chemical Industries 535

47. Shreir LL. “Corrosion”, vol. 1 and 2, Newnes-Butterworths, 1976.

48. Strong RC, Majeshi VK, Whilelm SM. “Basic steps lead to successful FCC corrosion control”,
Oil & Gas Journal, September 30, 1991, p.81.
49. Tillack DJ, Guthrie JE. “Select the right alloys for refiners and petrochemical plants”, Chemical
Engg. Progress, February 1999, p.59.
50. Uhlig HU. “The corrosion hand book”, John Wiley & Sons, 1963.
51. Walker HB. “Reduce FCC corrosion”, Hydrocarbon Processing, January 1984, p.81.
52. An T, Bird KW. “Know which reactive and refractory metals work for you”, Chemical Engineering
Progress, February 1992, p.65.
27
Energy Management in
Chemical Industry

27.1 INTRODUCTION
Per capita energy consumption is yardsticks for industrialization and urbanization of a
country. Industries are the major source of energy consumption, as the economy takes
off and prosperity level increases per capita consumption is bound to shoot up. Indian
chemical industry is one of the important sectors of the economy. Fast development
has taken place in Indian chemical industry with availability of raw materials and
energy resources. With increasing development in petroleum, petrochemical, fertilizer,
cement and other industries, energy requirement of India is also likely to increase.
India is now heavily dependent on fossils fuels like coal, oil and gas. Global energy
demand will be about 30% higher in 2040 compared to 2010. As economic output more
than doubles and prosperity expands across the world whose population will grow
to nearly 9 billion (Vasudeva, 2012). The global energy is expected to reach 17,100
million ton oil equivalent (MTOE) by 2030 as compared to 11,468 MTOE at presents
(Bhatia, 2008). Our energy consumption is just round 533 kg per annum as against
world average of 1795 kg per annum. Oil and gas sector has important role to play in
future for securing a sustainable energy system. Oil and gas sector has been the lifeline
of Indian energy system and a major pillar of Indian economy (Joshi, 2017). Strong
economic growth coupled with growing lifestyle and consumer needs, hydrocarbon
industry will play an important role in meeting the demand of oil and gas (Joshi, 2017.)
Our per capita consumption is just 4% of USA and 20% of world average (Ray and
Sunil Kumar, 2019). According to IBFE 2018 survey, India is the third largest consumer
of energy. Demand of primary energy in India is expected to increase by 2035 to
1.56 million tons of oil. Oil and gas industry is growing robustly in India and Government
has enacted various policies to encourage industrial investment ([Link]
industry/[Link]). Commercial primary energy in India has grown about
700% in last four decades. Primary energy consumption is below that of developed
countries. Energy consumption is likely to rise by population rise and quest for quality
of coal accounts for 55% of the country’s energy need (Annual Report 2019–20, Ministry
of Coal and Mines, Government of India).
The 2019 Word Energy Outlook of International Energy Agency projects that
the primary energy demand will be 25% in 2040 higher than 2019. Two factors are
responsible of increase in energy consumption—population growth and people’s
aspiration for the improvement of their quality of life (Thmoas and Francis, 2020).
536
Energy Management in Chemical Industry 537

To maintain an annual growth rate from 2012 to 2032, primary energy consumption
required to be scaled up from 537 million tons of oil equivalent in 2011–2012 to 1856
million tons oil equivalent. Oil consumption would rise from 166 million tons per
annum and gas would go up from 44 million tons oil equivalent to 197 million tons oil
equivalent (Vasudeva, Dr HL. Memorial lecture at CHEMCON 2012 at NIT Jalandhar,
December 27, 2012). Total energy requirement is given in Table 27.1. India is the world’s
fifth largest consumer of primary energy. All India annual per capita consumption of
electricity is increasing in India and reached about 1000 kWh in 2015 from 566.7 in
2002–03 and 704.2 in 2007–08 (IBEF 2016, Gharpure, 2010). India has taken a voluntary
commitment of reducing emission intensity of its GDP by 30–35% from a levels by
2030. (http./[Link]/file manager/annual report 2015–2016/EN/Chapter%201/
chaptere_1.htm)
India is the world largest energy consumer economy, and demand for primary energy
is expected to increase threefold by 2035 to 1,516 million tons of oil ([Link] ibfe.
org/oil gas industry/[Link])
India with high population and huge energy consumption needs technologies for
improved efficiency in processes and reducing per capita energy consumption. Looking
to increasing consumption in various sectors there is urgent needs for alternative source
of energy especially the renewable energy. Biomass-based diesel growth to outpace
ethanol by 2020 (Nura fiatin, 2017).

Table 27.1: Total energy requirements (MTOE)

Year Hydro Nuclear Coal Oil Gas Total
2016–17 18 31 375 241 64 729
2021–22 23 45 521 311 97 997
2026–27 29 71 706 410 135 1,351
2031–32 35 98 937 548 197 1,815
Source: IEPN Report, p.28,Table 2.10.

Power with shares in total installed capacity as per IBEF 2016 is given below:
• Thermal power—coal and gas (69.8%)
ƒ Coal: India has large reserves of coal. At the end of 2014 total reserves stood at
301.56 billion of which 60.6 billion tons was proven reserves
ƒ Gas: India proven natural gas reserves measure of about 1.4 trillion cubic meters
• Hydro power (15.2%): India has enormous potential for hydropower. In FY16 India
has 42.47 GW hydropower generation capacity
• Renewable power (13.0%): Wind energy is the largest renewable energy source in
India. Projects like Jawaharlal Nehru National Solar Mission (aims to generate 20,000
MW of solar power by 2022) are creating a positive environments. There are plans
to set up four solar power plants at 1 GW each.
• Nuclear power (2.1%): Currently India has 5.78 of net electricity generation capacity
using nuclear fuels and aims to increase it to 45 GW by 2020; with one of the world’s
largest reserves of thorium, India has a huge potential in nuclear energy.
Our energy consumption is around 533 kg per annum as against world average of
1795 kg per annum , oil and gas sector has important role to play in future for secure
and sustainable energy system (Pathan, 2017). Oil and gas sector has been the lifeline
538 Chemical Process Technology

of Indian energy system. Strong economic growth coupled with growing lifestyle and
consumer needs, hydrocarbon industry will play an important role in meeting the
demand of oil and gas (Joshi, 2017).
Demand for natural gas in India is likely to increase in power generation to transport
and feedstock for the fertilizer and petrochemical industry which heavily dependent
on naphtha as feedstock. Growth of natural gas based fertilizer and petrochemical will
be major driver for natural gas consumption in India (Joshi, 2017). With limited reserve
of petroleum and natural gas and restriction of hydel projects due to environment and
geopolitical perception of nuclear power coal will be main source of energy in India
(Annual Report 2019–20, Ministry of Coal and Mines, Government of India).

27.2 RENEWABLE ENERGY IN INDIA

With increasing demand of energy due to industrialization and increasing population
some of the alternative indigenous energy resources have to be developed. India needs
to ensure sustained energy supply and improve the quality and reliability of energy
supply. Some of the future sources of energy are:
• Solar power • Coal bed methane
• Wind power • Shale gas
• Hydroelectrical power • Nuclear power
• Biofuel • Waste to energy

Core drivers for development and deployment of new and renewable energy in India
has been energy security, electricity shortages, energy accesses and climate change. As
per IBFE Report June 2019, following major investments and developments in Indian
renewable sector interstate distribution of wind energy was started in August 2018 and
solar sector in India received investment of US$ 9.8 billion in 2018, and in first half of
2018, India installed 1 MW of solar capacity every year. According to 2018 Cimatescope
report, India ranked second among the emerging economics to lead to clean energy.
Over the years renewable energy sector in India has emerged as a significant player
in the grid connected power generation capacity. There has been visible impact of
renewable energy on the Indian energy scenario. There is perception that renewable
energy can now play a significant role in meeting the energy demand and support the
agenda of sustainable growth.
Process industries are also exploring and diversifyingin to alternative and renewable
energy sources solar, wind, biofuels, etc.
As per UBM by 2020, India is targeting the installation of 175 GW renewable energy
capacity. As of December 2016, India has installed capacity 57% of which is wind energy.
([Link]/.../eyeon-)
It is expected that by 2022 60 GW of large and medium scale grid connected solar
power projects, 60 GW wind, 40 GW solar roof projects, 10 GW bio-power and 5 GW
small hydro. Cumulative installed capacity of renewable as of December 31, 2016 is
given below (Source: [Link]/.../EYEON-):
• Wind: 28700.44 MW
• Solar: 9012.66 MW
• Small hydro: 433.85 MW
Energy Management in Chemical Industry 539

• Biopower: 7856.94 MW
• Waste to power: 114.08 MW
As per Ministry of Energy, new and renewable India has an estimated renewable
energy potential of about 900 GW from commercial exploitable sources viz Wind 102
vGW (at 80 meters mast height); small hydro 20 GW; Bioenergy-25 GW and 750 GW
solar power, assuming 3% waste land is made available… The ministry had taken up
a new initiative for implementation of wind resource assessment in uncovered/new
areas with an aim to assess the realistic potential at 100 m level in new stations across
the potential under National Clean Energy Fund (NCEF) (http./[Link]/ file
manager/annual report 2015–2016/EN/Chapter%201/chaptere_1.htm)
As per IBFE Indian Renewable report June 2019, Indian renewable energy sector
is the fourth most attractive renewable market in the world and in April 2019 total
renewable power installed (excluding large hydro) in the country stood 78.35 GW.
Off-grid renewable power capacity has also increased.

27.3 ENERGY CONSUMPTION AND CONSERVATION MEASURES

With continuous depletion of conventional source of energy (coal, crude oil natural gas)
and rising cost of coal, fuel oil, electricity, energy conservation has become a necessity for
chemical process industries to meet the global challenges. There has been considerable
development in chemical process industry to reduce energy consumption which has
been mandatory. The concept of more willing to satisfy than optimize energy usage
has to be discouraged. Enlightening the working personal at all levels about energy
conservation opportunities is very important for proper implementation of energy
management policies. Use of renewable energy is also getting importance in industry.
Now an integrated approach of total energy is used to convert all forms of energy in
a single unit. Losses can be calculated by quantitative rate and by defining the nature
and type (Goel, 2017). Threshold energy consumption has been notified by Bureau of
Energy Efficiency for nine energy intensive industries (Table 27.2).

Table 27.2: Threshold energy consumption for nine energy intensive industry
Threshold energy consumption in metric ton of oil
S. no. Notified sector
equivalent (MTOE) per year
1 Thermal power plant 30,000
2 Fertilizer 30,000
3 Cement 30,000
4 Iron and steel 30,000
5 Chlor alkali 12,000
6 Aluminum 7,500
7 Textile 3,000
8 Pulp and Paper 30,000
9 Petroleum refineries 90,000
Sources: Mission Director, BEE2016 newdc@[Link].
540 Chemical Process Technology

Some of the major approaches for energy consumption are:

• Good house keeping
• Prevention of unscheduled shut downs of plant
• Process and technological development
• Increasing capacity
• Achievement of high better capacity utilization
• Equipment and process modification
• Catalyst development to improve yield and quality of product and increase
productivity
• Reducing the waste generation,
• Steam conservation in steam network, distillation and other equipments
• Insulation of steam lines
• Recovery of condensate
• Co-generation
• Efficient waste heat recovery for maximum heat recovery
• Energy conservation in electrical equipments and illuminating system
• Efficient energy management and implementation of energy audit and waste audit
• Mobile energy diagnostic unit
• Proper sequencing of process operation during off-peak periods and pinch analysis
• Proper tuning of combustion equipments
• Use of steam turbine exhaust for process
• Use of higher efficiency equipments in the plant
• Utilization of agricultural residues, pet coke and other residues for power
generation.
Chemical process industries use large number of equipments like dryers, grinding
equipment, distillation columns, evaporators, heat furnaces, etc. Safety energy efficiency
performance of these equipments must be evaluated regularly. Over 60% of electrical
energy is consumed by utilities like pumps, refrigeration system, air compressors, cooling
towers, fans and blowers. One should not see in isolation and needs five parameters are
to be considered-production, environment safety Evaluation of performance of these
equipments is of vital importance (Dattar RM and Dixit SD, 2012).
Pumps are the integral part of chemical process industries for transportation of fluids.
Proper selection of pumps with right capacity, proper selection of motor matching the
pump size, use of throttling valves proper installation of pumps are some of the measures
for improving the efficiency of pumps. Installing an oversized pump for a given duty
will reduce the pump efficiency from 82% to 77% due to partially closed valve. So it is
advisable to select the right pumps at very design stage (Harendranath and Mahdev,
2019).

27.3.1 Management of Steam

Steam is important part of energy management in chemical process industry as energy
cost constitute major proportion of operating cost. Major Research show that process
plants can reduce about 15–25% by just minimizing stem losses across the plant (Datta,
2019).The management of steam, steam flow using proper sensor and sized correctly
and repeatable is very, important in steam flow measurement (Datta, 2019). Steam flow
is measurable input in most of the chemical process industries and constitute major
Energy Management in Chemical Industry 541

proportion of the energy input to the industry. The steam economy greatly, delivering
steam through properly designed stem distribution line (Dattar and Dxit, 2014). The
efficiency of steam distribution system can be by well design steam distribution system.
The losses in the steam distribution systems can be in the form of the following (Dattar
and Dixit, 2014):
• Radiation and convection losses
• Pressure losses in distribution pipe lines
• Steam leakages in joints, valves, gauges
• Steam losses due to improper selection, incorrect location and wrong positioning
and malfunctioning of steam traps
• Appropriate location and capacity of air vents
• Poor dryness fraction of steam
Some of the major steps in effective energy conservation in steam network are:
• Good house keeping
• Monitoring and repairing of steam leakages in pipelines and equipments
• Installation of flow sensing devices
• Insulation of steam networks and upgradation of insulating material by using
insulation having low thermal conductivity, uniform density, lower cost factors
stability after repeated removal and re applications. Use of wrong material and
wrong thickness and poor workmanship is to be avoided.
• Stem condensate recovery. There is lot of opportunities for recycle of condensate
from evaporators. Condensate recovery helps in reducing cost of energy, boiler feed
water treatment, waste water treatment cost.
• Minimizing steam venting
• Recovery of LP steam by flashing high pressure and medium pressure steam
• Supply of steam at requisite pressure and temperature. proper scheduling and
maintenance of steam traps. Functioning of steam traps is a major source of energy
wastage in the form of steam. Points to be considered in maximum efficiency are
correct sizing, proper maintenance of steam traps, life and reliability of the traps,
proper material of construction avoiding corrosion.
• Maximizing efficiency of boiler by controlling excess air, use of low ash coal,
monitoring of unburnt combustible gas like CO and reducing unburnt carbon in fly
ash by proper combustion, improving maintenance practices, minimizing radiation
loss. CO controls helps in direct fuel saving, auxiliary power saving, lower NOx
emission.

Energy Audit, Bench Marking and Energy Information System

Energy Audit is the key to a systematic approach for decision-making in the area of
energy management. It attempts to balance the total energy inputs with its use, and
serves to identify all the energy streams in a facility. It quantifies energy usage according
to its discrete functions. Industrial energy audit is an effective tool in defining and
pursuing comprehensive energy management program.
Good energy information system and cost accounting system helps in motivating
the operating professionals and management which helps in reducing fuel and
electricity cost. It helps in identification of fuel and electricity cost reduction investment
opportunities at various stages. Energy audit has been made mandatory now.
542 Chemical Process Technology

Establishment of effective energy management policy helps in understanding of energy

conservation and enlighten about the opportunities for reducing energy consumption.
It helps in targeting high energy consuming processes and equipment and controlling
the energy usage. There are two steps in energy audit: Preliminary energy audit (PPE)
and detailed energy audit (DEA). Energy audit and bench marking of energy have got
momentum in industry in recent year to reduce energy cost due to Bureau of Energy
Efficiency (BEE) (Bharat Yadav, 2019).
Benchmarking has become one of the important practices that produce superior
performance when adapted and implemented. Benchmarking is recognized as an
effective approach towards improving efficiency, productivity, quality, profitability
and other such dimensions of performance that determine competitiveness (Sil, et al.,
2005). Energy Management system ISO 50001:2018 has been implemented by many
plants to improve energy performance (Desmukh, 2019).

27.4 ENERGY CONSUMPTION IN PULP AND PAPER INDUSTRY

Pulp and paper industry uses large amount of power during various stages of pulp
and paper making. Specific energy consumption in Indian paper industry is high in
comparison to developed countries.
• World: 30–41 GJ per ton of paper
• India: 51.6–80 GJ per ton of paper
Energy conservation measures in pulp and paper industry are:
• High capacity utilization resulting in reduction in overall energy consumption
• High capacity chipper and maintaining uniformity of chip size
• Avoiding idle running of equipments
• Proper lagging of digester, steam line and blow tanks
• Indirect cooking in place of direct cooking
• High capacity digesters and replacement of batch digester with continuous digester
• Improvement in washing, screening and bleaching
• Effective cleaning of evaporator
• Increase in concentration of black liquor and use of falling film evaporator
• Use of vapor compression evaporator
• Proper scheduling of shoot blowing system
• Proper control of excess air
• Improvement in beating and refining of pulp by replacement of beaters with high
capacity disc refiner
• Improvement in water removal in press section to reduce steam consumption.

27.5 ENERGY CONSERVATION MEASURE IN CEMENT PLANT

Cement industry is highly energy intensive industry and total energy cost about 40% of
the total cost of production. Grinding and pyroprocessing are the two measure energy
consuming sections in cement plant and measure technological developments have been
in these areas. Specific energy consumption in cement plant is high in comparison to
other developed country. There has been considerable development in cement industry
to reduce the energy consumption:
• Replacement of the convention wet process which is most fuel intensive with dry
process
Energy Management in Chemical Industry 543

• Achievement of high capacity utilization

• Use of mineralizer for lowering clinker temperature
• Use of vertical roller mill and press roll resulting in increased output, reduction in
overall energy consumption in grinding, less space requirement and uniformity in
particle size
• Suspension preheater using 4–5 stage cyclones for preheating the raw material mix.
Resulting in reduced energy consumption in kiln.
• Precalcination technology resulting in increase in capacity of kiln and reduced energy
consumption
• Use of high efficiency separators resulting in increase in output and reduction in
energy consumption.
• Use of grinding aids for reducing grinding time and improved grinding efficiency
and reduced energy consumption
• Power generation from waste gases
• Use of alternative fuel
• Utilization of industrial wastes like slag, fly ash, red mud, phosphogypsum, lime
sludge fro paper industry, calcium carbonate from fertilizer industry.

27.6 ENERGY CONSERVATION IN FERTILIZER PLANTS

Fertilizer industry is one of highly energy intensive units. Ammonia which is the building
blocks for nitrogenous fertilizer and many phosphatic fertilizer using ammonia. Rising
cost of natural gas, naphtha which is the major feedstock and fluctuation in the price of
it has direct impact on the fertilizer production cost. The feedstock has also impact on
the overall cost of production. Increasing demand of fertilizer and rising cost of feed-
stocks and utilities, implementation of energy conservation measures has become very
important in order to reduce overall cost of production. Specific energy consumption in
fertilizers industry has been brought down by improving the technology and shifting
from heavier feedstock to natural gas, shale gas, naphtha. Better feedstocks and process
technologies, together with improved operation and maintenance the average specific
energy consumption in ammonia production has been brought down from 13.7 Gcal
per ton in 1985/86 to 9.14 Gcal/ton in 2003–04 (Ashokan and Jayachandra, 2010) and
presently 7 Gcal/ton. Further improvement is possible as theoretical energy requirement
is only 4.5 Gcal/ton of ammonia. FAI is targeting to reduce the specific energy
consumption to the level of 6.5 Gcal/ton. There has been continuous development in
processes in ammonia technology and new ammonia synthesis technology reduces plant
capital investment, operating cost and energy consumption. During FY 2016–17 Aonla
has been able to reduce its energy consumption to 5.484 Gcal/MT by commissioning
CO2 recovery from flue gases of primary reformer.
Now IFFCO has got measure breakthrough in energy consumption by installing
carbon dioxide recovery from flue gases of primary reformer. Now proprietary KS-1
solution being used for absorption of CO2. Based on MHI technology. MHI technology
employs structured packing in their fuel gas water cooler and CO2 absorber resulting
high liquid to gas contact efficiency and lower pressure drop, decreased equipment
sizing and decreased utility costs in flue gas blower/circulation pumps. MHI technology
claims to have relatively higher CO2 loading, low regeneration energy, low corrosion,
low degradation and low solvent loss for proprietary KS-1 solvent. CO2 recovered from
this process being used for urea manufacture reducing CO2 emissions and reducing
544 Chemical Process Technology

greenhouse gas and contributes to cleaner environment. Successful implementation of

CO2 recover project has contributed toward reduction in cost of production, contributed
to cleaner environment and helped in conservation of carbon intensive fossil fuels like
naphtha thus contributing to national energy security (Rao, 2017).

27.7 ENERGY CONSERVATION MEASURES IN PETROLEUM REFINERY AND

PETROCHEMICAL INDUSTRY
The Indian refinery segment is experiencing fundamental shift in its operation paradigm
owing to multiple changes at the business and operation level. With notification of
BS-6 fuel refiner are forced to achieve annual specific energy consumption (Gulbani,
2019) as per Bureau of Energy Efficiency. The primary energy source over the next two
decades and beyond will continue to be fossil fuels, with coal contributing 45–50% of
the coal requirement, followed by crude oil. Thus refining sector will have important
role in sustained supply of energy resources (Table 27.3). Refinery gas treating system
can contribute significantly toward the overall operation productivity (Gulbani, 2019).
Petroleum industry is energy intensive and the energy consumption is affected by
refinery configuration, type of feedstock processed, severity of operation, vacuum
system employed, steam and power balance, process technology, yield pattern, mandate
in product specifications, environmental regulations, flexibility in operation (Dey, et
al. 2003). Energy in atypical refinery is 60% of variable costs. A 1% improvement in
energy equals roughly $650,000 year saving for a 100,000 bpsd refinery (Krishnan, 2003).
Some of the major approaches for energy conservation are energy efficient design,
improving energy efficiency, energy efficient operation, benchmark energy performance,
continuous energy improvement. Some of the major energy conservation measures
taken in Indian refineries are (Mall, 2015; Gulbani, 2019):
• Provision of high efficiency burner
• Heat integration through pinch technology in crude distillation unit
• Use of pressure gas
• Installation of soaker technology
• High emissivity refractory coating in crude distillation furnace
• Residuum oil supercritical extraction process which consumes less energy than
conventional method.
• Replacement of existing refractory with ceramic fiber in crude distillation furnace
• Replacement of metallic fans with FRP blades
• Effective condensate recovery
• Installation of more efficient steam traps

Table 27.3: Typical energy consumption pattern in a petrochemical industry

Description Units Typical range
Specific electrical energy consumption kWh/MT 328–348
Specific thermal energy consumption M kcal/MT 1.4–1.5
Overall specific energy consumption M kcal/MT 1.72–1.85
Energy cost/ manufacturing cost % 3.4–4.4
Sources: Energy Management Policy, Ch 6, BEE, p.557.
Energy Management in Chemical Industry 545

• Replacement of old low efficiency reciprocating compressor with high efficiency

centrifugal compressors
• Installation of blow down recovery system
• Use of oxygen analyzer for regular checking of excess air and efficiency in furnace
• Hydrocarbon loss reduction by way of strict control and monitoring of flare (by use
of physical acoustic leak detector for detection of leakage of fuel gas from safety
valves, control valves and bypass valves of flare systems, handling losses, tank form
monitoring
• Installation of shell and tube type condenser, primary condenser using refinery
cooling water as cooling media and two stage ejector system in vacuum column
• Installation high efficiency boilers
• Installation of hollow FRP blades in cooling towers in place of GRP/aluminum blades
• Preheat improvement in Vis breaker unit by exchanger cleaning sequence to avoid
fast fouling of preheaters which uses very heavy residue as feedstock containing
high wax, asphaltene and metal contents
• Use of steam turbine for boiler feed pump
• Chemical treatment of cooling water, for improving exchanger fouling factor
• Steam trap auditing
• Better insulation management
• Increasing of LP burner trip
• Improvement in burner performance by nitrogen injection in sulfur recovery unit
• Installation of auto combustion control loop
• Installation of fugitive emission monitor
• Monitoring hydrocarbon losses
• Selecting solvent of high selectivity and capacity in gas treating system.
Crude distillation unit has the highest processing capacity in a refinery integrating a
flash drum in an atmospheric crude oil distillation unit offers the potential for savings
and capacity enhancement (Kumar, et al. 2014).
Petrochemical industry is an energy intensive unit. Energy cost counts for approxi­
mately 70% of production costs in typical ethane- or naphtha-based olefin plants. The
rising cost of energy inputs—coal, oil, electricity and raw materials—has forced the
industries to go for energy efficient technologies and energy resource conservation
measures. Energy conservation is one of the major activities in the petrochemical
industry and energy cost is a major component of total cost of production (Mall, 2014).
Various methods have been reported for better heat recovery, such as the application
of heat energy analysis and for achieving energy saving. Integrating a flash drum in
an atmospheric and crude distillation unit offers the potential for saving and capacity
enhancement as crude distillation is highly energy intensive in a refinery (Kumar,
et al. 2014).
Indian oil is a major energy company and efforts are being made to develop transport
fuels from renewable sources for sustainable development (Tuli and Gupta, 2010).
Biofuels are getting worldwide attention to explore the substitutes for petroleum derived
fuel. Biofuels incude ethanol derived from alcohol, biodiesel, DME and FT liquid made
from lignocellulosic biomass (Chemical Industry Digest, August 2010, p.88). Oil and gas
industry accounts for major of global energy cost and pinch analysis plays important
role in reducing cost of energy and enhancing energy efficiency (Ray and Kumar, 2019).
546 Chemical Process Technology

Steam cracking of naphtha/gas is the most energy consuming process in the

petrochemical plant and globally uses approximately 8% of the sector’s total primary
energy use. It has been reported that pyrolysis section of naphtha cracker approximately
consumes 65% of the total process energy and approximately accounts for 75% of the
total energy loss (Ren, et al. 2006).
Major energy improvements by revamp or by replacing the existing furnace sections
can be achieved by the following (Fiegel and Schmidt, 2007):
• Increased thermal efficiency
• Higher radiant efficiency and less excess air by new burner technology and better
instrumentation
• Reduced heat losses due to fewer and bigger furnace units or new refractory
• Higher yields by new radiant coils, reducing specific energy demand
• Higher availability by application of new and highly reliable technology, reducing
losses due to unplanned shutdowns.
27.7.1 Energy Recovery with Compact Heat Exchangers
Compact heat exchangers are finding wide application in industry for heat recovery
applications where high efficiency is vital and space and weight constraints apply.
Compact exchangers offer benefits in following four areas over conventional shell and
tube heat exchangers (Matsufugi, 2012). Pinch technology is best heat methodology for
best network of heat exchanger and utility system to minimize energy cost of a process
(Ray and Kumar, 2019).
27.7.2 Energy Management System ISO 50001
Due to environmental consideration and energy balance there is focus on energy
efficiency and improvement in energy performance. Several countries had developed
energy management guidelines prior to ISO 50001. ISO 50001 enable organizations
to establish the systems and processes necessary to improve energy performance,
energy efficiency, use and consumption. It addresses strategic management of energy
(Khalpada, 2012).

27.8 NUCLEAR ENERGY

Nuclear energy is considered most clean environmental friendly with less cost of
production. Uranium and thorium are the two major raw materials for nuclear power
generation. India’s nuclear energy self sufficiency extended from uranium exploration
and mining fuel through fuel fabrication, heavy water production, reactor design and
construction, to reprocessing waste management. It has a small fast breeder reactor and
is building and much larger one. It is also developing technology to utilize its abundant
resources thorium as a nuclear fuel.
The annual requirement of fuel for pressurized heavy water reactors for the years
2014, 2015, 2016 and 2017 is about 875, 875, 985 and 1330 tons, respectively of natural
uranium as uranium oxide. The total requirement of nuclear fuel over the next five years
(2015–16 to 2019–2020) is estimated to be about 5,940 tons of natural uranium as UO2 for
PHWRS, 60 tons of low enriched uranium as UO2 for Tarapur Atomic Power Stations
1 and 2 for billing water reactors and about 250 tons of LEU as UO2 for Kundankulam
Nuclear Power project for light water reactors (Source: Government of India, Department
of Atomic Energy, 2015).
Energy Management in Chemical Industry 547

India’s three stage nuclear power program was for mutilated by Homi Bhabha in
1950s to secure the country’s long-term energy independence through the use of uranium
and thorium reserves found in monazite sands of coastal regions of South India.
27.8.1 Profile of Nuclear Power India
The headquarter of Indian nuclear project is located under Department of Atomic
Energy which is located at Bhabha Atomic Research Centre, Trombay where all the
research projects are done. It was established in 1957. First Indian nuclear power project
was constructed at Tarapur in Mumbai. As per World Nuclear Association, India has
a flourishing and largely indigenous nuclear power program that expects to have
14.6 GWe nuclear capacity on the line by 2024 and 63 GWe by 2032. It aims to supply
25% of electricity from nuclear power by 2050. Due to earlier trade bans and lack of
indigenous uranium, India has uniquely been developing a nuclear fuel cycle to exploit
its reserves of thorium.
NPICL supplied 35 TWh of India’s electricity from 5.3 GWe nuclear capacity with
over all capacity factor of 83% and availability of 88% in 2013–14. Some 410 reactor-years
of operation had been achieved by December 2014. Major nuclear power locations and
proposed plants in India are given in Table 27.4.

Table 27.4: Major nuclear power locations and proposed plants in India
State Location
Maharashtra Tarapur, Jaitapur
Rajasthan Rajasthan Atomic Power Corporation, Rawathbhata (near Kota)
Uttar Pradesh Narola
Gujarat Kakrapar
Karnataka Kaiga
Tamil Nadu Kalpakkam, Kudarkulam
Andhra Pradesh Kowada
West Bengal Harpur
Madhya Pradesh Proposed
Haryana Proposed

27.8.2 Nuclear Power Generation

Nuclear reactors producing heat by splitting uranium atoms produce electricity in
the same way as the conventional way of generating power where steam generated
by burning fuel is used for generating power. Uranium atoms make heat by splitting
which is termed as fission.
In nuclear power plant, uranium is used as major nuclear fuel. Natural uranium
has two isotopes: U-235 and U-238 in the ratio of 1:139. Fission of the uranium atoms
liberate heat which is used to heat water and generate steam which is utilized to generate
electricity. Normally three stages are involved in nuclear power generation:
First Stage Nuclear Reactor
In the first stage nuclear power reactors indigenous uranium is used as fuel. As U-235
is fusible and U-238 is fertile but not fusible. Uranium is generally enriched to increase
U-235.
548 Chemical Process Technology

Here pressurized heavy water reactor is used. Heavy water is used as moderator, and
normal water is used as coolant. During the nuclear reaction, neutron is bombarded on
nuclei which splits the atoms in 2 parts and sometimes 3 parts and releases significant
amount of energy. Further fission reaction occurs by the excess neutrons. Some of the
surplus neutrons are get absorbed in other isotope U-238 and give plutonium.
Spent of first stage reactor which consists of plutonium (Pu239) and unconverted
U-238. Second stage involves reaction of plutonium in fast breeder reactor. Heavy water
moderates the speed of release of neutrons and increasing the probability of U-235.
Second Stage Neuclear Reactor
In second stage, fast breeder reactor is used. Here mixture of U-238 and plutonium-239
is used as fuel and fed to fast feed reactor without using and moderator. In second stage
reactor, U-232 present in the uranium is converted to U-233.
Third Stage Neuclear Reactor
Thorium-based reactor: Thorium is considered more effective and gives less radioactive
substance than the conventional first stage reactor.
In the third stage, the U-232 which is present in the uranium is converted to U-233
by thorium obtained from the second stage is reacted with thorium which is a blanket
material and produces Uranium-233b in thorium-based reactor. Spent fuel from the
second stage is processed to obtain plutonium.
Reactions involved in heat generation from uranium and thorium are as follows:
92
U238 + 0n1 92
U239 93
Np239 94
PU239

Fission reaction: 92
U238 + 0n1 38
Sr90 + 38Xe144 = 20n1 + +200 MeV

Reactor poisoning reaction: 52

Te135 53
I135 54
Xe135 55
Cs135 56
Ba135

Various type of nuclear reactors are fast beeder reactors, thermal reactors, heavy
water reactor, etc.

BIBLIOGRAPHY
1. Annual Report 2019–20, Ministry of Coal and Mines, Government of India.
2. Ashokan A, Jayachandra. “Indian Fertilizer Industry–Problems and Prospects”, Chemical
Industry Digest Annual, Jan 2010, p.129.
3. Bharat Yadav. Chemical Industry Digest, September 2019, p.65.
4. Chemical Industry Digest, August 2010, p.88.
5. Dattar RM, Dixit SD. “Great Potential to save energy in process Industries”, Chemical Industry
Digest, May, 2012, p.60.
6. Datta K. ”Innovations in steam systems in Process Plants”, Chemical Indsustry Digest, September
2019, p.47.
7. Feigl J, Schmidt G. “Consider furnace replacement for existing olefin units”, Hydrocarbon
Processing, June 2007, p.45.
8. Gulbani R. “Energy efficiency enhancement opportunities in refineries through optimal design,
capacity debottlenecking and operational optimization of gas treating systems”, Chemical
Industry Digest, March 2019, p.43.
9. Gharpure YH. Chemical News, July 2010, p.24.
10. Government of India. Department of Atomic Energy, 2015.
Energy Management in Chemical Industry 549

11. Goel OP. “Chemical Industry productivity addressing select pursuits“, Chemical News,
September 2017, p.25.
12. Harendranath N, Mahdev K. “Integration of energy efficiency concepts at the design stage in
process Industries”, Chemical Industry Digest, July 2007, p.76.
13. IBEF 2016. India Brand Equity foundation [Link]
14. India Energy Book 2012.
15. http./[Link]/ file manager/annual report 2015–2016/EN/Chapter%201/chaptere_1.htm
16. Joshi MK. “Refining- the challenege for green technologies”, Petrofed, January–March Vol 7
Issue 1 p.3.
17. Joshi P. “Special feature on future of oil and gas sector in India”, FIPI, Volume 16 issue 1 January–
March 2017.
18. Khalpada S. Chemical News, December 2012, p.22.
19. Krishnan V, Verma RP. “Energy conservation in Refineries”, Hydrocarbon Technology, Agust
15, 1993, p.47.
20. Kumar S, Nanoti S, Garg MO. “Maximising the use of process energy”, PTQ Q2 2014, p.81.
21. Mall ID. “Petrochemical process technology”, Second edition 2017, Laxmi Publication.
22. Mall ID. “Petroleum refining technology”, First edition 2017, CBS Publication.
23. Matsufugi M. “Energy with compact heat exchangers”, PTQ 2012, p.65.
24. [Link]
25. Ray A, Sunil Kumar. ”Pinch analysis in oil and gas sector”, Chemical Industry Digest, September
2019, p.56.
26. Ren T, Patel M, Blok K. “Olefins from conventional and heavy feedstocks: energy use in steam
cracking and alternative processes”, Energy, Volume 31, No. 4, 2006, p.425.
27. Sil K, Dey GK, Naryana CSS. “Bench marking in Refinery area”, Workshop on Energy
management and conservation, Lovraj Kumar Memorial Trust, New Delhi, November 11–12,
2003.
28. Tuli DK, Gupta RP. “Indian Oil and Renewable energy initiatives for sustainable development”,
Chemical Industry Digest, August 2010, p.83.
29. Vasudevams, Dr HL Memorial lecture at CHEMCON 2012 at NIT Jallandhar, Dec. 27, 2012.
30. World Nuclear Association http//www. World-nuclearorg./information-library/country-
profiles/countries-g-n/ [Link] energy
31. MatewTF, Rancis A. “Long Markets: A Global Perspective and Future outlook”, Chemical
Industry Digest, Annual-January 2020, p.56.
28
Environment, Health and Safety in
Chemical Process Industry

28.1 INTRODUCTION
Environment, health and safety have become important issues during recent years.
The problem has grown substantially during recent years with fast industrialization
and urbanization. Three pillars of sustainable development are economic growth,
environmental protection and social progress. Environment, health and safety issues
have received considerable interest during recent years with enforcement of various
regulations related to environment, health and safety. Environmental standards,
safety rules are becoming more and more stringent requiring special attention related
to environment, health and safety. Complexity of chemical process industries and
requirement of newer products have complicated the environmental management
problems. Environmental impact assessment has been made mandatory for set up
new industries and projects requiring more attention from project stage. However, the
problem in India is more complicated in comparison to developed country because
of existence of older and smaller products. Abnormal situations in the plant can be
managed by prevention, early detection, and mitigation, in order to reduce unplanned
outages and process viability that increase production, safety and environmental risks
to plant employees and local community (Bullemer and Reising, 2018).

28.2 ENVIRONMENTAL PROTECTION ACTS, RULES, AND VARIOUS AMENDMENTS

Although some of the Acts like Indian Boiler Act, 1923, Mines and Mineral Act
(Regulation and Development) Act, 1947, Wildlife Protection Act, 1972 came into
existence, Forest (Conservation) Act before independence and after independence,
however, specific Act related to environment was water Pollution Act came in 1974. Real
impetuous to environment pollution control was after constitution of Central Pollution
Control Board and state pollution control boards. Due to increasing environmental
concern there has been continuous upgradation of Environmental Protection Acts,
Rules and various amendments have been made.

28.3 ENVIRONMENT, HEALTH AND SAFETY MANAGEMENT IN PROCESS INDUSTRIES

Environmental hazards from chemical process industries are human health, impact on
animal, vegetation, material damage, human toxicology, severe respiratory and skin
irritant, Individual workers: Deaths due to exposure to gases like chlorine, ammonia,
bronchitis, impure sense of smell (hypoosmia) and gastritis, bleachery disease (bleachery
ranking), bronchial disease, hemoptysis, premature aging. Mining, metallurgical, pulp
550
Environment, Health and Safety in Chemical Process Industry 551

and paper industries are more affected by particulate matters. Chlorine plants, ammonia
plants, pulp and paper plants are more prone to toxic gaseous emissions. Now EHS has
been the prime focus area in most of the process industries, and it is being reviewed
continuously now by management and government agencies and now has become an
important part of the business activities. Environmental and safety audit, monitoring and
control of pollution, fire control accident/incident/near missing reporting, hazardous
waste management using good practices, good house-keeping, following safety culture
have become now a regular features in most of the organization.

28.3.1 Characteristics of Hazardous and Toxic Wastes

• Ignitability
• Corrosiveness
• Reactivity
• Toxicity
• Radioactivity

Modern chemical process industries have become increasingly more complex and
managing safety have become more difficult and challenging. Safety results in freedom
from accidents. Safety today is more important, since we are developing our industry
rapidly. Due to rapid development in information technology and communication,
safety awareness has grown so much that, today without safety very existence and
growth of industry is unimaginable. Several accident investigators have found that
80% corresponds to human errors and 20% corresponds to technical failure that has
been termed as the 80–20 rule. Basic causes of accident and their impact is given in
Figure 28.1. Disaster management plan is an important aspect in disaster mitigation.
Disaster management plan is given in Figure 28.2. Present state of art safety management
includes safety studies (HAZID, HAZAOP, risk analysis, safety instrumented systems
for fire and gas detection and emergency shut down, abnormal situation management
applications and operator guidance tools (Truk and Mishra, 2005). Executing Process
Hazard analysis and layer of protection analysis, specifying safety instrument func­
tions and preparing safety requirements specification, developing safe integrity level
verification are some of the further steps for better safety management. Knowing
the chemicals and its properties through material safety data sheet following safety
legislation and evolution of good safety practices are some of the basic steps for sound
safety management.
Safety and health management issue includes:
• Motivational and promotion activities
• Training, education and awareness activities
• Inspection, audit and testing
• Investigation and analysis
• System perfection.
One of the principle of safety management is to manage safety like any other
company function and management should make direct safety efforts by setting
achievable goals by planning, organizing and controlling to achieve safety efforts
(Mathur, 2007). Companies with well developed safety culture experience benefits of
552 Chemical Process Technology

Fig. 28.1: Basic causes of accident

Fig. 28.2: Disaster management plan (Source: Mall, et al. 2007)

superior performance in safety, workers involvement in process improvement, quality

improvement and lowering the overall costs (Doshi, 2015).
A major accident may be based on-site and off-site losses, and disaster management
plan may include on-site and off-site management plant.
Four pillars of risk based process safety are commitment to process safety, under­
standing the hazards and risks, managing the risk and analysis of past accidents, and
improving the basic safety issues.
Process industries include a great variety of processes that use basic feedstock
from petroleum industries for production of large variety of intermediate products,
which are used for the production of wide spectrum of products: polymers, synthetic
fibers, synthetic rubbers, explosives, pesticides, dyes and intermediates, paints, dairy,
metallurgical, electroplating, etc. Various pollutants from major process industries are
given in Table 28.1. In addition to various pollutants, large number of catalysts, additives
and chemicals are being used during various stages of operation. VOC emission is
common phenomena in most of the process industries.
Environment, Health and Safety in Chemical Process Industry 553

Table 28.1: Environmental pollution from process industries

Industry Pollutants
Pulp and paper industry High BOD, COD, color, AOX, lignin, chlorinated phenols, resins,
particulate, mercaptans, H2S, SO2, chlorine, chlorine dioxide, carbonate
sludge, mercury, chlorides, lime sludge, VOC, odor
Fertilizer industry Ammonia, SOX, NOX, CO2, arsenic, chromium, urea, chromium carbon
slurry, phospho gypsum, fluorine and fluoride, particulate matter,
carbonate sludge, oil and grease, heavy metals, radioactive substances,
VOC, spent catalyst, rock phosphate pile, phospho gypsum sludge piles
Distillery industry High BOD and COD, color, chlorides, potash, sulfate, high potassium
fermenter sludge
Oil and gas exploration, Oily water, sediments, spent caustic, sour water containing hydrogen
production and sulfide, emission of hydrocarbons, hydrogen sulfide, CO2, surfactant,
processing polymer alkali
Petroleum industry Phenols, oil and grease, particulate matter, cyanide, spent caustic, sulfur,
oily sludge, VOC, spent catalyst, contaminated blow down waste, SOX,
NOX, CO2, mercury
Petrochemical and Spent caustic, vinyl chloride, chlorinated hydrocarbon, HCN, various
chemical industry toxic organic compounds, pyridine picoline, acrylonitrile, etc. VOC, spent
catalyst, SOX, NOX, CO2
Caustic-chlorine plant Emission from cell house, chlorine, mercury, brine mud, spent sulfuric
acid
Mineral acids: sulfuric SO , NO , chlorine, ammonia, acid mist, HF vapor, silicon tetra fluoride
X X
acid, hydrochloric acid, spent catalyst, HCl vapor
nitric acid, hydrofluoric
acid
Cement plant SOX, NOX, CO2, mercury, particulate matter, lime stone piles leachate
Synthetic fiber industry Carbon disulfide, high alkalinity, BOD, COD, SOX, NOX, CO2 particulate
matter
Agrochemicals Toxic pesticides, BHC, COD, maliathon, toxic chemicals
Textile industry Dyes, toxic chemicals, high COD,
Dyes and intermediates Dyes, metals, COD, BOD, toxic chemicals, heavy metals, Pb, zinc, copper,
and pigment etc.
Soap and detergent Caustic soda, oil, HF, hydrocarbon waste, spent catalyst, SOX, NOX, CO2
Coke oven plant, iron Cyanide, aromatics, SOX, NOX, CO2, VOC, tar, phenol, picoline, pyridine,
and steel particulate matter, oil and grease
Metallurgical industry Heavy metal, copper, cadmium, nickel, lead, cobalt mercury, silver, zinc,
(non ferrous) beryllium, particulate matter, SOX, NOX, CO2, cyanide waste
Automobile industry Particulate matter, hydrocarbon, paint, VOC
Dairy and food High COD, BOD, suspended solids, sludge, milk waste, odor, microbes,
processing industry food raw material waste
Tannery Chromium, high COD, suspended solids, odor
Electroplating industry Heavy metals like nickel, cadmium, silver, cyanide, etc.
Paint and varnish, ink Pigments, resins, plasticizers, VOC, hydrocarbon emission, particulate,
and adhesive odor
Coal fired boilers Particulate matter, SOX, NOX, CO2, mercury, fly ash, scrubber sludge,
coal pile runoff
554 Chemical Process Technology

Layer protection analysis (LOPA) has become one of the most important risk analysis
techniques in the process industry. LOPA is commonly used risk analysis methodology
in the process industries.
Some of the important facts for safety and health in a chemical industry are (Rao,
2017):
• Risk of accidents and harmful exposure area of concern
• Toxic and hazardous material environment
• Flammable vapor, gases and dust
• Hazardous chemical reactions
• Hazardous operations
• Health hazards due to corrosion
• Entry to confined spaces
• Working with pipelines and not following safety rules
• Plant alteration and modification
• Sampling and gauging
• Hazards due to instrument failures.
Average percentages and ranges for the three types of sources of abnormal situation
identified in planned incident reports had following ranges (Bullemer and Reising,
2018):
• People and work context (35–38%)
• Equipment (30–45%)
• Process equipment (3–35%)
Finding of Chemical Manufacturers Association that up to 80–85% of human
error contributed to process safety incidents. For the involving people and works
context factors following root causes were reported (Bullemer and Reising, 2018;
Lorenza, 1990).
• Inadequate or no procedure (27%)
• Fail to follow procedure (24%)
• Inadequate or incorrect action (24%)
• Inadequate work practice (15%)
• Fail to recognize problem (5%)
• Defective installation (5%).

28.3.2 Categorization of Industrial Sectors

Industrial sectors have been characterized based on the pollution index and requirement
of EIA depends on its pollution index:
• Red category: Industrial sectors having pollution index score of 60 and above
• Orange category: Industrial sectors having pollution index score of 41–59
• Green category: Industrial sectors having pollution index score of 21–40
• White category: Industrial sectors having pollution index score of up to 20.
There shall be no necessarily of getting consent to operate for white categories
industries. An intimation to concerned SPCB/PCC shall suffice. No red categories
of industries normally be permitted in the ecological fragile area and protected area.
Environment, Health and Safety in Chemical Process Industry 555

MOEF has issued a Gazette notification (GSR 608 (E) dated July 21, 2010) on organic
chemicals manufacturing industry. This includes effluent standards, process emission
(specific pollutants) and process emissions (General pollutant), standards for fugitive
emission, Standard for storage of Benzene, vinyl chloride monomer and acrylonitrile
(Chemical News, 2010).

28.4 ENVIRONMENTAL POLLUTION FROM PETROLEUM AND PETROCHEMICAL INDUSTRY

Petroleum and petrochemical industry is a complex and an integrated industry that
includes a large variety of processes and products. Because of a large number of
processes, use of wide variety of raw materials, catalysts, additives, chemicals, presence
of explosives and hazardous materials; the environmental pollution problem from
petroleum and petrochemical industries is quite complex. Wide variety of pollutants
are discharged into water stream and emitted into the environment.
Some of the major sources of pollutants in petroleum refinery are crude oil storage,
crude processing–desalting and distillation, secondary processes–thermal, catalytic
cracking, hydrocraking units, reforming, catalyst regeneration units, hydro processing
units, lube refining and lube treatment processes, boiler blow downs, power plants,
effluent treatment plants, etc.
Major pollutants are free and emulsified oils, phenols, cyanides, inorganic salts,
naphthenic acids, heavy metals, sulfides, spent catalyst; tars; H2S, NH3, NOX, SOX, CO,
CO2. Averaged total hydrocarbon release to refinery sewers range 0.5–4.0% of the total
crude charge. Typical emissions from refinery include particulate matters, SOX, NOX,
BTX and VOC emissions. Managing refinery spent caustic is another important issue
due to increasing polishing and sweetening processes in the refinery.
Many of the gases emitted by refineries are harmful to humans, and can cause
permanent damage and even death. They can cause respiratory problems (such as
asthma, coughing, chest pain, choking, bronchitis), skin irritations, nausea, eye problems,
headaches, birth defects, leukemia, and cancers.
Petroleum refining and petrochemical processes are very complex and contribute
to wide spectrum of pollutants found in effluent streams which include process oily
waste water, spent caustic waste, desalter and sour water effluent, tank farm effluent,
demineralization (DM) and condensate polishing unit (CPU), waste, cooling tower blow
downs (CTBD), contaminated rain water (CRW), and sanitary waste. Emission from
petroleum and petrochemical complex can be classified into four major categories:
• Storage and handling emissions
• Process emissions
• Fugitive emissions
• Secondary emissions.
28.4.1 Gasoline Benzene Reduction
With new fuels regulation for reduction in benzene in gasoline below 1%, there is big
challenge for refiners to meet the tightening gasoline specifications for benzene at the
lowest cost and without significant octane loss (El-Mekki, El-Malki, et. al. 2013.). Benz
OUT process has been developed by Exxon Mobil Research which provides a low cost
alternative solution for benzene regulation without octane and hydrogen debits. The
process uses liquid phase fixed bed technology using a propriety highly active zeolite
catalyst with long cycle lengths (El-Mekki, El-Malki, et. al. 2013). MINAS for oil refineries
and petrochemical plant is given in Tables 28.2 and 28.3.
556 Chemical Process Technology

Table 28.2: MINAS for effluent oil refineries

Parameter Limit (mg/L, except for pH) Limit for quantum (kg/1000 MT of crude
processed except for pH)
pH 6.0–8.5 –
Oil and grease 5 2
BOD3 @ 27ºC 15 6
COD 125 50
SS 20 8
Phenols 0.35 0.14
Sulfides 0.5 0.2
CN 0.2 0.08
Ammonia as N 15 6
TKN 40 16
P 3 1.2
Cr (VI) 0.1 0.04
Total Cr 2 0.8
Pb 0.1 0.04
Hg 0.01 0.004
Zn 5 2
Ni 1 0.4
Cu 1 0.4
V 0.2 0.8
Benzene 0.1 0.04
Benzo (a) pyrene 0.2 0.08
Sources: EIA Notification, 2006.

Table 28.3: MINAS for petrochemicals

Parameters Limit (mg/L, except for pH)
pH 6.5–8.5
BOD 30
Phenol <1
Sulfide 2
Cyanide 1
Fluoride <5
Total suspended solids 100
Hexavalent chromium 0.1
Total chromium 2
Sources: EIA Notification, 2006.
Environment, Health and Safety in Chemical Process Industry 557

Major pollution caused by petroleum industry is given in Figure 28.3.

Fig. 28.3: Major pollution caused by petroleum industry

Oily sludge, spent catalyst and spent caustic are some of the major sources of solid
waste generation in petroleum and petrochemical complexes: Olefin plant (Naphtha/
Gas Cracker Units), Ethylene Oxide and MEG plant, Aromatic Production Unit, Catalytic
Reforming, Methanol Plant.
558 Chemical Process Technology

MOEF has issued a notification for emission standards for petrochemical industry
which is available in Gazette notification-GSR. No 820(E) dated November 9, 2012
(Chemical News, 2013) (Tables 28.4 to 28.7).

Table 28.4: Standards for equipment leaks

General hydrocarbon (ppm) Benzene (ppm)
Component Till 31st Dec. w.e.f. Jan 01st, Till 31st Dec. w.e.f. Jan 01st,
2008 2009 2008 2009
Pump/compressor 10000 5000 3000 2000
Valves/flanges 10000 3000 2000 1000
Other components 10000 3000 2000 1000
Sources: EIA Notification, 2006.

Table 28.5: Standards for loading of volatile products

Gasoline and Naphtha i. VOC reduction, % 99.5

ii. Emission, mg/m3 5

Benzene i. VOC reduction, % 99.99

ii. Emission, mg/m3 20

Toluene/xylene i. VOC reduction, % 99.98

ii. Emission, mg/m3 150

Sources: EIA Notification, 2006.

Table 28.6: Emission standards for furnace and boiler

Parameter Fuel type Existing refineries limiting
concentration (mg/Nm3)

SOX Gas 50
Liquid 1700

NOX Gas 350

Liquid 450
PM Gas 10
Liquid 100
CO Gas 150
Liquid 200
Ni + V Liquid 5

H2S in fuel gas Liquid/gas 150

Sulfur content in liquid fuel, wt % Liquid/gas 1

Sources: EIA Notification, 2006.
Environment, Health and Safety in Chemical Process Industry 559

Table 28.7: Emission standard for FCC regenerators

Parameter Existing refineries limiting concentration (mg/Nm3)
Hydro processed FCC feed Other than hydro processed FCC feed
SOX 500 1700

NOX 400 450

PM 100 100
CO 400 400
Ni + V 2 5
Opacity % 30 30
Sources: EIA Notification, 2006.

28.4.2 Hazards in Petroleum and Petrochemical Industry

Petroleum and petrochemical industries are inherently hazard prone because (Table 28.8):
• Large inventory of petroleum-highly inflammable
• Processing at high pressure, temperature
• Using hazardous chemicals
• Complexity and process integration
• Loss of containment results in fire/explosion.

Table 28.8: Water and air pollutant emission from various processes in petrochemical complex
Plant Pollutants
Olefin plant (Naphtha Inorganic sulfides, mercaptans, soluble hydrocarbons, polymerized
gas cracker units) product, phenolic compounds, sulfide, cyanide, heavy oils, coke, spent
caustic, SO X, NO X, hydrocarbons, particulates, water borne waste
containing BOD, COD, suspended solid, oil
Ethylene oxide and Dissolved organics, ethylene oxide, ethylene glycol, acetaldehyde,
MEG plant formaldehyde, heavy metals (Cd, Pb, Ni, Mn, Cu), hydrocarbons, water
borne waste containing BOD, COD, suspended solid, oil, odor, spent
silver catalyst.
Aromatic production Dissolved organics, volatile organic compounds, heavy metals, hydro­
unit catalytic reforming, carbons, particulates, H2S, SOX, NOX, CO, water-borne waste containing
anaerobic separation BOD, COD, suspended solid, oil and grease, toluene, benzene, xylenes,
HCl, chlorine, cadmium
Methanol plant Zinc, chromium, copper, methanol, ethers, esters, etc.
Formaldehyde plant Methanol, silver, iron, molybdenum, water borne waste containing BOD,
COD, suspended solid, oil and grease, heavy metals
p-Xylene plant Hydrocarbons, H2S, SOX, NOX, CO, oil, heavy ends, catalysts, water borne
waste containing BOD, COD, suspended solid, oil and grease, spent clay.
Caprolactam plant Ammonia, hydrocarbons, ammonium sulfate, water-borne waste
containing BOD (bio sludge), COD, Suspended solid, oil and grease,
waste liquor from cyclohexane section and high boiling products from
distillation unit
Acrylonitrile Ammonia, cyanide waste, hydrocarbons, water-borne waste containing
BOD (bio sludge), COD, suspended solid, oil, polymerized cyanide with
catalyst particles
560 Chemical Process Technology

28.4.3 Safety in Cracker Plant

Cracker plant is heart of petrochemical plant. Cracker is one of the more accident prone
plants due to large temperature and pressure ranges either due to chemicals, equipment
related, physicals agents, human factors.

28.5 ENVIRONMENTAL POLLUTION IN PULP AND PAPER INDUSTRY

Paper is a global commodity product. Per capita consumption of paper is yardstick
for the measurement of industrialization, social and cultural development. The paper
industry accounts for about 2.5% of world’s production and 2% of world trade.
Forces affecting the paper demand are global developments, social trends, electronic
media, economic factors, environmental preservations, changing technologies and
substitutions. Environmental pollutants from pulp and paper industry are given
in Figure 28.4.

Fig. 28.4: Environmental pollutants from pulp and paper industry

Environmental pollution from pulp and paper industry can be described as off-plant,
in-plant and application generated pollution:

28.5.1 Air Pollution from Craft Pulping

Major air pollutants released from craft pulping process are sulfur compounds like
H2S, mercaptans, etc. Causes, sources and characteristics of various air pollutants are
given in Table 28.9. Soda recovery is the major source of air pollution. New emission
standards for soda recovery units (SRUs) are given in Table 28.10.
Environment, Health and Safety in Chemical Process Industry 561

Table 28.9: Various air pollutants from craft pulping process

Pollution Cause Source Characteristic and effect
H2S Hydrolysis of Na2S Digester, BSW, Odor threshold value 4.7
evaporator, rec. Fouling smell, irritant to
furnace, lime kiln eye and respiratory system,
weakly acidic
Methyl mercaptan By reduction of Digester, BSW, Odor threshold value 2.1,
CH3SH hydrosulfide and evaporator, offensive odor, causes nausea
methoxy lignin recovery furnace, and headache, weakly acidic,
lime kiln BP 5.8
Dimethyl sulfide Reaction of mercaptan Digester, BSW, Nonacidic, odor threshold
(CH3)2S with methoxy lignin evaporator, value 1.0, BP 38
recovery furnace,
lime kiln
Dimethyl By oxidation of methyl Recovery furnace, Odor threshold value 5.6,
disulfide (CH3)2S2 mercaptan smelt dissolving BP 118ºC, offensive odor
tank, lime kiln
Chlorine Accidental leakage, Bleaching section Highly toxic, pungent,
residual chlorine in suffocating bitter, corrosive,
chlorina­tion stage Od. Th. V. 5.6.
SO2 Oxidation of reduced Recovery furnace, Acid gas having pungent
sulfur compound lime kiln smell
SO2 Oxidation of reduced Recovery boiler Mildly acidic, readily absorbed
sulfur compounds by BL in DCE
H2S From BL below pH 8 Evaporator Feebly acidic
due to hydrolysis of recovery furnace,
Na2S digester, BSW
Methyl mercaptan By reduction of Digester relief BSW Dissociate above 12 pH
CH3CH hydrosulfide and
methoxy lignin
Dimethyl sulfide Reaction of mercaptan Recovery furnace,
with methoxy lignin smelt dissolving
tank, lime kiln
Dimethyl Oxidation of methyl Retention high due to higher
disulfide mercaptan BP
Chlorine During bleaching Bleach plant

Table 28.10: Emission standards for SRUs

Parameter Plant capacity (tons/day) Existing SRU
S recovery % >20 98.7
H2S mg/Nm 3 >20 15
S recovery % 20-May 96
S recovery % 5-Jan 94
NOx, mg/Nm 3 All capacity 350

CO, mg/Nm3 All capacity 150

562 Chemical Process Technology

Toxicity Removal of Bleach Plant Effluent

Various approaches for reducing toxicity of bleach plant effluent are:
• Delignification of pulp as much as possible before chlorination stage to decrease
residual lignin pulp
• Improved brown stock washing and screening
• Improvement in bleaching sequence to reduce or eliminate use of elemental chlorine.
Options for lowering the emission of chlorinated organic matters including dioxins
and furans are:
• Lowering chlorine, consumption increasing, chlorine dioxide use
• Use of hydrogen peroxide and oxygen in extraction stage
• Bio bleaching
• Split addition of chlorine
• Adjusting the operating parameters in the chlorination stage
• Total chlorine-free bleaching (TCF) lowering pulp brightness
• Environmental hazards in pulp and paper industry can be defined as the hazards
associated with some serious environmental problem like discharge of highly polluted
and toxic material bearing waste water, mission of particulate matter, dust, flue gases,
production of hazardous solid waste and noise pollution.
Bring here Table 28.11 standard for pulp and paper industries.

Black Liquor Oxidation

To facilitate odor control and chemical recovery
2Na2S + 2O2 + H2O Na2S2O3 + 2NaOH
• Weak black liquor oxidation
• Strong black liquor oxidation
Lesser tendency to foam and off gases from black liquor oxidizer contain less sulfur
compound)
Advantages: High sulfidity, possible reuse of evaporator condensate, reduced corrosion,
uniform operation of evaporator, increased recovery.

28.5.2 Categorization of Pulp and Paper Mills

• Forest-based Pulp and Paper Mills (Large Scale): Eucalyptus, bamboo, popular, pine
• Agro-based Pulp and Paper Mills: Bagasse, wheat straw, rice straw, sarkanda, sabai grass
• Waste Paper based Paper Mills: Waste paper, imported purchased pulp/waste paper.

Specific to Ganga River Basin States

A1: Wood-based pulp and paper mills producing bleached grades of chemical pulps,
paper, paper boards and newsprint
A2: Wood-based pulp and paper mills producing unbleached grades of chemical pulps,
paper, paper boards and newsprint
B1: Agro-based pulp and paper mills producing bleached grades of chemical pulps,
paper, paper boards and newsprint
B2: Agro-based pulp and paper mills producing unbleached grades of chemical pulps,
paper, paper boards
Environment, Health and Safety in Chemical Process Industry 563

Table 28.11: Environmental standard for pulp and paper industries

Parameters Large pulp and paper mill Small pulp and paper mill
capacity above 24000 MT/ capacity up to 24000 MT/
annum annum
pH 7.0–8.5 5.5–9.0
TSS, mg/L 50 50
BOD, mg/L 30 30 (discharge into
inland surface water 100
(discharge on land)
COD, mg/L 250 250
AOX, kg/ton of paper produced 8 8
SAR 26 (discharge on land)
Color

28.5.3 Innovation in Technology for Waste Management in Pulp and Paper Industry
There have been significant innovation and developments in technology in pulp and
paper manufacture to improve quality, minimize the energy consumption, reduce the
toxicity of bleach plant effluent, waste water generation and reduce the color in the
effluent to improve better recycle. Pulping and bleaching are one of the major areas
where major technological development has taken place in the pulp and paper industry.
Some of the technological development in pulping and bleaching for reducing toxicity
and waste generation are given in Table 28.12.

Table 28.12: Technological development in pulping and bleaching for

reducing toxicity and waste generation
Process modification Delignification of pulp as much as possible before chlorination
stage to decrease residual lignin, improved brown stock
washing and screen, improvement in bleaching sequence to
reduce or use of eliminate the elemental chlorine
Control of outside contamination Elimination of use of defoamer containing dioxin precursors
External control measures Stabilization ponds, activated sludge, aerated lagoons,
membrane process, adsorption, electrochemical process

28.5.4 Potential health and safety hazards in pulp and paper production
• Wood preparation
• Pulping
• Sheet forming and converting
• Other operations like power generation, water treatment, effluent treatment, chlorine
dioxide generation, turpentine recovery, tall oil production, etc.
• Explosions can occur in electrolytic cells, chlorine pipelines, chlorine liquefier and
hydrochloric acid units, chlorine cylinders, chlorine pipeline.
• Liquid chlorine increases considerable in volume when evaporated. Handling
chlorine should be kept away from direct source of heat.
• Explosion in the chlorine gas line has been observed due to failure of gasifier.
• Leakage of gas line due to severe corrosion because of moisture has been observed.
564 Chemical Process Technology

• Explosion in the blower in a malodorous gas collection system has been observed.
• Fire in the waste paper due to human factor has been also observed.
• Major accidents can result in releases, fires and explosions during handling and
transport outside processing unit.
• There is generation of highly toxic compounds at various stages of pulp and paper
manufacture and cause very adverse affect to human health.
• It includes many chlorinated organic compounds viz adsorbable organic halogens
(AOX), elemental-free chlorine (ECF), dioxin, furans, Talcum powder, dust and H2S.
• Environmental health hazards can be minimized by evolving eco-awareness,
implementation of environmentally friendly approach with minimization of toxicity
and releases of malodorous gases.
• Several accident investigators have found that 80% corresponds to human errors
and 20% corresponds to technical failures that have been termed as the 80–20 rule.

28.5.5 Major Accident Reported in Pulping Section

• Burned by hot digester
• Cooking liquor
• Digester crack and explosion
• Burst, burned by exploding oxygen tank
• Flash fire vapors in digester house, resulting in death due to trapping of worker in
hot digester liquor

28.6 RISK AND HAZARD IN CHLORINE HANDLING AND PROCESSING

Chlorine is being used extensively in pulp and paper industry for bleaching and
preparation of bleach liquor. Chlorine is also used in various chemical industries for
making chlorinated organics, bleaching powder, water treatment plants. Some of the
major risk and hazard in chlorine handling and processing are:
• Explosions
• Fire
• Physical injury like-burns, etc. due to physical contact with liquid chemicals
• Chemical poisoning due to long exposure
• Short-term exposures to toxic gases during leakages, etc.
• Some of the areas where major chlorine accident has been reported are water supply/
wastewater treatment plant, swimming pool, pulp and paper, chlorine plant, optical
fiber manufacturing, dairy/poultry, textile, pesticides, petrochemical.
Chlorine accident in storage or transport, vessel filling line, process equipment,
compressors, liquefiers, vaporizers, pump, abatement equipment has been reported in
some of the areas where major chlorine accident has been reported are water supply/
wastewater treatment plant, swimming pool, pulp and paper, chlorine plant, optical
fiber manufacturing, dairy/poultry, textile, pesticides, petrochemical.

28.7 ENVIROMENTAL POLLUTION FROM FERTILIZER PLANTS (Tables 28.13 To 28.18)

1. Off-plant pollution:
Coal 2.6 T solid waste
Environment, Health and Safety in Chemical Process Industry 565

Limestone and rock phosphate 2–4 times their weight

Health hazard during mining of these raw materials.
2. In-plant pollution: Solid, liquid and gaseous pollutants (Table 28.13).

Table 28.13: Feedstocks, manufacturing process and pollutants

Feedstock Manufacturing process Pollutants
Naphtha Steam reforming Ammoniacal nitrogen
Natural gas Steam reforming Ammonical nitrogen
Fuel oil Partial oxidation Ammonical nitrogen, carbon particles, cyanide,
vanadium sulfide
Coal Gasification Ammonical nitrogen, cyanide, ash, sulfide

• Major solid wastes: Carbon slurry, calcium carbonate, sludge, phosphogypsum,

chrome sludge, fly ash, bottom ash, coal dust, lime stone dust, gypsum dust.
• Major pollutants: Arsenic, ammonia, cadmium, lead, chromium, fluorine, oil and
grease, mercury, uranium, urea, SOX, NOX, acidity, alkalinity, acid mist, phenols,
aldehydes, oil and tar
Total quantity of waste water generation from ammonia, urea plant including
utility varies from 5–10.2 m3/T of urea.
3. Application generalized pollution
• Retention of potassium
• Leaching of ammonia resulting in increase of nitrate level
• Phosphorus reacts with aluminum and oxides insoluble phosphate
• Phosphatic fertilizer results in increase in Cd level
• Off-plant pollution: Rock phosphate: As, Cd, Cr, Hg, Pb, U

Table 28.14: Pollutants from fertilizer industry

S. Pollutant Sources Health/toxic effects
no
1 Arsenic Gas purification plant in Causes cancer, poison at high levels gastro­
ammonia and urea units intestinal disorders, black foot disease, affects
plant
2 Ammonia Ammonia and urea plant Toxicity to fish and aquatic life, fish kills,
eutrophication
3 Cadmium Phosphoric and superphosphate Cardiovascular diseases, and hyperten­sion,
plant cancer, degenerative bone disease
4 Chromium Cooling tower blow downs Cancer
5 Fluorine Scrubber effluents in phospho- Dental and skeletal fluorosis, affects fish egg
ric acid and superphosphate hatching
units
6 Lead Phosphoric and superphosphate Brain damage, nausea, convulsions,
units behavioral disorders, death cancer
Contd...
566 Chemical Process Technology

Table 28.14: Pollutants from fertilizer industry (Contd...)

S. Pollutant Sources Health/toxic effects
no
7 Mercury Phosphoric and superphosphate Nerve damage, death, skeletal fluorosis
unit
8 Oil Compressors in ammonia and Reduces dissolved oxygen of water, reduces
urea manufacture photosynthesis
9 Phosphate Phosphoric acid complex Algal blooms
fertilizer units
10 Uranium Phosphoric acid and Radiation damage, cancer
superphosphate
11 Urea Urea plant Toxicity of ammonia after hydrolysis,
eutrophication
12 Soot particles Synthesis gas unit Reduced bacterial activity, respiratory
problem
13 SO Synthesis gas unit Irritation and respiratory problem, vege­tation
2
injury affect building structure
14 NOx Nitric acid plant, power plant Irritation, bronchitis, edema of lungs
15 Acidity Condensates, cooling tower Affects aquatic fauna and flora
bleed and floor washing of acid
range plants
16 Alkalinity Wastewater from all source of Affects aquatic fauna and flora
NH3 plant except cooling tower
bleed.
17 Particulate Granulation unit, prilling tower Affect vegetation, animal material and human
matter material, fluorosis in animals, plant damage,
corrosion soiling effect
18 Acid mist H7SO4 plant Irritation and respiratory problem affect
animal and plant corrosion
19 Phenols, Gas compressors in ammonia Toxic to fish, causes water treatment
alde­hydes and urea manufacture problem
oils and tars

Table 28.15: Chemical analysis of nitrogenous and phosphatic compounds and their complex
Plant type Unit Nitrogenous Phosphatic Complex
Total suspended solids mg/L max 100 100 100
Temperature Deg C Recycling water
temp + 5
pH mg/L max 6.5—8.0 7.0–9.0 6.5–8.0
Oil and grease mg/L max 10 10 10
Ammoniacal nitrogen mg/L max 50 50
Free ammonia mg/L max 4 4
Total Kjeldahl nitrogen as N 100
Nitrate nitrogen mg/L max 20 20
Phosphates as P mg/L max 5 5
Contd...
Environment, Health and Safety in Chemical Process Industry 567

Table 28.15: Chemical analysis of nitrogenous and phosphatic

compounds and their complex (Contd...)
Plant type Unit Nitrogenous Phosphatic Complex
Fluorides as F mg/L max 10 10
Cyanide as CN mgL max 0.2 0.2
Hexavalent chromium mg/L max 0.1 0.1 0.1
Arsenic as As mg/L max 0.2 0.2
Vanadium as V mg/L max 0.2 0.2

Table 28.16: Water pollutants from fertilizer industry

Parameter Ammonia Urea Phosphoric acid
3
Waste water, (m /ton) 1.53 1.30 12–18
pH 9–10 1.00 1.0–2.0
NH3-N (mg/L) 550 5550 –
Urea (mg/L) – 8750 –
Phosphate (mg/L) – – 600
Fluoride (mg/L) – – 3000–4850

Table 28.17: Particulate matter from fertilizer industry

S. no. Plants Dust emitting steps
1 Ammonia Coal and coke dust in coal based plant, coal dust in steam
generating plants. Urea dust from prilling
2 Urea Urea dust from prilling tower and handling unit
3 Ammonium sulfate Gypsum dust, sulfur, pyrite and pyrite cinder dust.
4 Calcium ammonium Lime stone and product dust from grinding, crushing,
granulation, drying and handling process
5 Mixed fertilizers Product dust from handling arid granulation.
6 Phosphatic fertilizers Rock phosphate dust, sulfur, pyrite, pyrite cinder
7 Power generation Coal dust, fly ash, bottom ash

Table 28.18: Solid waste from fertilizer industry

Name of plant Solid waste
Ammonia plant Carbon slurry (total carbon 1.45–1.47 kg per ton of NH3) in fuel oil
based plant, ash slurry in coal based plant, spent catalyst discharge,
used tower packings, arsenic sludge, scrubber waste
Ammonium sulfate plant Chalk slurry (1 ton per ton ammonium sulfate)
Phosphoric acid and sulfuric Phosphogypsum (4–6 ton per ton of P O ) sludge from effluent
2 6
acid plant containing phosphoric acid, sulfur sludge
Urea plant Urea due to spillage in conveying and bagging
Water treatment Chrome sludge (cooling water treatment), sludge from water
treatment plant, used resins
Power generation Fly ash, bottom ash
568 Chemical Process Technology

28.7.1 Hazardous Waste from Fertilizer Industry

Major hazardous waste for fertilizer industry are spent catalysts, spent carbon, arsenic
and vanadium-bearing waste, sludge, waste oil, carbonate sludges, Sulfur muck,
chromium bearing waste sludge, etc. (Sukummaran, Nair, 2013). Fertilizer industry
making phosphatic fertilizer also generate various hazardous waste like rock phosphate
fluorine-bearing waste, phosphor gypsum, etc.
Effluent Treatment Process
• Air stripping of ammonia
• Steam stripping of ammonia
• Ion exchange with recovery of ammonia salt
• Biological nitrification followed by denitrification.
Air stripping: pH of effluent 10.5 packed column
Steam stripping: Ammonium–hydroxide, carbonate, bicarbonate, dissociates to ammonia.
Ion exchange: First oil, organics, free chlorine, SS to be removed.
Cation exchange unit → Ammoniacal nitrogen
Regeneration with acid
Biological treatment process: Nitrification and denitrification process is given in
Figure 28.5.
Biological nitrification and denitrification: Reactions are as follows:
Organic carbon
Aeration denitrification
Ammoniacal nitrogen Nitrate nitrogen H2 + CO2
Nitrifying organism Denitrifying organism
7.5–8.5 pH
20–35ºC

Urea removal: Biological hydrolysis

Ammonia, ammonium carbonate CO2

Fig. 28.5: Biological treatment process in fertilizer industry

Environment, Health and Safety in Chemical Process Industry 569

28.7.2 Environmental Impact of Fertilizer Manufacture and Use

Major environmental apprehensions from fertilizer manufacture are:
• Deterioration of environment due to off plant activity which include oil processing
for naphtha and natural gas, mining of coal, gypsum, rock phosphate, beneficiation,
resulting in solid waste, waste water, particulates, heavy metals, etc.
• Deterioration in air quality due to emission of fluorine, particulates, NOX, SOX, acid
fumes, etc.
• Deterioration in the surface and ground water quality due to presence of high nitrate,
fluoride, suspended and dissolved solids, ammonia, oil and grease, heavy metals,
cyanide, etc.
• Environmental deterioration due to noise pollution at various stages like ammonia
manufacture, urea manufacture, rock phosphate mining, grinding, boiler blow
downs, boiler, turbine, etc.
• Adverse impact on biological environment due to various toxic pollutants discharge
in water and air during production and application of fertilizer.
• Fertilizer use efficiency in India is low. Increasing use of fertilizers and over
fertilization has resulted in deterioration of surface and ground water quality through
loss of nutrients. Undesirable over supply in mobile form in the soil resulting in the
presence of nitrates, phosphates, heavy metals and fluorine in the ground water.
Concentration of these pollutants is well above the prescribed limits in the ground
water at many parts of the country.
• Social-cultural disruption due to influx of labor force, migration from outside,
movement of heavy machinery, etc.
• Reducing emissions of ammonia at various levels of operation.
• Reducing the emission of fluorine at various stages of operation by scrubbing the
fluorine-laden gases and their subsequent utilization by use of computer base dual
scrubbing system consisting of venture scrubber combined with packed column.
• Reduction in the waste water generation by more and more recycling and utilization
of zero discharge technologies.
• Reduction in emission of SO2 and acid mist through better controls of operating
parameters during conversion and absorption stages by on-line control, as in many
plants emissions are still at higher value.
• Use of molecular sieve absorber to recover trace quantity of toxic pollutants
• Improvement in the acid mist eliminator
• Online monitoring of pollutants
• Proper utilization of carbon, phosphor gypsum, coal fly ash. Some of the applications
of phosphor gypsum may be in gypsum plaster, gypsum ceiling tiles, gypsum marble
products, gypsum board and cement.

28.8 ENVIRONMENTAL POLLUTION FROM CEMENT PLANT

• Major environmental issues are dust pollution of the atmosphere and emission of
green house gases (GHG), ecological concern arising from the degradation of mined-
out areas, noise transport pollution and emission of mercury.
• GHG emission from cement industries is about 1.4 × 103 million tons of CO2 equivalent
against the total world greenhouse gas emissions of 44 × 103 million tons of CO2
equivalent.
570 Chemical Process Technology

• Cement related GHG emissions originate from fossil fuel combustion at cement
manufacturing operation (40%), transport activities (5%), combustion of fossil fuel
that is required to make the electricity (5%) and manufacturing process (about 50%)
• Present in raw materials; both natural and recycled inputs
Sources of pollution and control strategies in cement plant are given in Table 28.19.

Table 28.19: Sources of pollution and control strategies in cement plant

S. no Point/unit Equipment/collection method
1 Lime stone quarrying Water spraying
2 Drilling unit Air suction and bag filters
3 Lime stone crushing Hoods, suction, cyclones
4 Raw mill and spraying Bag filters/ESP(for dry processes)
5 Coal mill Bag filters, wet scrubbers, cyclones, ESP (if used in
conjunction with raw mill exhaust)
6 Kiln Wet scrubbers (high energy type)/ESP/fabric filters.
• Wet process Multiclones/cyclones (high efficiency type) in conjunction
• Semiwet process with either bag filters or conditioning tower and ESP.
• Dry process Preheater cyclones in conjunction with either bag filters
(high air to cloth ratio type) or ESP. Preconditioning with
regard to temperature reduction is must.
7 Clinker cooler Multiclones and gravel bed filter (for grate type coolers)
followed by ESP (in few plants)
8 Cliker transport/conveying Water spraying, bag filters
and storage
9 Cement mill Bag filters, ESP
10 Cement conveying and storage Hoods, ventilation with bag filters
11 Packing/loading Hoods, suction with bag filters

28.9 ENVIRONMENTAL POLLUTION FROM CAUSTIC CHLORINE PLANT

1. Mercury cell
• Mercury emission/discharge through liquid, gaseous and solid waste routes
• Leakages of chlorine
• Leakages of HCl
• Leachates from brine storage
• Sludge from brine sludge
• Lime sludge
2. Mercury emission
• Cell room
ƒ End box ventilation
ƒ End box sampling
ƒ End box cleaning of mercury sludge
ƒ Cell maintenance
ƒ Leakage from mercury circulation
ƒ Pump brine pump
ƒ Hot hydrogen leakage
Environment, Health and Safety in Chemical Process Industry 571

ƒ Accidental mercury spills

ƒ Cell failure
As per WHO maximum 0.05 mg/cubic meter of air
3. MINAS for caustic chorine
• pH 5.5–9.0
• Mercury in final effluent 0.01 mg/L
• Mercury-bearing waste water 10 kilo liter/ton of caustic
• Mercury 0.2 mg/m3, chlorine 15 mg/m3
4. Sources of mercury loss:
• Brine mud  10–20 mg/g of mud (Hg)
 0.03 ton/ton of caustic
• Handling loss 40–50 g/ton of NaOH
• Through NaOH 0.44–2 g/ton of NaOH
• Hydrogen 20 mg/cm3
• Water 0.3% of total loss
• Unknown 62 g Hg/ton
5. Mercury emission control (Good house-keeping)
• Liquid route:
ƒ Good house keeping
ƒ Good material of construction
ƒ Control of overflow and leakage. Leakage to be passed through catch pot
Demercurization
ƒ To build catch post to collect all sorts of waste water.
ƒ Proper mercury handling.
• Control of mercury emission from solid waste:
ƒ Debrining of brine mud.
ƒ Demercurization after washing of sodium chloride.
ƒ Addition of hypochlorite can keep mercury in soluble form.

28.9.1 Demercurization of Waste Water

Reduction Method
Metal like copper, zinc, aluminum is added to mercury-bearing waste water.
• Amalgam is formed which appears on surface. By adding reducing agent like
hydrazine, hydroxyl amine, hypochlorous acid, formaldehyde
• Mercury is precipitated.
Sulfide Treatment
By addition of sulfide of hydrosulfide, mercury will be converted to insoluble mercury
sulfide.
Ferrous Chloride Treatment
Reduces mercury salt in alkaline condition to an insoluble mercuric oxide which
precipitates with ferric oxide.
Magnetic Ferrite
Ferrous sulfate is added to the mercury bearing waste water + alkali dark green
hydroxide complex is formed.
Then, air is blown to this for oxidation Black ferrite is formed.
572 Chemical Process Technology

Ion Exchange/Adsorptions
Mercury is removed by ion exchange process.

28.9.2 Coke Oven Plant

Coke is produced from coal from coke oven plants, and they are integral part of iron
and steel industry. Some of the major pollutants from coke oven plants are particulate
emission, fugitive emission from various processes, benzopyrine emission, emission
from quenching operation, waste water containing toxic material including inorganic
and organic matter, effunet plant hazardous waste, stack emission including SOX, NOX,
green house gases and SPM. Steel plant generation include thermal pollution, fugitive
emission blast furnace sag and steel melting shop waste. CPCB has recommended action
plan for control of pollution from coke oven plant (Sengupta, 2007).

28.9.3 Thermal Power Plant

Thermal power plants are integral part of many chemical process industries,. Some of the
major pollutants are cooling water discharge, ash pond effluent, emission of particulate
matter, SOX, NOX, green house gases, emission of mercury, fugitive emissions, etc. Fly
ash and bottom ash are two major sources of solid waste, chromium sludge, effluent
treatment plant. CPCB has recommended action plan for control of pollution from
thermal power plant (Sengupta, 2007).

28.9.4 Aluminum Industry

Aluminum industry is one of the important metallurgical industries. Fluoride emissions
and red mud generation are two major source of pollution. Apart for this, some of the
other sources of pollution are effluent treatment plant waste, emission from anode
baking oven plant, spent pot lining. CPCB has recommended action plan for control
of pollution from aluminum plant (Sengupta, 2007).

28.9.5 Copper and Zinc Plants

Although copper and zinc are part of metallurgical industry, however in addition to
mining of ore, beneficiation of ore, roasting of ores in smelter, sulfuric acid plant is
integral part to utilize the SO2 bearing gases. Some of the major pollutants are particulate
matter and fugitive emissions, smelter plant emissions SO2 emission, ETP sludge, spent
catalyst from sulfuric acid plant. CPCB has recommended action plan for control of
pollution from zinc and copper industries (Sengupta, 2007).

28.9.6 Sugar and Distilleries

Distilleries are one of the highly polluting industries and discharges high COD effluent
even after anaerobic digestion of Spent wash which is integral part of distilleries
followed by secondary treatment. Sugar and distilleries integrated plant discharges
colored effluent and are responsible for emission of particulate matter, SOX, solid waste
like bagasse, press mud , fly ash and bottom ash from bagasse fired boiler. Some of the
mills have gone for reverse osmosis and composting. Road map for distilleries for 100%
utilization of spent wash. Now CPCB has also fixed up norms for effluent standards,
for disposal into water stream and land irrigation and particulate matter emission from
bagasse fired boilers (Sengupta, 2007). Now sugar mills are equipped with primary and
secondary treatment for odor emission from sugar and distilleries.
Environment, Health and Safety in Chemical Process Industry 573

28.10 CLEANER TECHNOLOGY AND GREEN CHEMISTRY

Industrialization, and its impact on social and economic development, has proven to
be at a cost to both public health and the environment, and has been at the center of the
debate on sustainable development for more than a decade. Industry has recognized
that it has a key role to play in achieving the goals of sustainable development, not only
because of the rising threshold of public concern and expectations, but also because of
the need for business to fulfill a significant role in helping to solve both local and global
environmental problems.

28.10.1 Principle of Green Chemistry and Cleaner Technology

• Prevent waste
• Design safer chemicals and products
• Design less hazardous chemical synthesis
• Use renewable feedstocks
• Use catalysts, not stoichiometric reagents
• Avoid chemical derivatives
• Maximize atom economy
• Use safer solvents and reaction conditions
• Increase energy efficiency
• Design chemicals and products to degrade after use
• Analyze in real time to prevent pollution
• Minimize the potential for accidents
Cleaner production is the continuous application of an integrated preventive
environmental strategy.

28.10.2 Clean Production Technologies in Chemical Process Industries

• The double conversion double adsorption (DCDA) process for manufacture of sulfuric
acid which minimizes generation of SO2 emissions
• Super clause process with great sulfur removal efficiencies and SCOT process for off
gas treatment in oil refineries
• Catalytic hydrogenation, use of spent acid after nitrification for acidification of fusion
mass for elimination of iron and gypsum in the dye and dye intermediate industries.
• Caustic soda production using “membrane cell” process in place mercury cell process
to eliminate use of mercury in production of caustic soda and its discharge into
environment through effluent and solid waste
• Use of chlorine dioxide and oxygen at alkali extraction stage to reduce generation
of adsorbable organic halides (AOX) and use of oxygen/ozone for bleaching in the
pulp and paper industries instead of chlorine or hypo
• Re-calcination of lime sludge for reuse in the pulp mill
• Recovery of chemicals from black liquor to make the effluents from the pulp mill
more amenable and economically viable for treatment
• Adoption of dry process kilns for cement manufacture
• Adoption of suspension preheater in dry process
• Use of alternative fuels in cement plant
574 Chemical Process Technology

• Use of fluidized bed combustion (FBC/CFBC) in local based thermal power plant
technology for the solid fuel containing higher ash and sulfur
• Adoption of integrated coal gasification combine cycle (IGCC) technology
• Beneficiation of coal to reduce fly ash generation from thermal power plants
• Higher efficiency catalyst based fuel gas denitrification (selective catalytic reduction,
SCR systems
• Use of chemical substitutes, with less pollution potential, in sizing, mercerizing,
dyeing, printing sections of textile industry
• Elimination of cyanide and hexavalent chrome from zinc plating units using substitute
chemicals
• Adoption of vertical shaft brick kiln (VSBK) to manufacture bricks to save coal and
reduction in air pollution
• Fixed chimney and settling chambers for bull’s Trench brick kilns (BTKs) help in
saving coal and reduction in air pollution.

28.10.3 Cleaner Technology in Pulp and Paper Industry

Greener production in pulp and paper industry can be achieved by upgrading
raw materials, through better forest management, upgradation of technology and
equipments in pulping and bleaching, washing, screening, paper making. Recovery
of chemicals especially agro-based mills; better process control and instrumentation,
better forest management plan, upgrading product quality, product diversification,
improved recycling, better energy and environmental strategies.
Some of the major cleaner technologies being implemented in pulp and paper
industries are:
• Efficient management of depleting resources with sustainable forest productivity
through improved resource planning, better plantation technique, good harvest
management
• Conservation of natural resources
• Effective waste utilization and recycling of fiber
• Better environmental management for reducing or eliminating toxicity
• Better fiber properties.
• Improved product appeal (higher brightness)
• Odorless mill
• Modification in pulping
• Improved brown stock washing and screening
• Modification of bleaching process through elemental chlorine free (ECF), and total
chlorine free (TCF), biobleaching
• Recycling of waste paper
• Recovery of chemicals from agro-based mills
• Recycling and reuse, etc.

28.10.4 Clean Production Technologies in Petroleum and Petrochemical Industry

• Cleaner alkylation processes by solid acid catalyst replacing the sulfuric acid or HF
in Petroleum refinery and petrochemical production (LAB)
• Cleaner fuel using ultra desulfurization processes
• Gas to liquid technology
Environment, Health and Safety in Chemical Process Industry 575

• Methanol to olefin technology

• Alkylation for production of high octane gasoline from olefin and isobutane
• HF and H2SO4 conventionally used as alkylation catalyst in refinery
• HF and H2SO4 highly toxic and corrosive
• Anhydrous HF is highly toxic and an accidental release can have serious consequences
• Low risk alkylation process
• Alkyclean catalyst robust zeolite solid environmentally friendly process eliminates
corrosive liquid acid use
• Removes safety risks associated with liquid acids. Lower maintenance and monitoring
requirement
• Low pressure, liquid phase operation in the temperature of 50–90ºC. Eliminates
costly refrigeration
• Does not produce acid soluble oil by product
• No emissions to air, water or ground
• Reducing emissions of ammonia at various levels of operation.
• Reducing the emission of fluorine at various stages of operation by scrubbing the
fluorine laden gases and their subsequent utilization by use of computer base dual
scrubbing system consisting of venture scrubber combined with packed column.
• Reduction in the waste water generation by more and more recycling and utilization
of zero discharge technologies.
• Reduction in emission of SO2 and acid mist through better controls of operating
parameters during conversion and absorption stages by on-line control, as in many
plants emissions are still at higher value
• Use of molecular sieve absorber to recover traces quantities of toxic pollutants.

Selection of control strategy

• Relationship of process emulsion (uncontrolled) to quality of emission need to meet
objectives
• Characterization of pollutants.
• Requirements for removal efficiency.
• Minimum removal efficiencies as per applicable local, State National regulation.

Source Correction Method

• Raw material changes
• Process changes
• Regulate the location of the operation
• Equipment modification
• Good house-keeping, proper equipment maintenance, cleanliness, general leakage
control change in design of local exhaust hood.

Extent to Clean Polluted Gas

• Concentration levels harmful to humans, physical structures, plant and animal
life
• Legal limitations imposed by the country, state, city, etc. for protection of public health
• Reduction of air pollution to establish civic goodwill
• The reduction and/or elimination of potential liability patterns.
576 Chemical Process Technology

BIBLIOGRAPHY
1. Bulmer PT, Reising DV. “Human reliability and process Safety Metrics: considerations from an
abnormal situation management perspective”, Chemical News, Jan 2018, p.45.
2. Chemical News 2013. “Notification on Environment (Emission Standards) for Petrochemical
Industry” . Feb 2013, p.38.
3. Chemical News, 2010. ”Organic chemicals manufacturing Industry”. October 2010, p.68.
4. Doshi V. “Process Safety culture”, Chemical News, May 2015, p.3.
5. Jin H, William B, Summers L, Summers A. “High /Continuous Demand hazardous Scenarios
in LOPA”, Chemical News, November 2017.
6. Lorenzo DK. “A manager’s guide to reducing human error”, Chemical Manufacturer Association
Washington DC, 1990.
7. Mall ID. “Petrochemical Process Technology”, Macmillan India, 2006; Laxmi Publication, Reprint
2016, Second edition 2017.
8. Mall ID. “Petroleum refining technology”, CBS Publication, Fist edition, 2015.
9. Mal ID. “Cleaner technology in Chemical Industries”, Key note address: “Recent Advances
in Chemical and Environmental Engineering”, Jan 20–21, 2012 Dept. of Chemical Engg. NIT
Rourkela.
10. Mall ID, Srivastava VC, Singh S, Sinha S. “Safety management in Pulp and Paper industry”.
Proceedings of Safety Convention 2007, organized by Institution of Engineers (India) Delhi state
centre.
11. Manahan Stalney E. “Environmental chemistry”, Third Edition, 2009 CRC press.
12. Mathur SB. “Safety management concepts and realities” industrial safety and socioeconomic
growth. Proceedings of Safety Convention 2007 organized by Institution of Engineers (India)
Dehli state centre.
13. Metcalf and Reddy. “Waste water Engg” by Franklin L. Burton, H. David Stensel Metcalf George
Tchobanoglous, Fourth Edition 2003 Tata Mc. Graw Hill edition.
14. “Pollution Control Acts, Rules, Notifications Issues thereunder”, Central Pollution Control Board,
Ministry of the Environment and Forest, Govt. of India, Third Edition, 2006.
15. Peavy HS, Rowe DR, Tchobanoglous. “Environmental Engineering”, McGraw Hill International
edition 1985.
16. Turk MA, Mishra A. “Process Safety management: Going beyond functional safety”, Hydrocarbon
processing, March 2013, p.55.
17. El-Mekki El-Malki, Benjamin Umansky, Erik Moy, Grant Donahoe and Timothy. Thom’ gasoline
benzene reduction, PTQ 2013, p.45.
18. Rao NP. Private communication, 2017.
19. Sengupta B. ”Clean technology options for 17 catagories of highly polluting Industries”,
Proceedings of International Conference on Cleaner Technologies and Environmental
Management. January 4–6 2007, Organized by Pondicherrry Engineering College, Pudhucherry,
India
20. Sukumaran Nair MP. “Management of Hazardous waste from fertilizer Complexes”, Chemical
Industry Digest 2013, p.59.
Appendices

APPENDIX 1: QUANTITIES AND SI UNIT

Quantities SI units Symbol
Length Micrometer mm
Millimeter mm
Meter m
Kilometer km
Area Square meter m2
Square kilometer km2
hectare Ha
Volume Liter L
Cubic meter m3
Mega liter ML
Time Second sec or s
Minute min
Hour hr
Velocity Meter/second m/s
Flow rate Cubic meters/second m3/s
Liters/second L/s
Mega Liters/day ML/day
Mass microgram mg
milligram mg
Kilogram kg
Force Newton N
Kilo Newton KN
Pressure Pascal Pa
Energy Joule J
Power Watt W
Kilowatt kW
Temperature Kelvin K
Degree Celsius °C
Contd...

577
578 Chemical Process Technology

Quantities SI units Symbol

Acceleration meter per second square m/s2
Concentration mole per cubic meter mol/m3
Current density Ampere per square meter A/m2
Density Kilogram per cubic meter kg/m3
gram per cubic centimeter g/cm3
Kinematic viscosity Square meter per second m2/s

Conversion to Metric System

Length 1 inch 2.54 cm
1 foot 0.3048 m
1 yard 0.914 m
1 mile 1.609 km
Area 1 ft2 0.0929 m2
1 acre 0.4047 hectares
1 sq mile 2.59 km2
Volume 1 cu inch 16.39 cc
1 US gallon 3.785 l
1 cu ft 0.0283 m3
1 US barrel 0.159 m3
Weight 1 grain 0.0648 g
1 ounce 28.35 g
1 pound (lb) 454 g
1 short ton 907.2 kg
1 long ton 1,016 kg
1 ton 1,000 kg
Velocity 1 ft/min 0.00508 m/s
1 mile/hr 0.447 m/s
Temperature °F 1.8 × °C + 32
°C (°F-32)/1.8
Viscosity 1 cp 10-3 Kg/m s
Thermal conductivity 1 Btu/hr ft °F 0.5778 W/m K
1 Btu/hr ft °F 241.75 cal/s cm K
Heat transfer coefficients 1 Btu/hr ft2 °F 0.1761 W/m2 K
1 Btu/hr ft2 °F 7,368.6 cal/s cm2 K
Appendices 579

Conversion of Weight Units

Grams Kilograms Ounces Pounds Tons

Grams (g) 1 1,000 28.35 453.6 1.016 × 106
Kilograms (kg) 0.001 1 2.835 × 10–2 0.4536 1,016

Ounces (oz) 3.527 × 10–2 35.27 1 16 3.584 × 104

Pounds (lb) 2.205 × 10–3 2.205 6.250 × 10–2 1 2,240

Conversion of Energy Units

kg-m m-cal Joule KW-Hour HP-Hour

kg-m 1 0.00235 9.81 0.27 × 10–5 0.365 × 10–5
m-cal 427 1 4,179 0.001161 0.001556
Joule 0.102 0.000239 1 27.77 × 10–8 37.23 × 10–8
KW-hour 366.973 860 3.6 × 10–10 1 1.3411

HP-hour 273.745 642.5 2,685.5 0.74565 1

Conversion of Power Unit

kg m/s Kcal/s kW HP
kg-m/s 1 0.00234 0.00981 0.0133
Kcal/s 427 1 4.17 5.59
KW 101.97 0.239 1 1.341
HP 76 0.178 0.746 1

Conversion of Pressure Units

psi kg/cm2 Atm. Bar mm WG Pascal Pieze

psi 1 0.07031 0.06804 0.069 703.1 6,896 6.895

kg/cm2 14.233 1 0.9678 0.981 10,000 98,087 98.08

Atm 14,069 1.033 1 1.0133 10,331 1,01,325 101.32

Bar 14.5 1.019 0.986 1 10,200 1,00,000 100

mm WG 14.233 × 10–4 1 × 10–4 96.78 × 10–6 9.81 × 10–5 1 9.808 98.04 × 10–4

Pascal 145 × 10–6 10.19 × 10–6 9.869 × 10–6 10–5 0.1019 1 0.001

Pieze 0.145 0.01019 0.00986 0.01 102 1000 1

580 Chemical Process Technology

Main Conversions Used in Petroleum Industry

Item Conversion factor
Crude oil 1 ton 7.33 barrels
1.165 cubic meters (kiloliters)
1 barrel 0.136 tons
0.159 cubic meters (kiloliters)
1 cubic meter 0.858 tons
6.289 barrels
1 million ton 1.111 billion cubic meters natural gas
39.2 billion cubic feet natural gas
0.805 million tons LNG
40.4 trillion british thermal units (BTU)
Natural Gas 1 million ton 35.3 billion cubic feet natural gas
0.90 million tons crude oil
0.73 million tons LNG
36 trillion british thermal units
6.29 million barrels of oil equivalent
LNG 1 million ton 1.38 billion cubic meters natural gas
48.7 billion cubic feet natural gas
1.23 million tons crude oil
52 trillion british thermal units
8.68 million barrels of oil equivalent
CNG 1 kilogram 1.244 standard cubic meters natural gas
1.391 liters of petrol
1.399 liters of HSDO

1 cubic feet of natural gas = 1000 Btu; One m3 of natural gas = 9,000 kcal = 37,656 KJ
One KWh = 3,412 Btu = 860 kcal
Source: 1. BP Amoco Alive Statistical Review of World Energy
2. OPEC Annual Statistical Bulletin

Conversion Factors for Petroleum Products

Products TOE/ton Barrel/ton
Refinery gas 1.150 8.00
Ethane 1.130 16.85
LPG 1.130 11.60
Aviation gasoline 1.070 8.90
Motor gasoline 1.070 8.53
Jet gasoline 1.070 7.93
Jet kerosene 1.065 7.93
Contd...
Appendices 581

Contd...
Products TOE/ton Barrel/ton
Other kerosene 1.045 7.74
Naphtha 1.075 8.50
Gas/diesel oil 1.035 7.46
Heavy fuel oil 0.960 6.66
Petroleum coke 0.740 5.50
White spirit 0.960 7.00
Lubricants 0.960 7.09
Bitumen 0.960 6.08
Paraffin waxes 0.960 7.00
Non specified products 0.960 7.00
TOE : Tons of oil equivalent
Source: International Energy Agency Statistics

Exact Equivalences

Imperial Metric
1 inch 2.540 vm
1 foot 0.3048 meter
1 yard 0.9144 meter
1 rod 5.029 meter
1 mile 1.609 km

Metric Imperial
1 cm 0.3937 inch
1 decimeter 0.3281 foot
1 meter 3.281 feet
1 meter 1.094 yard
1 decameter 10.94 yards
1 kilometer 0.621 mile

Exact Equivalences
Imperial Metric
1 inch 2.540 cm
1 foot 0.3048 meter
1 yard 0.9144 meter
1 rod 5.029 meter
1 mile 1.609 km
582 Chemical Process Technology

APPENDIX 2: PHYSICAL AND CHEMICAL CHARACTERISTICS OF

MAJOR INORGANIC AND ORGANIC CHEMICALS

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Ammonia, Colorless –33.5 Gas –77.7 0.77 16.0 27.0 650
NH3 gas liquid
with sharp,
intensely
irritating
odor; lighter
than air; toxic
and irritant;
tolerance 25
ppm in air.
Aluminum Made from
bauxite ore and
caustic soda
Acetylyene Made from –84°C –123.5
calcium carbide
and water and
partial oxida­­
tion of hydro­
carbons and
Wolf process
Aniline, Colorless 184.4 –6.2 1.0235 70 1.3 20.25 615
C6H5NH2 oily liquid; (Closed
characteristic cup)
odor and
taste; toxic;
an allergen;
tolerance
2 ppm in air
Asphalt Black solid or 371 >204 93 1.0 132 – – 485
viscous liquid;
moderately
toxic by inhala­
tion of fumes
Benzene, Colorless to 80.1 5.5 5.0 0.879 (at –11 1.3 7.1 562.2
C6H6 light yellow 20/4 °C) (Closed
cup)
liquid with
aromatic odor;
flammable,
dangerous
fire risks;
tolerance limit
in air 10 ppm,
carcinogenic
Contd...
Appendices 583

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
1,3- Colorless gas, –4.4.3 –108.9 0.6211 76.0 2 11.5 417.8
Butadiene, non corrosive (liquid) (vol.%)
CH2 = CH- with mildly (at 20 °C)
CH = CH2 aromatic odor;
highly flamm-
able gas or
liquid. Used
for plastic and
ruber
Butane, Colorless gas 0.6 -138.3 –135 0.6 - 60 1.6 8.4 405
C4H10 with natural gas
odor; highly
flammable; ana-
sphyxiant gas
n-Butanol, Colorless liquid; 117.7 –89.0 0.8109 28.85 365
C4H9OH toxic on prolong (Closed
cup)
inhalation;
irritant to eyes;
tolerance 50
ppm in air
1-Butene, Colorless gas; –6.3 –185 –130 0.5951 –79 1.6 9.3 371
CH3 CH2 highly flamm­- (at 20/4
CH = CH2 able; dangerous °C)
fire and explo-
sion hazard
Carbon Colorless or 46.3 –111 1.260 –30 100
disulphide, faintly yellow (at 25/25
liquid; highly °C)
CS2
flammable;
dangerous fire
and explosion
hazard
Carbon Colorless; –190 Gas –206 0.967 Gas 12.5 74.2 609
monoxide, highly toxic
CO by inhalation;
solidification
point: –207°C
Carbonyl Colorless gas 50.2 –138.8 –138 2.10 11.9 28.5 —
sulfide, COS with typical (1 atm)
sulphide odor;
flammable
Carbon Colorless 76.8 –22.9 –22.6 1.595 none
tetra- liquid; toxic
achloride, by ingestion
inhalation;
CCl4
tolerance
5 ppm in air
Contd...
584 Chemical Process Technology

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Chloro-form, Colorless, 61.2 –63.5 1.485
CHCl3 highly refrac-
tive, heavy
liquid with
characteristic
odor; toxic by
inhalation;
narcotic; pro­
long inhalation
or ingestion
may be fatal;
tolerance
10 ppm in air;
carcinogenic
Caustic soda Available in
Caustic lye and
solid caustic
form hygro­-
scopic in nature
Chlorine Dense, greenish Liquid
yellow, toxic gas chlo-
in nature with rine
pungent smell –35 °C
and very corro­ at 1 atm
sive gas and is
made from
brine. Also
available in
gaseous and
liquefied form
Chlorine Red yellow gas, 10°C –59.5
dioxide very reactive
in nature toxic
nature. made
from sodium
chlorate
Chloro- Colorless gas, –23.7 –97.6 0.92 0 8.1 1 632
methane, etheral odor, 7
CH3Cl sweet taste;
flammable;
dangerous fire
risk
Chloroprene, Colorless liquid; 59.4 0.9583 –20 4 20
H2C=CH– flammable;
C(Cl)=CH2 dangerous fire
risk; toxic by
Used for
ingestion and
ruber inhalation
Copper Copper is made
from various
oxides and iron
pyrite and sul­
fide ore
Contd...
Appendices 585

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Cumene Colorless liquid, 152.39 –96.03 0.8619 44 0.9 6.5 424
(Isopropyl aromatic odor; (at (vol.%)
benzene), moderately 20 °C)
toxic by inges­
C6H5CH
tion; inhalation;
(CH3)2
tolerance
50 ppm in air
Cyclo Colorless gas 13 –80 10
butane
C4H8
Cyclo- Colorless 80.7 6.3 0.779 (at –18.3 1.3 8.4 245
hexane, mobile liquid 20/4 °C)
C6H12 with pungent
odor
Cyclo- Colorless 160.9 23 0.9429 67.7 299.7
hexanol, viscous liquid, (at 25/4
C6H11OH hygroscopic. °C)
Cyclo- Colorless 44 –135.2 0.772 –29
pantane liquid
C5H8
Cyclo- Colorless 42.5 0.805
pentadiene, liquid; decom­
C5H6 poses violently
at high tempe­-
rature; tole­
rance 75 ppm
in air
n-Decane, Colorless 173 –30 –32 0.729 44 0.67 2.6 250
C10H22 liquid; mode­ (closed
rate fire risk cup)

Diacetone Colorless 169.1 –42.8 140 0.9406 23–38 1.8 6.9 603
alcohol, CH3 liquid with (at 20/20 (de-
COCH2 pleasant odour; °C) pend-
flammable; ing
C(CH3)2 OH
dangerous upon
fire risk; toxic grade)
and irritant;
tolerance 50
ppm in air
Di n-butyl Colorless 159.6 –62 0.7613 51.6
amine liquid with
(C4H9)2NH amine odor
Di butyl Colorless oily 280.6 –85 0.9964 140.4
maleate liquid
(DBM)
Di-cyclo- Chemical 172 33.6 0.979 32.2
pentadiene, intermediate
C10H12 for pesticide;
flammable;
Contd...
586 Chemical Process Technology

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
moderate fire
risk; toxic by
ingestion,
inhalation;
tolerance
5 ppm in air
Iron and Pig Iron is
Steel made from iron
ore and lime
and coke. Steel
made from Pig
iron oxygen
or Air 12%
Chromium
minimum.
Nckel, Sulphur,
Phosphorous
Ethane, Colorless, –88.63 –183.23 –172 0.446 –135 3.12 15.0 515
C2H6 odor­­less gas; (Liquid,
severe fire risk 0°C)
if exposed to
sparks or open
flame
Ethanola- Colorless, 170.5 10.56 1.029 93.3
mine mono hygroscopic, (de- (open
ethanol viscous liquid; comp) cup)
amine moderately
(MEA), toxic.
(HOCH2
CH2)NH2 Colorless 270 28 1.092 152 228.9
Diethano- crystal or (at 30/20 (open
lamine liquid, toxic; °C) cup)
(DEA) tolerance in air
(HOCH2 3 ppm
CH2)2NH 1.13
19.5 371
triethanol Colorless 360 21.2
amine (TEA) viscous, (Open
(de-
(HOCH2 hygroscopic cup)
comp)
CH2)3N liquid;
combustible;
low toxicity
Ethyl Colorless 136 –95 0.867 15 432 432
benzene, liquid with (20°C)
aromatic odour;
C6H5C2H5
flammable,
dangerous fire
risk; moderately
toxic; tolerance
10 ppm in air
Contd...
Appendices 587

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Ethanol, Clear, colorless 78.32 –114.1 –117 0.7893 14.0 3.3 19.0 423
C2H5OH liquid with (25 °C) (Closed (vol.%)
pleasant odour; cup)
flammable,
dan­gerous fire
risks; tolerance
in air 1000 ppm
in air
Ethylene Colorless 10.4 –111.7 0.8711 < –18 3 100 429
oxide, gas; highly (TOC)
C2H4O flammable;
dangerous fire
and explosion
risk; tolerance
10 ppm in air
Ethylene, Colorless, –103.71 –169.15 –169 0.610 –135 3 36 543
C2H4 slightly sweet
odor; highly
flammable;
dangerous fire
and explosion
risk
Ethylene Colorless 83.5 –35.5 1.2554 13.3 6 16
dichloride, oily liquid;
C2H4Cl2 flammable,
dangerous
fire risk; toxic
by inhalation,
ingestion;
tolerance limit
in air 10 ppm
Ethylene Colorless liquid 197.6 –13.5 1.1155 116 412
glycol with sweet taste;
MEG, combustible;
toxic by
CH2OH
ingestion and
CH2OH
inhalation
DEG, Colorless 245 –8.0 1.1184 123.9 228.9
(CH2CH2 liquid
OH)2O
TEG, Colorless, 287.4 ­–7.2 1.2544 176.6 371
HO hygroscopic
(C2H4O)3H liquid

Ethylene Colorless 171.2 0.9019 61 244

glycol liquid with
monobutyl mild odor;
ether, toxic; tolerance
HO.CH2. limit in air
CH2.O. C4H9 25 ppm.

Contd...
588 Chemical Process Technology

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Ethylene Colorless liquid; 135.6 –85.1 0.9311 48.9 237
glycol moderately
monoethyl toxic by
ingestion and
ether,
inhalation;
CH3OCH2 Tolerance limit
CH2OH 5 ppm in air.
Formal- Colorless gas, –19 –118 0.8153 7.0 7.3 430
dehyde, pungent suffo- (at –20°C) (mol.%)
HCHO cating odor
Gas oil Made from 232–426 – – 65.5 – – 338
crude oil
frac­tionation
in between
kerosene and
diesel
Glycerin Clear, colorless, 290
odorless, by
product of soap
manufacture,
soluble in
water and
alcohol, used
in alkyd resins
and dynamite
Furfural Colorless 161.7 –36.5 –38 1.1598 60 2.0 – 393
liquid when (20/4°C)
pure, toxic,
absorbed by
skin, tolerance
2 ppm in air,
irritant to eyes,
skin, and
mucous
membrane
Gasoline Highly flamm- 38–204 –45.6 <45.6 1.3 6.0 257
able, dangerous
fire and explo-
sion risk
n-Heptane, Volatile, 98.428 –90.595 –90 0.684 –3.89 1.0 6.0 222
C7H16 colorless liquid,
flammable,
dangerous fire
risk, tolerance
400 ppm in air.
Hexane, Colorless 69 –95.6 –94 0.659 –22.7 1.2 7.5
C6H14 volatile
liquid with
fa int odour;
flammable
dangerous fire
risk; tolerance
500 ppm in air.
Contd...
Appendices 589

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Hydrazine, Colorless, 113.5 1.4 1.004 (at 52.2 270
H2N.NH2 fuming, 25/4°C) (Open
hygroscopic cup)
liquid; highly
toxic by
ingestion,
inhalation
and skin
absorption;
tolerance
0.1 ppm in
air, a known
carcinogen.
Hydrogen, Highly –252 –259 –260 0.069 4.1 74.2 580
H2 flammable
and explosive,
dangerous
when exposed
to heat or flame
Hydrogen Colorless, –85 –114 1.268
chloride, fuming
HCl gas with
suffocating
odor; toxic by
inhalation,
strong irritant
to eyes and
skin. Tolerance
in air 5 ppm
Hydrogen Made from –150.25
peroxide anthroqenone3
using catalyst
nickel or palla­
dium used
widely used
for oxidation
purposes
Helium Noble gas –268
made from air
Hydrogen Colorless gas 26 –13.3 0.688 –17.7 6 41 538
cyanide or liquid with (liquid) (Clo-
characteristic (at sed
odor, highly 20/4°C) cup)
toxic by inges-
tion, inhalation
and skin
absorption
Hydrogen Colorless gas –60 –83 1.189 4.3 46 260
sulfide, H2S with offensive
odor; toxic by
inhalation;

Contd...
590 Chemical Process Technology

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
highly flamm­­
able, dangerous
fire risk; tole­
rance 10 ppm
in air
Iron and Pig iron is
steel made from
lime stone
coke; Steel is
made from
pig iron 12%
chromium
minimum and
small amount
of nickel, phos­
phorous, sulfur
Iodine Heavy non- 184
metallic halogen
element having
grayish black
color used in
pharmaceuti-
cals, dyes,
water treat­
ment, obtained
from brine,
toxic by
inges­­tion and
inhalation
Isobutene, Colorless –6.9 –139 0.6 1.8 8.8 465
(CH3)2C= volatile liquid
CH2
1-3 isobuta Colorless gas –4.4 –108.9 0.64 –85
diene C4H6
Isopentane, Colorless 27.85 –159.89 0.6197 –57 420
CH3CH liquid, pleasant
(CH3)CH3 odour; highly
flammable
Iso-phorone, Water white 215.2 –8.1 0.9229 96 462
C(O)CH–C liquid; toxic, (at 20/
(CH3)CH2 irritant to skin 20°C)
C(CH3)2 and eyes
CH2

Isopropyl Colorless liquid, 82.3 –86 0.78634 11.7 2.0 12 453

alcohol, pleasant odor; (at 20/20 (Clo- (vol.%)
C3H7OH flammable, °C) sed
dangerous fire cup)
risk; toxic by
Contd...
Appendices 591

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
ingestion and
inhalation;
tolerance
400 ppm in air
Kerosene Moderate fire – 180– – 0.81 37.7– 0.7 0.5 228
risk, moderately 300 65.5
toxic by
inhalation
Leather Made from
tanning of
animal skin
Lime Used in
calcium oxide,
bleaching
powder
obtained from
limestone
Lignin A phenyl­pro­
pane polymer
of amorphous
structure
available in
wood 17–30%.
Used as drilling
fluid additive,
source of
vanillin and
phenol
Lignin Used in
sulfonate pesti­­cide
formulation,
commercially
available as the
salts of most
metals and of
ammonium
Lime stone Manufacture
of lime,
cement
Linseed oil Golden-yellow,
amber, or
brown drying
oil; peculiar
odor, used in
paints, varnish,
oil cloth,
printing inks.
Obtained from
seeds.
Contd...
592 Chemical Process Technology

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Ammo-nium Used as ferti­
nitrate lizer and explo­
sive
Methane, Colorless, –161 –184 0.554 537
CH4 odorless
tasteless gas
MIBK Colorless, 115.8 –85.5 0.8042 22.7 - - 460
stable liquid,
pleasant odour

MEK, CH3 Colorless 80 –86.4 0.8256 (at –4.4 1.81 11.5 515
liquid; flamm­­- 0/4°C) (TOC)
COCH2
able, dangerous
CH3 fire risk
Methanol, Clear, colorless 64.7 –97.8 0.7924 463 6 (vol.%) 36 464
CH3OH mobile liquid (at 25°C)
Methyl Colorless –23.7 –97.6 0.92 0 632
chloride, compressed
CH3Cl gas or liquid
Methyle Colorless liquid 100.8 –126.9 0.769 –3.89 285
cyclo hexane
CH3C6H11
Methyl Colorless 55 –100 8.4 0.74
cyclo- pungent
pentane smelling
Methyl tert
butyl ether,
(MTBE)
Methyl Colorless 79.57 –85.9 0.806 –4.4 1.8 10 515
ethyl ketone, liquid, acetone 20°C (TOC)
CH3CO like odor
CH2CH3
2-methyl Colorless 202 –24 1.027
pentane liquid
N-Methyl
pyrrolidine
(NMP)
Naphtha- White solid 218 80.5 1.14 79.87 525
lene C10H8 crystal, odor of
coal tar.
Highly flamm­
able used as
infectant
Newtonian With
liquid Newtonian
flow having
Newtonian
behavior
Contd...
Appendices 593

Contd...
Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition
odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Nitro- Colorless 101–131 –28 to 0.983 28 to 38
paraffin mobile liquid –104 to
CnH2n+1 Pleasant odor 1.131
NO2
Nitro- Oily liquid, 210.5 5.7 1.19867 87.7 482
benzene, greenish
C6H5NO2 yellow crystal
Nonane Colorless 151 -53 0.728 31 205
C9H20 liquid
n-Octane, Colorless 125 13.3 –56 0.7026 (at 13.3 220
C8H18 liquid 20/4°C)
Nitrogen Used for –195.5
making
acrylonitrile
and ammonia,
etc. commonly
made from air
liquification.
Used for
blan­ke­ting
as neutral in
nature
Nitric acid Transparent
colorless or
yellowish in
color, suffo­
cating, highly
toxic gas in
nature. Used
for making
explosive
and fertilizer
and organic
synthesis (dyes,
drugs, rubber
chemicals, etc.)
Fuming White or red
nitric acid toxic gas and
corrosive to
skin
Nitro- Used as
cellulose explosive
Nitro- Used as explo­-
glycerin sive, in manu-
facture of dyna­­
mite and used
in medi­cine as
vasodi­lator,
pale yellow,
toxic in nature
Contd...
594 Chemical Process Technology

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Wet Made by acidi­
phosphoric fication of rock
acid phosphate with
sulphuric acid.
Used in manu-
facture of super
phos­phate and
triple super-
phosphate
Electric Made by rock
furnace phosphate air
Phosphoric and electricity
water via
acid
phosphorous
Palm oil Yellow-brown
in color, iodin
number 13.5,
saponification
number 247.6
buttery, edible
solid, available
from trees
Pentane, Colorless 36 –129.7 0.62624 –40 1.4 8.0 309
C5H12 liquid with
pleasant
odor; highly
flammable
Pesticides It may be
herbicides,
insecticides,
fungicides.
Phenol, White, crystal­ 182 79.4 42 1.07 78 – – 715
C6H5OH line mass, (Clo-
burn­ing taste, sed
distinctive odor cup)
Polymeri- A chemical
zation reaction addi­
tion, bulk,
sus­pension
techniques
Potassium Soft silvery 770
metal
Propane, Colorless –42.2 –187.1 0.531 (At –105 2.3 9.5 468.7
C3H8 gas, highly 0°C)
flammable,
dangerous fire
risk
Producer gas Made from coal
used as fuel
Contd...
Appendices 595

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Sodium Used in salt
carbonate puri­fication
and sodium
silicate and
glass industry,
etc.
Sodium Used as pig­
chromate ment in leather
industry
Sodium Used in blast,
silicate silica-based
catalyst, soaps
and detergents,
pigments and
glass. Made by
fusing sodium
carbonate and
silica
Sodium Used in
Thiosulfate photo­graphy.
It is made
from sodium
sulphite liquor
from pulping
process.
Sulfur Made from – – 232
mining of
sulfur. Used for
manufac­ture of
sulfuric acid.
vulcanizing
agent for
rubber. Used in
paper industry
and CS2. also
made by sulfide
pyrite ore
Sulfuric acid 50% fertilizer
grade acid
o ileum: by
dis­solving
SO3 in sulfuric
acid. Used
in detergent
industry
Tereph-thalic White crystal Sub- 1.51
acid, or powder, limes
C6H4 insoluble in >300
water and
(COOH)2
many solvents
Contd...
596 Chemical Process Technology

Contd...

Compound Appearance/ BP FP MP Specific Flash Flamma- Autoignition

odor (°°C) (°°C) (°°C) gravity point bility Temp. (°°C)
(20/20°°C) (°°C) limit Lower Upper
(°°C) (°°C)
Toluene, Colorless, 110.7 –94.5 –95 0.860 (at 5 1.2 7.1 536
C6H5.CH3 distinctive 20/4°C) (vol.%)
aromatic odor
Trinitro Pale yellow 295 80.35 1.654
toluene needle-
shaped crystal
Poisonous and
allergic
Titanium Use as pigment
oxide in pigment
industry and
used in paper
industry
Urea, NH2 White crystal­ 132 1.335
line solid,
CONH2
readily soluble
in water and
alcohol
Vinyl Colorless, 72.7 –100.2 0.9345 –8 Exp. 2.6 13.4 426.9
Acetate, CH3 flammable (Clo- (vol.%)
COOCH = liquid sed
CH2 Cup)
–1.1
(Open
Cup)
Vinyl Colorless –13.4 –159.7 0.9195 (at 77 4 22 472
chloride or liquid or gas, 15/4°C) (COC)
chloroethy- faintly sweet
odor
lene CH2 =
CH-Cl
m-Xylene, Colorless 139 –47.9 0.8684 (at 28.9 1.1 7.0 527.7
C6H4 (CH3)2 liquid 20/4°C)

o-Xylene, Colorless 144 –25.5 – 0.88 (at 46.1 463.8

C6H4 (CH3)2 liquid 20/4°C)
p-Xylene, Clear liquid 138.3 13.2 0.861 (at 27.2 1.1 7.0
C6H4 (CH3)2 20/4°C) (TOC)

Water gas Used as fuel

made from
coal
Zinc Made by
Hindustan
Zinc Ltd fused
for electro-
galvanizing
of steel and
explosive and
as nutrient.
Appendices 597

APPENDIX 3: MAJOR PETROLEUM, PETROCHEMICAL, FERTILIZER AND

CHEMICAL INDUSTRIES IN INDIA
Name of Unit Address Product
Aarti Industries Ltd. Udyog Kshetra, 2nd floor, o-Nitrochlorobenzene, oleum,
Mulund-Goregaon Link Road, sulfur trioxide and sulfuric acid.
LBS Marg, Mulund (W), Mumbai–400080
Tel.: 022-5690412/5918195
Fax: 022-5653185
Factory: Plot 801, GIDC Estate,
Phase III, Vapi, Gujarat–396165
Abhideep Chemicals 208, Keshava Bldg., Inorganic chemicals, organic
Pvt. Ltd. Bandra-Kurla Complex, chemicals, alpha naphthol, beta
Bandra (E), Mumbai-400051 naphthol, beta-oxynapthoic acid
Tel.: 022-6407778/6424736 and sodium sulphate.
Fax: 022-6443283
Factory: A-2, MIDC Indl Area,
Ghugus Road, Chandrapur–442401
Tel.: 87618/87718 Fax: 87617
[Link].
Abir Chemicals Ltd. 74, Madhuban, Near Madalpur Dye intermediates, dyes, organic
Under­bridge, Ellisbridge, intermediates, acetani­lide,
Ahmedabad, Gujarat–380006 broenner acid, dimethoxyaniline,
Tel.: 079-6447174 J acid, reactive dyes, rhoduline
Fax: 079-6568204 acid, sulfo tobias acid, tobias acid
Factory: Plot no. 901/1, Phase III, and vinyl sulphone.
GIDC, Vapi, Valsad, Gujarat-396195
Tel.: 32898 Fax: 31895
Acharya Chemicals B-2/11, Jawahar Darshan, Drug intermediates, drugs and
Manpada Road, Dombivli (E), pharmaceuticals, 2-amino-
Thane–421201, Maharashtra 5-bromobenzo-nitrile, 2-amino-
Tel. 0251-470415 5-chlorobenzophenone,
Fax: 0251-473857 2-aminobenzonitrile,
[Link] p-aminobenzonitrile and
p-nitrobenzonitrile.
Acme Petrochem 30, Baroda Co-op Indl Estate, Drug intermediates, dye interme­
Chhani Road, Baroda, Gujarat–390002 diates, fine chemicals, acetic acid,
Tel.: 0265-773785, 771648 chloranil, ferrous sulfate, hydro­
Fax: 0265-771648 chloric acid, sulfanilamide, sulfuric
Factory: 3812, GIDC Estate, acid and vinyl sulphone.
Ankaleshwar, Distt. Bharuch,
Gujarat–393002
Tel.: 02642-26190
[Link]
Acme Synthetic 308, Veer Savarkar Marg, Dadar, Organic chemicals and methyl
Chemicals Mumbai, Maharashtra acetate.
Tel.: 022-4465127, 4452706
Fax: 022-4440282
email : aacash@[Link]
[Link]
Contd....
598 Chemical Process Technology

Contd...

Name of Unit Address Product

Adarsh Chemicals Post Box No. 13, Udhna, Fertilisers, inorganic chemicals,
and Fertilisers Ltd. Surat, Gujarat–394210 organic chemicals, adipic acid,
Tel.: 0261-677233 maleic anhydride, malic acid,
Fax: 0261-677049 oleum, single superphosphate and
[Link] sulfuric acid.
Ahmedabad Manu­ Outside Jamalpur Gate, Textiles chemicals and polyster
facturing and Calico Ahmedabad–380022 fibers.
Printing Co. Ltd. Gujarat
Ajanta Fine Block 23, Rameshwar Bldg., Organic intermediates, bromo
Chemicals 4th Floor, Ram Gully, SV Road, benzene, ethyl bromide, isopropyl
Kandivli (W), Mumbai-400067 bromide, n-butyl bromide and
Tel.: 022-8192177,8070818 n-propyl bromide.
Factory: V-10, Panchal Udyog
Nagar, Goddeo, Bhayander, Thane,
Maharashtra–401101
Tel.: 8192177, 8191713
Alembic Chemical Alembic Road, Drugs and pharmaceuticals,
Works Co. Ltd. Vadodara, Gujarat–390003 butyl acetate, ethyl alcohol, ethyl
Tel.: 0265-380880 Fax: 0265 382134 chloride and polypropylene glycol.
Factory: Panelav, Taluka Halol,
Distt: Panchmahal, Gujarat.
Alkyl Amines 207-A, Kakad Chambers, 132, Ethyl amines (mono-, di-, tri),
Chemicals Ltd. Dr AB Road, Worli, Mumbai-4400018 methyl amines (mono-, di-, tri-),
Tel 4931390/4931385/4925564 cyclohexylamines (mono-, di-) and
Fax No. 49307010 isopropylamines (mono-, di-).
E-mail alkyl@[Link]
Works: Plot No. A-7 and A-25
MIDC Patalganga Industrial Area,
Vill Kaire, Taluka Khalapur,
Distt. Raigad–410220 (MS)
Allied Resins & 13, Camac St. Kolkata– 700017, WB Organic chemicals, organic inter­
Chemicals Ltd. Tel.: 033-22832865 mediates, polymers and plastics,
Fax: 033-22832857 synthetic resins, formal­dehyde,
Factory: Vill. Rampur, hexamine, paraformaldehyde,
PO Govindapur, Budge Budge Road, pentaerythritol, phenolic resin
24 Parganas, West Bengal and sodium formate
Tel. : 033-4784027/4028
[Link],arcl@[Link]
Alpha Chemie 30 Sapthagiri, Bharat Thirtha Soc., Accelerators, additives, anti-
Sion-Trombay Road, Chempur, fungal chemicals, defoamers and
Mumbai, Maharashtra–400071 dispersions, fillers, hardeners and
Tel.: 022-5550908 auxiliaries, inorganic chemicals,
Factory: A/2-622, GIDC, Panoli, metallic salts, specialty chemicals,
Dist Bharuch, Ankaleshwar, stabilisers, methyl ethyl ketone,
Gujarat–394116 oxime, napthenates and octoates
Tel.: 72169
Contd....
Appendices 599

Contd...

Name of Unit Address Product

Amal Rasayan Contractor Building, Chemical products both organic
Limited (Formerly Ramji Bhai Kamani Marg, and inorganic and in particular
Piramal Rasayan) Ballard Estate, Mumbai–400038 naph­thalene based dyes and inter­
Grams: ‘NAPTHACHEM’ mediates
Works: 136/137, GIDC
Industrial Area
Ankaleshwar, 393002,
Near Bharuch, Gujarat
25/MIDC Industrial Area,
Roha–402116, Distt. Raigad,
Maharashtra
Amar Dye-Chem Rang Udyan, Bldg. No. 1, Sitadevi Synthetic org. Dyestuff and
Ltd. Temple Road, Mahim, pig­ments, syn. Resin binders,
M/s KCA Ltd. is a Mumbai–400 016 org. Peroxides, phenyl beta
subsidiary company Ph.: 022-4461033, 4453251 napthylamine, PVC stabilisers
Grams: “AMARCHEM” and orthophexylene diamine.
Telex: 1171524 AMAR IN
Fax: (91) 22-4449024
[Link]
Amarjyot Chemical 66/5 Kalshi Sadan, Jyotiba Phule Rd, Agrochemicals, drug inter­me­
Corporation Dadar, Mumbai–400014 diates, dye intermediates, o-nitro­
Tel.: 022-4134374,4077431 chlorobenzene sulphonic acid,
Fax: 022-5653234 p-nitro chlorobenzene o-sulfonic
Factory: Plot No. 211/2/2 MIDC, acid, p-nitrophenol sodium salt
Tarapur, Thane, Maharashtra–401506 and potassium fluoride
Tel.: 02525-70374
Amines and D-Bldg, Shiv Sagar Est Dr AB Road, Industrial gases, organic
Plasticisers Ltd. Worli, Mumbai–400018 chemicals, plasticisers, rubber
Tel.: 022-4935282/87/88 chemicals, diethanolamine,
Fax: 022-4938162 diisodecyl phthalate, diisooctyl
Factory: Thane-Belapur Road, phthalate, dimethyl monoethanol
Turbhe, New Mumbai–400705 amine, dioctyl maleate, dioctyl
Tel.: 7681321 Fax: 022-7681332 phthalate, ethanol amine,
e-mail amines@[Link] methyl diethanol amine,
Website [Link] methyl monoethanol amine,
amines@[Link] monoethanol amine, morpholine,
n-methyl morpholine, n-methyl
morpholine oxide, nitrous oxide,
propyl diethanol amine and
triethanolamine.
Andhra Petro­ 2-F, Subhodaya Apts, 4-1-1233, Petrochemicals
chemicals Ltd. Boggulakunta Abids,
Hyderabad–500001, Andhra Pradesh
Tel.: 040-233719 Fax: 040-235019
Factory: Opp. Naval Dock Yard, P.B.
No. 1401, Visakhapatnam,
Andhra Pradesh–530014
Tel.: 0891-578342; Fax: 0891-577751
Contd....
600 Chemical Process Technology

Contd...

Name of Unit Address Product

ARLABS Ltd. 6-Malhotra House Opp. GPO Stabilized vats, stabilized azoics,
Mumbai 400001 vat dyes, naphthol, bases, pd, oil
Ph.: 2612077-78-79 soluble dyes, dispersed dyes, dyes
Telex: 011-81037 RLAB-IN and intermediates
Fax: 2613234
Factory: Bhatghar, Bhor (Post)
Pune Distt.–412 206
[Link]
Ashok Organic 406, Sharda Chambers, 33, Mew Marine Alco chemicals, chlor alkali,
Industries ltd. Lines, Mumbai–400020 inorganic chemicals, organic
Tel.: 022-2002236/2006410 chemicals, organic intermediates,
Fax: 022-2009456 acetaldehyde, acetanilide, acetic
Factory 1: acid, acetic anhydride, caustic
318-319 GIDC Estate, Ankaleshwar, soda, ethyl acetate, ethyl alcohol,
Bharuch, Gujarat-391001 monochloroacetic acid, NTA,
phenoxy acetic acid, sodium
Factory 2:
acetate, sodium chloride, sodium
Ankaleshwar-Hansot Rd, PO Boridra,
monochloroacetate and sodium
Tal Ankaleshwar, Gujarat
monochloroacetic acid
Factory 3:
41/A, GIDC Industrial Estate,
Nandesvari, Gujarat–391340
[Link]
akadkia@[Link]
Assam Regd. office Lamb Rd, Ambari, Formaldehyde and methanol
Petrochemicals Ltd. Guwahati, Assam–781001 Carbon dioxide
Tel.: 0361544147, 0361543484
Fax: 0361547643
Factory: Namrup, PO Parbatpur,
Dist Dibrugarh, Assam-786623
Tel.: 037535-4331/4212
Atul Products Ashoka Chamber, Rasala Marg Synthetic cresols and its by
Limited (Formerly Mithakhali Cross Roads products, viz., sodium sulfite,
Gujarat Aromatics Ellisbridge, Ahmedabad–380006 sodium sulfate, gypsum and soda
Ltd.) Ph.: 079-233261,233331 ash.
Fax:079-233619,233029
Grams: TULA
Works: Ankaleshwar Division
297, GIDC, Industrial Estate,
Ankaleshwar–393002,
Distt. Bharuch, Gujarat
Works: Ankaleshwar Division
297, GIDC, Industrial Estate,
Ankaleshwar–393002,
Distt. Bharuch, Gujarat
Atul Divisions,
Atul–396020, Gujarat
Contd....
Appendices 601

Contd...

Name of Unit Address Product

Baroda Rayon Fatehnagar, Nylon yarn, polyester filament
Corporation Ltd. Surat–394220, Gujarat yarn, nylon tyre cord, fabrics, poly­
Ph.: 0261-690371-75 ester filament yarn and auxi­liary
Fax: 0261-89454 chemicals such as carbon di sulfide,
Grams: RAINBOW sulfuric acid, anhy­drous hydrous
[Link] sodium sulfate and sodium sulfide
Bajaj Plastics Ltd. Imambada Road, Hdpe/pp, woven sacks and fabrics.
Nagpur–440018
Ph.: 48711; 0712-2720071
Fax: 07122728050;
Grams: BAJAJPLAST
BASF India Ltd. Poulene House, AK Ahise Marg, Expandable and expanded polys­
Mumbai–400 025 tyrene (styropor) tanning agents,
Ph: 022-4390703; leather auxiliaries, oil and well
Fax: 022-4950993 chemicals, leather auxiliaries and
Works: finishing agents and pesticides
1. Thane-Belapur Road, Turbine, basic production
Maharashtra
Bok Bokaro Industrial Area, Bokaro, Bihar
[Link]
email: ghosha@[Link]
Bayer (India) Ltd. Express Towers, Nariman Point, Agrochemicals, rubber chemicals
Mumbai–400 021 and health care products
Grams: BAYERIND
Factory: Kolshet Road, Thane–400607
66/1 to 75/2, GIDC Estate,
Himmatnagar–383001, Gujarat
Bakelite Hylam 7-2-1669, Sanathnagar, PO Box. 1908, Industrial plastics, raw
Limited Hyderabad–500018, Andhra Pradesh materials, such as phenolic
040-3708913, molding materials, polyester
Grams: ‘BAKELITE’ resins and other allied products
Fax: 040-3702672 and industrial and decorative
Works: P-1/1, Industrial Development laminates
Area, Nacharam, Hyderabad–501507
(AP) Sanathnagar, Hyderabad
Bhivkund Nala, Chandrapur
Beardsell Ltd. 47 Greams Rd., Madras–600006 Expanded polystyrene, insulations,
(Formerly Mettur Grams. : BEARDSELL etc. trading in chemicals, electric
Beardsell Ltd.) Ph.: 044-8272542 Telex: 041-7665 motors, exports of fabrics etc.
Benzo 5, Welcome Shopping Centre, Drug intermediates, fine
Petrochemicals Ltd. Opp. Punit nagar, Old Padra Road, chemicals, organic chemicals,
Baroda, Gujarat–390007 speciality chemicals, benzyl
Tel.: 0265-333302 Fax: 0265-330640 alcohol, meta nitro benzo
Factory: Plot No. 130/131, GIDC nitrile, o-chloro benzo nitrile,
Estate, Nandesari, Baroda, Gujarat o-chlorobenzyl amine,
Tel.: 0265-840308 Fax: 840628 o-cyanotoluene and p-cyano
[Link] toluene
Contd....
602 Chemical Process Technology

Contd...

Name of Unit Address Product

Berger Paints India Berger House, 129 Park Street, Manufacture of synthetic resins,
Ltd. Kolkata–700017 paints, varnishes, enamels
Subsidiaries: Ph.: (033) 2299724
BeePee Coatings Telex: 021-5482/5791;
Ltd. Cables: ‘BERGERISE’
Fax : 91-33-2499009, 9729
berger@[Link]
Bharat Petroleum PO Box No 1725, Mumbai–400001 Petroleum products, propylene,
Corporation ltd. Mahul, Mumbai–400074 greases, refineries, toulene, bitumen,
Phone 022 -2617398 carbon black, diesel, furnace oil,
Fax 5562970 hexane, kerosene, LPG, naphtha,
Gram Bharefin petroleum ether, propylene, rubber
[Link] processing oil, sulfur, transformer oil
and turpentine
Blue Blends 3, Balaji Textile Market, Dyes and dyes intermediates,
Petrochemicals Ring Road (1st Floor), vinyl acetate monomer (VAM)
Limited Surat–395 002, Gujarat and nitric acid
Ph.: 621670, 622102
Factory: 5904/2, GIDC,
Ankaleshwar, Gujarat
Plot No. 806–807, GIDC Vapi, Gujarat
Bongaigaon PO Dhaligaon, Distt Bongaigaon, Petroleum products (gasoline,
Refinery and Assam–783385 kerosene, diesel, lubricating oil
Petrochemicals Ltd. Tel.: 03664-241231 Fax: 03664-241230 bitumen, p-xylene, DMT and
[Link] polyester
Chambal Fertiliser Gadepan-325208 Ammonia and urea from natural
and Chemical Ltd Distt. : Kota (Rajasthan) gas
Phone: 07455-270121-127
Fax: 45017
Capri Hans India Block D, Shivsagar Estate, Dr. Annie Rigid and flexible PVC sheets,
Ltd. Beasant Rd., Worli, Mumbai–400018 plastic extruded sheets, polythene
Works: sheets and films, phenolic and
Ph: 022-4921900 Fax: 022-4934042 melamine laminate, phenolic
Plot No. C-13/16, Road No. 16/T, resin varnishes and melamine
Wagle Industrial Estate, Thane–400601 formaldehyde resin.
Plot no. 157, 158A, Akbar camp Rd.,
Kolshet, Thane-400061
Plot no. 76, MIDC Induatrial Estate,
TRIMBAK Road, Satpur Distt.,
Nasik–422007
Plot no. 111, MIDC Industrial Estate,
Roha, Distt. Kulaba–402116
Camphor and Plot No. 3, GIDC Industrial Estate, Camphor, isoborenol, pine oil,
Allied Products Ltd. Nandesari–391340, Vadodara, tupineols and esters, isobarnyl
(Formerly Gujarat acetate, polyterpene resin, methol,
M/s Profeel Sentinel office@[Link] thymol and fenvelerate.
Ltd.) [Link]
Contd....
Appendices 603

Contd...

Name of Unit Address Product

Cellulose Products National Chambers, Office Nos. 4 and 5, Sodium carboxy methyl cellulose,
India Ltd. 2nd Floor, Near Dipali Theatre, Ashram modified starch and gum, cellulose
Road, Ahmedabad–380 009, Gujarat powder, cotton linter pulp, straw
Works: board, polyvinyl alcohol, industrial
Kathwada (Distt. Ahmedabad) alcohol, tamarind kernel powder
Ramol (Distt. Ahmedabad) and acetic acid.
Kappalur (Distt. Madurai, Tamilnadu)
Pungam (Distt. Bharuch,
Ta. Ankaleshwar)
Citurgia Nevlille House, JN Herdia Marg, Citric acid, dibutylpthalate,
Biochemicals Ltd. Ballard Estate, calcium carbonate and tributyl
Mumbai–400038 citrate
Coates of India Ltd. Transport Depot Road, Printing ink, printers sundries,
Taratala Kolkata–700 088 synthetic resins and other surface
Ph.: 450 011 (6 lines), 451877 coating materials
Grams: ‘SPECTRUM’; Telex: 7762
Colour-Chem Ltd. Ravindra Annexe, Dinshaw Vachha Synthetic org. dyestuff, pigment
Road, 194 Churchgate Reclamation, dyestuffs and their dispensions,
Mumbai–400 020 syn. Resin binder material and
Ph.: 2022161,2830882; auxiliaries, intermediates for dyes,
Fax: 22029781 pesticides, pharmaceuticals
Grams: PIGMENTDYE;
Telex: 011-3365
Works: Mumbai-Agra Road,
Balkum Village, Thane–400608
113/114, MIDC Industrial Estate,
AV Roha, Dhatav, Distt.
Raigad–402 116
Subsidiary: Kudikadu, PO Cuddalore–607003 Syn. org. compounds,
Vanavil Dyes and Ph.: 2059, 2077 and 2159 intermediates and dyestuffs
Chemicals Ltd. Grams: VANAVIL
Telex: 462209-VDCL IN
[Link]
[Link]@[Link]
Cosmo Films Ltd. 30 Community Centre, Saket, Biaxially oriented polypropylene
New Delhi–110017. film.
[Link]
Grams: COSMOPHAIN
Ph.: 011-26863968,9
Fax: 01126868093
Telex: 031-61219, 031-62147
Works: J-4, MIDC Ind. Area,
CIDCO, PO Chikalthana,
Aurangabad–431210
B-14/9, MIDC Ind. Area, Waluj,
Aurangabad–431133
Telex: 0745-257
Contd....
604 Chemical Process Technology

Contd...

Name of Unit Address Product

Cochin Refineries Ambala mugal, Ernakulam, Distt. Gasoline, kerosene, diesel and
Ltd. Kerella–682302 lubricating oil.
Ph: 0484-706100
Consolidated Offtel Towers, 6th Floor, Carbon black.
Petrotech Industries RC Dutt Road, Vadodara–390005
Ltd. (Formerly Gujarat
Gujarat Carbon Ph.: 326406, 326407
Ltd.) Telex: 0175-376; Grams: ‘Tufblack’
Works: National Highway No. 8,
Palej, District Bharuch, Gujarat
DCM Shriram Kanchenjunga Bldg., Urea, PVC resins, caustic soda,
Consolidated Ltd. 18, Barakhamba Road, liquid chlorine, cement, yarn and
New Delhi–110001 cloth, ammonia and hydrochloric
Ph.: 3316801; Telex: 03162632 acid
Fax: (91) 011-3318072
Unit: Shriram Fertilisers & Chemicals
Shriram Nagar, Kota (Rajasthan)
Phone 91-744-423391098
Fax 91-744-423296-97-98,422136
[Link]
DCW Ltd. 1. Dhrangadhra–363315 (Gujarat) Soda ash, soda bicarbonate, salt,
Subsidiary: Ph.: 28001, 281288, 280329 bromine, hydrochloric acid,
DCW Home Fax: 04639-280611; liquid chlorine, caustic soda and
Products Ltd. Grams: ‘CHEMICALS’ trichloroethylene
Arumuganeri
PO Sahupuram–628 202 (Tamil Nadu)
Kuda (Gujarat State)
Vedaraniam (Tamil Nadu State)
Deepak Fertilisers Shivshakti BG, Kher Marg, Ammonia and nitric acid.
and Petrochemicals Worli, Mumbai–400018
Corp. Ltd. Ph.: 4933162; Grams: DEEPAMMON
Telex: 011-76278; Fax: (91) 224949426
Works: Plot K-1, MIDC Industrial
Area, Taloja, MS
Deepak Nitrile Ltd. 9/10, Kunj Society, Alkapuri, Sodium nitrate and other allied
Baroda–390 005 chemicals, hexamethylene
Grams: “SELENICA” tetramine, dyes and dyes
Subsidiary: Ph.: 325113 intermediates.
Nova Synthetics Factory:
4/12, GIDC Chemical Complex,
Nandesari–391340 Distt. Baroda
Ph.: 60231 to 60233;
Telex: 0175-589
Sahyadri Dyestuffs & Chemicals, 117,
Parvati, Vithalwadi,
Pune–411 030
Contd....
Appendices 605

Contd...

Name of Unit Address Product

Dharamji Morarji The Prospect Chambers, 317/21, Agrochemicals, Fertilisers,
Chemical Co Ltd. Dr DN Road, Fort, Mumbai–400001 Inorganic chemicals, acetyl
Tel.: 022-2834308 sulfonyl chloride, alpha naphthol,
Fax: 022-2843280 alumina sulfate, aluminum
Factory: Plot No. 105, MIDC fluoride, ammonium chloride,
Indl Area, Dhatav, Roha, Raigad, ammonium silico-fluoride,
Maharashtra-402116 ammonium sulfamate, benzene
Tel.: (02144) 63553, 63870 Fax: 63557 sulfonyl chloride, benzene
[Link] sulfonamide, beta naphthol,
chlorosulfonic acid, cryolite,
2,4-dichlorofluoro-benzene,
diethyl sulfate, EDTA, ethyl
alcohol, methane sulfonic acid,
resorcinol, silica, single super-
phosphate, sodiumfluoride,
sodium silico fluoride, sulphamic
acid, sulfur trioxide, sulfuric
acid, thiophenol and triple super-
phosphate.
Diam Organic 312/313, Nirmal Kendra Alco chemicals, emulsions,
Chemical Inds. Pvt. Dr E Moses Road, Mahalaxmi oil field chemicals, organic
Ltd. Mumbai–400011 intermediates, petrochemicals,
Tel.: 022-4970577/4970578 specialty chemicals, surfactants,
Fax: 022-4970703 alcohol ethoxylate, diethyl glycol,
Factory: Plot No. C-11, MIDC, Mahad, monoethyl ether, ethylene glycol
Distt Raigad, Maharashtra monoethyl ether, glycol ether and
Tel.: 02145-320-56/57 nonyl phenol
[Link]
Diamines and Premises of Bharat Vijay Mills Ltd. Ethylene diamine and
Chemical Limited Kalol 382721, North Gujarat, polyamines, diethylene triamine,
Grams: BHARATMILL triethylene triamine, and other
Works: Plot No. 13, PO Petrofils, polyethylene polyamines used
Baroda 391347, Gujarat mainly for the manufacture of
pesticides and fungicides, textile
auxiliaries, paints and adhesives,
drug intermediates and paper
DUNCAN Panki Fertilisers Works, Ammonia and urea
Fertilisers Ltd. P.B. No. 7, Udyognagar,
Kanpur-208022
EAP Industries Ltd. 145, Jessore Road, Cellulose acetate, molding
Kolkata–700 089 powder, PVC compounds,
Grams. : ‘INSTANGLIA’ Coloring of polyethylene
Ph.: 248176/79 (4 lines) granules, barium sulfate
compounds, pthalate plasticizers,
lamination of thermoplastics,
PVC polyethylene and cellulose
acetate on variety of plastic
finished products, substrata and
leather goods.
Contd....
606 Chemical Process Technology

Contd...

Name of Unit Address Product

Fertiliser Madhuban, 55, Nehru Place, Fertilisers, Industrial gases,
Corporation of India New Delhi–110019 Ammonia, ammonium
Ltd. Tel.: 011-6410758,6212966 bicarbonate, ammonium nitrate,
Fax: 011-6224311 nitric acid, nitrogen gas, oxygen
Factory: PO Sindri, Dhanbad, and urea.
Bihar–828122
Tel.: 0326-51235/51427/51364
Fax: 0326-514-23/27
[Link]
Fertilisers and PB No. 14, Udyogamandal, Kochi, Fertilizers, inorganic chemicals,
Chemicals Kerala–683501 petrochemicals, ammonia, ammo­
Travancore Ltd. Tel.: 0484-541101 to 541104, 541045 nium sulfate, capro­lactam, nitric
Fax: 0484-532475, 540486, 541072 acid, phosphoric acid, soda ash
[Link] and sulfuric acid.
FICOM Organics G-12, Tulsiani Chambers, Nariman Malathion, technical and
Ltd. Point, Mumbai–400021 formulation based on malathion
Works: 3204, GIDC Industrial Estate, technical
Ankaleshwar Distt. Bharuch, Gujarat Dodecyl phenol nonyl phenol.
Tel.:2855481, 82 and 2955882
[Link]
Ganesh Benzo Plast 145-A, Dr. Viegar Street, High performing plasticizers–
Ltd. Mumbai 400002, benzoplast.
Ph.: 317993, 292768
Grams: BENZACID;
Telex: 011-3906 GNES
Works: D-5/2, MIDC, Tarapur
(Maharashtra)
Gas Authority of UP Petrochemical Complex, Ethylene propylene, polyethylene
India Ltd. Pata, Distt. Etawah (UP)–206241 (HDPE, LDPE), butene LPG,
Phone: 05683-24355; Fax: 24446, 24356 propane and pyrolysis gasoline.
Gas Authority of GAIL, Vijaipur (UP) LPG, gas processing unit.
India Ltd., Vijaipur
Gharda Chemicals 5-6, Jer Mansion, WP Varde Marg, Agrochemicals, insecticides,
Ltd. Off: Turner Road, Bandra (W), speciaty chemicals, anilofos,
Mumbai–400050 cypermethrin, isoproturon,
Tel.: 022-6452492/93/6405466 o-phenylene diamine and vanilin
Fax: 022-6404224
Factory 1: B/29 MIDC, Dombivli (E),
Thane, Maharashtra
Factory 2: D 1/2 MIDC Lote Parshuram,
Tal Khed, Distt. Ratnagiri, Maharashtra
Tel.: 02356-72187/88/89
Fax: 02356-72190, [Link]
Goa Carbon Ltd. Dempo House, Campal, Panaji, Calcine and deal in raw and
Goa–403 001 calcined petroleum coke and
Ph.: 832-226281, other by-products and to utilise
Telex: 0194-217; the waste gases for industrial
Fax: 91-832-5098 uses and purposes
Contd....
Appendices 607

Contd...

Name of Unit Address Product

Works: St. Jose de Areal, Curtorim
Salcette, Goa
Ph: 21071 and 21112 www.
[Link]
Godrej Industries Pirojshanagar, Eastern Express High Refined glycerine, stearic aid, oleic
Limited way, Vikroli, Mumbai-400 079 acid, fatty alcohol and alpha olefin
(Chemical Division) Tel 91-022-5188010, 20, 30 sulphonate (AOS)
Fax 91-22 5188068, 51880 96
[Link]
Gujchem Distillers ‘Chaitanya’, F-1, Sheth CG Road, Chemicals, soaps, preservatives,
India Ltd. Ellisbridge, Ahmedabad–380006 syn. Resins, etc.
Factory: Bhilimora, Dist. Valsad,
Gujarat
Ankaleshwar, Distt. Bharuch, Gujarat
Gujarat Alkalies and Yashkamal, Sayajiganj, Chlor alkali, effluent treatment
Chemicals Ltd. PO Box No. 2505, chemicals, inorganic chemicals,
Vadodara, Gujarat–390005 phosphatising chemicals,
Tel.: 0265-361611-2-3 carbon tetrachloride, chlorine,
Fax: 0265-362528 chloroform, chloromethane,
Factory: PO Petrochemicals, hydrochloric acid, hydrogen
Vadodara, Gujarat–391346 peroxide, methyl chloride,
Tel.: 0265-372681-82/372701 methylene chloride, phosphoric
Fax: 0265-372130/370031 acid, potassium carbonate,
potassium hydroxide, sodium
cyanide, sodium ferrocyanide,
sodium hydroxide, sodium
hypochlorite
Gujarat Apar Bldg. No. 5, Corporate Ark, Nr. Swastik Synthetic rubber, nitrile butadiene
Polymers Ltd. Chambers, Sion-Trombay Rd, Chembur, rubber and styrene butadiene
Mumbai–400071 rubber
Tel.: 022-5242371 Fax: 022-5246326
Factory: Vill. Dongri, Tal. Valia,
Nr. Ankaleshwar, Dist Bharuch, Gujarat
Tel.: 02643-72042
Gujarat Binil Plot No. 2701, GIDC, Industrial Estate, Engineering thermoplastics,
Chemicals Limited Ankaleshwar–393002 acrylonitrile butadiene styrene
Ph.: 20857, 20641 (ABS), styrene acrylonitrile (SAN)
Telex: 0189264 GBCL IN and high impact plastics.
Gujarat S/No. 16/3, 26 and 27, Ranjitnagar– Chlorofluorocarbon and hydro­
Fluorochemicals 389380, Devgarhsaria Taluka, fluoric acid
Ltd. Distt. Panchmahal, Gujarat
Gujarat Narmada PO Narmadanagar–392015, Fertilizers and chemicals,
Valley Fertilisers Co. Distt. Bharuch, Gujarat viz. ammonia, urea, methanol, etc.
Ltd. Ph.: (02642) 32001, 32424 generation of electricity.
Telex: 01813-201/202/214/215
Grams: GNFC
Fax: 02642-31595
Contd....
608 Chemical Process Technology

Contd...

Name of Unit Address Product

Gujarat Petro National House, 6, Tulloch Road, Polybutene
Synthese Ltd. Mumbai–400039
Tel.: 022-2022031, 2022376
Fax: 022-2022135
Factory: Petrochemical Complex,
PO Petrofil, Dist Baroda,
Gujarat–391347
Tel.: 0265-372994
Gujarat State P.O. Fertilisernagar, Distt. Vadodara, Ammonia urea, ammomium
Fertiliser Co. Ltd. Gujarat–391750 sulfate, diammonium phos­
Ph. 72451, 72641, 72651, 72751 phate, nylon 6, cyclohexane,
Grams: ‘FERTILISER’ cycohexanone, cyclonone-cyclo­
Telex: 0175-211/384; Fax: 0265-72966 hexanol mixture caprolactam,
argon, melamine, monomer,
sheets, pellets, nylon filament
yarn, nylon chips, mek oxime,
sulfuric acid, oleum, nitric acid,
methyl methacrylate polymer,
methacrylic acid and gypsum
Gwalior Chemical 1 and 2 GTZ India Ltd., Western India Organic chemicals, pigments,
Ind. Ltd. House, Sir P M Rd, Fort, Mumbai–400001 acetyl chloride, aluminum
Tel: 022-287-3541/415 chloride, benzal chloride,
Fax: 022-2851809 benzaldehyde, benzotrichloride,
Factory: Birlagram, Nagda, MP–456331 benzoic acid, benzoyl chloride,
Tel.: 07366-43347 Fax: 07366-46283 acetyl chloride
Haldia 1 Auckland Place, Kolkata Organic chemicals,
Petrochemicals Ltd. West Bengal–700017 petrochemicals, polymers and
Tel.: 033-247 1024/1023 plastics, specialty oils, synthetic
Fax: 033-2471361 rubber, benzene, butadiene,
[Link] carbon black, ethylbenzene,
isobutylene, gasoline, hdpe,
ethylene, propylene isobutylene,
lldpe/hdpe, polypropylene,
pyrolysis gasoline, styrene
butadiene rubber
Herdillia Chemicals Air India Bldg., Nariman Point, Phenol, acetone, diacetone,
Ltd. Mumbai–400021 alcohol, pthalic anhydride,
Ph.: 9122-22024224 cumene, a-methyl styrene and its
Grams. : HERDILLIA; Telex: 1183754 dimers, fumaric acid, capacitor
HCL IN, Fax: 22042379 fluids and other speciality fluids,
Works: Plot No. 2-1, TTC Industrial dodecyl and other alkyl phenols,
Area, Thane, Belapur Road, KV Bazar isobutyl benzene, diphenyl oxide,
Post Vashi, Navi Mumbai-400705 cumyl phenol, etc.
Ph. : 0215, 681153
[Link]
Herdillia Polymers Earnest House, 13th floor, Nariman Speciality chemicals, polybutene.
Ltd. Point, Mumbai– 400021
Ph.: 022-2830672 Fax: 022-2830771
Contd....
Appendices 609

Contd...

Name of Unit Address Product

Factory: Plot No. 802, TTC Indl
Area, MIDC Central Avenue, Thane-
Belapur Road, Navi Mumbai–400701
Tel. : 022-7691210 Fax : 022-7691761
Herdillia Unimers 2/2 TTC Industrial Est., D Block, Synthetic rubber, epdm rubber
Ltd. Thane Belapur Road, Turbhe, New
Mumbai–400705
Tel. : 022-7671838/7671853
Fax : 022-7672049
HICO Products Mahim, Mumbai, Glycol ethers and ethanol
Limited Maharashtra- 400016 amines, alkyl phenols, chemicals
Ph: 91224377231, 224221526 for petroleum recovery and
transportation, leather auxiliary
chemicals, silicon oils, greases,
rubber and emulsions, mono
alkyl benzene and polyalkyl
benzene
Hindustan R and D Centre, Sector 20, Agrochemicals, biopesticides,
Insecticides Ltd. Udyog Vihar, insecticides, BHC, butachlor,
Gudgaon–122016, Haryana dicofol, endosulfan, malathion,
Ph: 951242341336 monocrotophos, phosphamidon.
www.hil_india.com
Hindustan Organic Rasayani, Distt. Raigad–410207, Nitro products, hydrogen, aniline,
Chemicals Ltd. Maharashtra acetanilide acids, formaldehyde,
(Govt. Enterprise) Ph.: 02192250041; chlorobenzene, acetyl products,
Fax: 02192250050 phenols, acetone, propylene
Telex: 1304-202; cumene and other chemicals.
Subsidiary: Grams: HINORCH, RASAYNI Plastics, synthetic resins,
Hindustan 1402, Babukhan Estate, Basheerbagh, synthetic rubber and synthetic
Fluorocarbons Ltd. Hyderabad 500001 fibers of all kinds
Gram: ‘HINFLON’; Ph.: 237125, 234604
Works: PO Rudraram–502329,
Sangareddy Taluq, Medak Distt., AP
Hindustan Petroleum House, 17, J Tata Road, Petroleum products, coke, LPG,
Petroleum Corpn Churchgate, Mumbai–400001 lube oil base, naphtha, propane,
Ltd. Tel.: 022-2026151 Fax: 022-2872992 propylene, sulfur.
Factory 1: Corridor Road, Mahul,
Mumbai
[Link] 18820, BD Patil Marg
Factory 2: P B No. 15, Visakhapatnam,
AP–530001
Ph: 2564606
Indian Farmers Phulpur Unit, Ghiya Nagar, Ammonia, urea.
Fertilisers Allahabad 212400
Cooperative Ltd., Phone: 0532-641935, 642201;
05332-52250, 52252
Fax: 05332-52253
Contd....
610 Chemical Process Technology

Contd...

Name of Unit Address Product

Indian Farmers Aonla Unit P.O. IFFCO Township, Ammonia, urea
Fertilisers Distt. Bareilly 243403 (UP)
Cooperative Ltd. Regd office; 34, Nehru Place
New Delhi-110019
Phone: 0581-476556, 476758, 457211
Fax: 457227, 457213
Indian Farmers Kandla, Ghandinagar Ammonia, urea
Fertilisers Coop. Ltd.
Indian Farmers Kalol unit, P.O. Kasturinagar-382423 Ammonia, urea
Fertilisers Dist Gandhinagar, Gujrat
Cooperative Ltd., Phone: 02764 20202,20209,21056
Fax: 91-2764-20572,2712-75523,
Web site: [Link]
India Glycols Ltd. A-1, Industrial Area, Bajpur Road, Ethyl alcohol, ethylene, glycol,
Kashipur Distt. Nainital, UK–244713 ethylene oxide, diethylene glycol,
Cable: GLYCOLS heavy glycol
Ph.: 86273, 86690, 86641, 86670
Fax: 75315
Indian Oil P.O. Oil refinery Petroleum products.
Corporation Ltd. [Link]
Barauni Refinery Oil refinerry
Dist. Begusarai (Bihar)
Phone: 06243 23257, 75271
Fax 06243 24005, 23258, 24038
[Link]
Indian Oil PO Jawahar Nagar, Distt. Vadodara, Petroleum products, MTBE
Corporation Ltd. Gujarat 391320
Gujarat Refinery, Grams: Guajrat refinery
Indian Oil PO Haldia Oil Refinery, Petroleum products
Corporation Ltd. Distt. Midnapore-721606 (W.)
Halidia Refinery Phone: 03224-52147, 52151
Grams: Oil Refinery
Fax 91-3224-52204, 52141,52284
Indian Oil Mathura 261 005 (UP) India Petroleum products
Corporation Ltd. Phone: 845315
Mathura Refinery Fax 0565 842167, 842169, 430019,
430298
Telegram: Oil Refinery
Internet sit [Link]
Indian Oil PO Panipat Refinery Petroleum products
Corporation Ltd. Panipat-132140 (Haryana)
Panipat Refinery Fax: 01742 78833/43,4478825/26
Indian Oil PO Digboi Petroleum products
Corporation Ltd. Dist Tinsukia (Assam)
(formerly Assam Oil
Company)
Contd....
Appendices 611

Contd...

Name of Unit Address Product

Indian PO Petrochemicals–391346, Petrochemicals, viz. aromatic
Petrochemical Distt. Vadodara, Gujarat chemicals (DMT and xylenes)
Corporation Ltd. Ph.: 72011, 72031 and olefins (ethylene, propylene,
Telex: 0175-365 butadiene, benzene and pyrolysis
Grams: PETCOMPLEX gasoline), other chemicals such as
butadiene, ethylene propylene,
acetonitrile, benzene, heavy
paraffins and carbon black feedstock,
trading in polymer, fiber and fiber
intermediate and chemicals
Indian Plastics Ltd. Poisar Bridge, Kandivili, Bakelite powders, phenol form­
Mumbai-400067 aldehyde, urea formaldehyde,
Ph.: 661241/42/43/44 melamine formaldehyde, molding
Grams: ‘PLASTICS’ powders, industrial resins and
Works: Suri, Birbhum–731010 WB plastic products
Indu Nissan Oxo Bajwa Chhari Road, GSFC Complex, Oxo alcohols, isooctyl alcohol,
Chemical Industries Vadodara–391310 isononyl alcohol, isodexyl alcohol
Ltd. Ph.: 73391 and di-isobutylene and poly
Telex: 175-486 INOC IN butylene
IG Petrochemicals 401/404, Raheja Centre, Free Press Organic chemicals and phthalic
Ltd. Journal Marg, 214, Nariman Point, anhydride
Mumbai–400021
Tel.: 022-2840714 Fax: 022-2040747
Factory: T-2, MIDC Area, Taloja,
Raigad, Maharashtra
Tel.: 022-7410230 Fax: 022-7410192
ICI India Ltd. PO Box 9093, 34 Commercial blasting explosives,
Chowringhee, Kolkata–700071 cypermethrin (cymbush),
Grams: “INDEXPLO” detonating fuse, detonators,
Ph.: 296840/298688 gramoxone, military powder,
Telex: 21-5788 ACCI IN, 21-5795 IELIN nitrocellulose, paints stuff, paints
Fax: 033-29-6330 liquid, polyester stable fiber,
Corporate office: pharmaceuticals, pretreatment
DLF Plaza tower, DLF Qutab Enclave, chemicals, primary steam, naphtha
Phase I, Gurgaon-122 002 reformation catalyst, rubber
chemicals and diphenyl amine,
safety and military fuse, thinners,
textile auxiliaries and urea.
Indian Dyestuff Mafatlal Centre, Nariman Point, Dyes, dyes intermediates, org.
Industries Ltd. Mumbai-400021 Inorganic heavy chemicals
Ph.: 2024643
Telex: 113080 IDI IN
Gram: NAVICET
Works:
Kalyan, Distt Thane 421304
Boisar Distt. Thane 401506
Baroda, Distt. Baroda
Contd....
612 Chemical Process Technology

Contd...

Name of Unit Address Product

Indian Oil Scope Complex Core-2, 7 Institutional Petrochemicals, refineries, benzene,
Corporation Ltd. Area, Lodi Road, New Delhi–110003 diesel, gasoline, hydrogen, LPG,
Factory No 1: PO Barauni Oil methyl tert-butyl ether, paraffin
Refinery, Begusarai, Bihar–861114 wax and phenol.
Tel.: 06342-24036
Factory No 2: PO Mathura Refinery,
Mathura UP
Factory No 3: PO Haldia Refinery,
Dist Midnapur, W. Bengal–721606
Factory No 4: Gujrat refinery,
PO Jawahar Nagar, Dist Vadodara
Phone 91-265-373195, 307161
Fax no 0265-373195
Factory No 5: Gauhati Refnery,
Gauhati, Assam
Factory No 6: Assam Oil Company
Digboi, Assam
Factory No 7: Panipat Refinery
Panipat (Haryana)
Factory No 8: BRPL Assam
Indian Organic New Excelsior Bldg., Wallace Street, Polyester chips, polyester
Chemicals Ltd. Fort, Mumbai–400001 filaments, partially oriented yarn,
Ph.: 204-4587; Grams: “Tezab” Bombay methanol, alcohol based chemicals,
Telex: 011-75147 IOCL IN benzyl products, benzaldehyde,
Fax: 91-22-8281453 plasticizers, glyoxal, etc.
Indo-Gulf Fertilisers Jagdishpur Industrial Area, Fertilizers, chemicals and allied
and Chemicals Sultanpur–227817 (UP) products.
Corporation Ph.: 0535-802623, 802678 0536-2749, 2781
Grams: INGFECH
Telex: 0533-240 and 244 IGFC IN
Fax: 0536-2752
Jayalakshmi oil and Dokiparru–522438, Medikondur, Fatty acids, glycerine and toilet
Chemical Industries Mandal, Guntur Distt. AP soap.
Ltd.
Subsidiary of
M/s Andhra Sugars
Ltd.
Kanoria Chemicals ‘Park Plaza’, 71, Park Street, Caustic soda, liq. chlorine,
and Industries Ltd. Kolkata–700016 hydro­chloric acid, benzene
Subsidiaries: Ph.: 29-9472 (3 lines) hexachloride, stable bleaching
M/s Aekta Ltd., Telex: 021-4484 powder, yarn, cloth, penta­
M/s Kanoria Agro Fax: 91-33-299466 erythrital, sod. Formate and
Products Grams: KANORCHEM acetaldehyde.
M/s Vidun Dealers Factory: Renukoot Chemicals Works,
PO Renukoot, Distt. Sonebhadra, UP
Ankaleshwar (PO), Distt. Bharuch,
Rakhial Road, Ahmedabad, Gujarat
Contd....
Appendices 613

Contd...

Name of Unit Address Product

KCA Limited Rang Udyan, Sitladevi Temple Road, Synthetic organic dyestuff and dye
Mahim, Mumbai–400016 intermediates
Kothari Sugars and 114-117 MG Road, Nungambakkam, Leather chemicals and auxiliaries,
Chemicals Ltd. Chennai, TN–600034 organic intermediates, nitric acid,
Tel.: 044-8276036/8274892 o-nitrochlorobenzene,
Fax: 044-8266695 p-nitrochloro benzene and
Factory: Kattur, Lalgudi Taluk, polybutene
Trichy, Dist Manali, Chennai, TN
Krishik Bharti KRIBHCO Nagar, Surat-394515 Ammonia, urea
Co-perative Ltd. Phone 0261 8320034
Fax 91-261-8320038
Madhya Pradesh United House, 4, Press Complex, Electric grade biaxially oriented
United Polypro­ Zone-1, Maharana Pratap Nagar, polypropylene (BOPP-E) film, etc.
pylene Ltd. Bhopal–462011
Ph.: 550295
Telex: 0705-406 POLY IN; Grams:
UNIPHANE
Works: 26/6, Kilometer, Chiklod
Road, Distt. Raisen, via Bhopal, MP
Ph.: 51216
Madras Refineries Madras Refineries Ltd. Refining of crude oil and
Ltd. Chennai- 600068 manufacture of petroleum and by
Subsidiary: Ph: 044 541100 products
M/s Indian
Additives Ltd.
Mafatlal Dyes and Hoecht home, 193, Backbay Reclamation, Synthetic resins dispersions
Chemical Limited Nariman point, Mumbai–400021 and marketing of dye stuffs and
Grams: HYFDYECHEM polyester staple fiber
Ph.: 233832
Telex: 011-2556 MDC
Works: Lal Bahadur Shastry Marg,
Mumbai–400080
Manali SPIC Centre, 97, Mount Road, Propylene oxide, propylene
Petrochemicals Ltd. Guindy, Chennai–600032 glycol & Polyol.
Factory: Ponnery High Road, Manali
Chennai–600068
Manish Organics 7-A, Ratnam Sheth, CG Road, Glyoxal 40%, 2-methyl- 5-nitro
India Ltd. Ellisbridge, Ahmedabad–380006 imidazole, monochloroacetic acid
Ph.: 407535, 405865 and dimetridazole.
Grams: MORAL; Telex: 0121-6940 JBIN
Works: 5/1 GIDC Industrial Estate
NH 8, Ankaleshwar, 393002, Distt.
Bharuch, Gujarat Ph.: 20007
Mysore Acetate and Myrugar Bldgs, Sri Jaya Chamaraja Cellulose triacetate, secondary
Chemicals Co. Ltd. Wadiyar Road, Bengaluru–560002 acetate molding compounds,
Ph.: 211999, 211360, 211462 plasticisers, acetic acid, acetic
Telex: 0845236 anhydride and all kinds of
Contd....
614 Chemical Process Technology

Contd...

Name of Unit Address Product

Grams: MYACETATE materials used in film, plastic and
Works: Acetate town, Sathnur farm, rayon industries and all kinds of
Mandia 571404, Karnataka chemicals and alkalies with their
Ph. : 20134, 20261, 20524, 20523, 21056 derivatives and by-products
Mysore D/4 Jyothi Complex, 134/I, Infantry Rd, Phthalic anhydride and plasticisers
Petrochemicals Ltd. Bengaluru–560001
Factory: Phthalic Anhydride Plant:
Near Chicksugar Railway Station
Raichur, Karnataka
Maleic Anhydride Plant:
T-1, MIDS Indl Area, Taloja, MS
Synthetic Diamonds Division:
Shed No. 1102-1103
GIDC Panoli, Distt. Bharuch, Gujarat
Narmada Chematur 2nd Floor, Skyline Bldg., Organic chemicals, aniline and
Petrochemicals Ltd. Near Bharuch Rly Stn., Old toluene diisocyanate
National Highway No. 8, Bharuch,
Gujarat-392001
Tel. 02642-47190/47191
Fax: 02642-47180
Factory: Opp Hotel Nyay Mandir,
National Highway No. 8, PO
Narmadanagar, Bharuch, Gujarat
Tel.: 02642-47160,47161
Fax: 02642-46497
National Fertliser Nagal unit, Naya nangal (Punjab) Ammonia, urea and methanol
Ltd Nangal Unit, Naya Nangal 140126 (PB)
Phone: 01887-20649; Fax: 20541
National Fertliser National Fertiliser Limited, Ammonia and urea
Ltd., Bhatinda unit Kothi No. 50 Green Avenue,
Bhatinda, 151001
[Link]
National Fertliser Gohana Road, Panipat-132106 (Haryana) Ammonia and urea.
Ltd., Panipat Phone: 01742-20481 to 85, 20445
Fax: 45515
National Organic Mafatlal Centre, Nariman Point, Petrochemicals, agrochemicals
Chemical Industries Mumbai–400021 besides marketing and distri­bu­
Ltd. Plants: 5, Trans-Thane Creek, tion of industrial and agri­cultural
Industrial Area, Thane, Belapur Road, chemicals and animal vaccine
Thane, Maharashtra
A-1, Parshuram Industrial Area,
Taluka Khed, Ratnagiri, Maharashtra
Nirma Pvt. Ltd. Nirma House, Ashram Road, Detergents and Soaps,
Ahmedabad, Gujarat-380005 Petrochemicals, surfactants,
Tel.: 079-6586512-16, Fax: 079-6589136 Alpha olefin sulphonate and
[Link] linear alkyl benzene
Factory: Mandali, Mehsana, Gujarat
Contd....
Appendices 615

Contd...

Name of Unit Address Product

Nirmal Chlorants Phthalcocypin (Blue), Phthalco
and Chemicals cyamine (Green) and pigment
Manufacturing emulsion
Company Ltd.
(Subsidiary of
Hindustan Spinning
and Weaving Mills
Ltd.)
Nivedita Chemicals A-14, MIDC Cross Road-B, Detergents and soaps, drugs and
Pvt. Ltd. Street No. 5, Andheri (E), pharmaceuticals, paper chemicals,
Mumbai–400093 brompheniramine maleate,
Tel.: 022-8327321/9337 cetrizine dihydrochloride,
Fax: 022-8364256 chlorpheniramine maleate and
sodium phosphate, etc.
Nixon Chemicals 2nd Floor, Copper Rollers Premises, Aromatic and perfumery
Pvt. Ltd Opp PO Office LBS Marg, Bhandup (W), chemicals, leather chemicals and
Mumbai–400078 auxiliaries, organic intermediates,
Tel.: 022-5679134 Fax: 022-5676519 speciality chemicals, acetyl
chloride, benzaldehydride,
benzoic acid and benzyl chloride
Numaligarh Numaligarh, Assam Petroleum products including LPG
Refinery Ltd.,
Numaligarh, Assam
Orgo Chem Gujarat 305, Parekh market, Kennedy Bridge, Dye intermediates, organic inter­
Pvt Ltd Opera House, Mumbai–400004 mediates, aniline, 2,5- disulfonic
Tel.: 022-3826953/3885767 acid, metanilic acid, o-nitro-
Fax: 022-3806903 chlorobenzene, p-sulfonic acid,
Factory: Plot No. 256, GIDC, Sachin, p-nitrochlorobenzene-sulfonic
Gujarat–394230 acid and resist salt
Tel.: 0261-872515 Fax: 0261-872616
Oriental Carbon and 31, Netaji Subhas Road, Kolkata–700 001 Sulfuric acid, single super­
Chemicals Ltd. Ph.: 20-6831(20 lines) phosphate, liquid sulfur trioxide,
Telex: CA-7317 and CA-7791 oleum and carbon black
Fax: (033) 207063
Oswal Antriksh Bhavan, Petrochemicals
Petrochemicals Ltd. 7th Floor, 22 Kasturba Gandhi Marg,
New Delhi–110001
Tel.: 011-3715242/225
Fax: 011-3716276
Bindal Fertiliser and Shahjahanpur (UP) Ammonia and urea
Chemicals
Periyar Chemicals Calvetty, Cochin-1 Formic acid, sodium sulfate and
Ltd. Ph.: 24331 (3 lines) other chemicals
Telex: CN 212;
Grams: ‘ASPINWALCO’
Factory: Kadumganullur Village
Parur Taluk, Ernakulam
Contd....
616 Chemical Process Technology

Contd...

Name of Unit Address Product

Pentasia Chemicals East Coast Chambers, 92, GN Chetty Petaerythritol, sodium formate &
Ltd. Road, T. Nagar, Chennai–600017 formaldehyde
Works: B5–B10, SIPCOT Indl.
Complex, Kudikadu PO,
Cuddalone–607005
Polychem Limited 7, Jamshedji Tata Road, Churchgate Polystyrene, styrene monomer,
Reclamation, Mumbai–400020 industrial alcohol, potable
Ph.: 220048 and 220166 liquors, acrylonitrile, butadiene,
Telex: 1182203 KDCO IN, 1183434 ICC IN vinylacetate monomer and
Fax: 2041432 polyvinyl alcohol
Grams: POLYCHEMIC
Works: 45A, SV Road, Goregaon (W),
Mumbai–400062
Anil Mahul, Chembur, Mumbai–400074
Nira, Taluka, Baramati, Distt. Pune
14 PCC, Area PO Petrofils, Vadodara
Nimbur Village, Distt. Pune
Polyolefins Mafatlal Centre, 11th Floor, High density polyethylene
Industries Ltd. Nariman Point, Mumbai–400021 (Hostalen), processed
Ph.: 2024226,Telex: 011-83478 PIL IN polyethylene products, Ziegler
Grams: ‘PILENE’, Fax: 022-2020691 catalysts, n-Butene-1 and rubber
Factory: Thane-Belapur Road, chemicals
PO Ghansoli, Thane–400 701,
Maharashtra
Ph.: 922-2351, Grams: ‘PILTHA’
C-37, TTC, Ind. Area, Thane, MS
C-1, MIDC, Ind. Area, Akola, MS
Priya Polymers Pvt. 114, Cama Indl Estate, Nigols Bldg., Polymers and plastics, phenol,
Ltd. Goregaon (E), Mumbai–400 063 vinyl acetate monomer and vinyl
Tel.: 022-8731501 chloride monomer
Factory: T-35, MIDC Tarapur, Boisar,
Thane–401506
Punjab Chemicals SCO 371-72, Sector 35B, Diethyl oxalate and oxalic acid
and Pharmaceuticals Himalaya Marg, Chandigarh–160036
Ltd. Ph.: 0172-24955, 33121, 29836
Grams: PUNJXEL; Telex: 0395-288
PXEL IN Fax: 0172-43620
Works: Milestone-18, Ambala,
Kalka Road, PO Bankharpur-140201
Ph.: Derabassi 70, 82, 86, 87
Raj Prakash 114, Mittal Chambers, Monomeric acrylic esters such as
Chemicals Ltd. Nariman Point, Mumbai-400021 butyne acrylate, ethyl acrylate,
Ph.: 2020227, 2025583, 2048909 methyl acrylate, 2-ethyl hexyl
Grams: ACRYSTAR acrylate and miscellaneous
Telex: 011-85594 RPCL IN; Fax: 2024993 acrylates
Factory: Plant No. E-48, Tarapur,
MIDC Area, PO Boisar–401506, Thane
Contd....
Appendices 617

Contd...

Name of Unit Address Product

Rallis India Ltd. Ralli House, PO Box 166, 21 D S Marg, Agrochemicals, antifungal
Mumbai–400001, Tel.: 022-2078221 chemicals, antibiotics,
Factory 1: Thane Belapur Road, antioxidants, cleaning chemicals,
Thane, Maharashtra-400614 drug intermediates, drugs
Tel.: 022-7631999/2306; and pharmaceuticals, dye
Fax: 022-7632310 intermediates, emulsions,
Factory 2: GIDC, Plot No. 3301, enzymes, fertilisers, fine
Ankaleshwar, Bharuch, Gujarat–393002 chemicals, solvents
Tel.: 02646-51264/21075;
Fax: 02646-51388
Rama 812 Raheja Chambers, Nariman Point, Organic chemicals, methanol
Petrochemicals Ltd. Mumbai–400021
Tel.: 022-28341-23/82; Fax: 022-2049946
Factory: Savroli-Kharpada Road,
Vill. Vashivalli, Patalganga, Raigad,
Maharashtra-410220
Tel.: 02192-50326/50305
Fax: 01192-50166
Rashtriya Chemicals Rashtriya Chemicals and Fertilisers Ltd. Ammonia, urea, nitophosphates,
and Fertilisers Ltd. A Govt. of India Undertaking, Chembur, ammonium bicarbonate,
Mumbai-400074, Maharashtra monomethyl amine, dimethyl
Ph: 5561455 amine, trimethyl amine,
sodium nitrite, sodium nitrate,
ammonium nitrate, sulfuric
acid, gypsum, argon gas, hydro-
fluosilisilic acid, dimethyl
acetamide, dimethyl formamide
methanol, nitric acid
Reliance Industries Maker Chambers IV, 3rd Floor, 222, Organic intermediates,
Ltd. Nariman Point, Mumbai–400021 petrochemicals, benzene, carbon
Tel.: 912230325000; Fax: 022-2042268 black, diethylene glycol, ethylene,
Factory: B-4, MIDC indl Area, ethylene glycol, ethylene oxide,
Patalganga Off Mumbai-Pune formalin, linear alkyl benzene,
Road, Near Panvel, Raigad, LLDPE, HDPE, xylene, vinyl
Maharashtra-410207 chloride, etc.
Tel.: 02192-502015/50601-5
[Link]
Reliance Vill. Mora, Bhatha, PO. Surat Hazir Road Monoethylene glycol, higher
Petrochemical Ltd. Distt. Surat, Gujarat–394510 ethylene glycols, high density
Ph.: 96307, 96211, 96203, 96205 polyethylene, polyvinyl chloride,
Telex: 188-447 RIL IN Fax: 0261-42332 chlorine and caustic soda.
Reliance Petroleum 15, Walchand Hirachand Marg, Ballard Petroleum products.
Ltd. Est, Mumbai–400028
Tel.: 022-30327000; Fax: 022-22870072
Factory: Village Motikhavadi
PO Digvijaygram
Jamnagar, Gujarat–361140
Tel.: 0288-510000
Contd....
618 Chemical Process Technology

Contd...

Name of Unit Address Product

Rock Hard 102/A, Alankar Point, 5 Rajgarh Kothi, Fine chemicals, organic chemicals,
Petrochemical Agra-Bombay Td, Indore, MP-452001 formaldehyde and hexamine
Industries Ltd. Tel.: 0731-491185,492678
Fax: 0731-492679
Factory: Vill Kundla, Tehsil Agar
(Malwa), Dist Shajapur, MP
Tel.: 07362-52176/52880
SD Fine Chem Ltd. 315–317 TV Indl Estate Biochemicals, fine chemicals and
248, Worli Road, Mumbai-400025 lab chemicals
Tel.: 022-4936114/4932429
Fax: 022-4937232
Factory: E-27, 28 MIDC Tarapur Indl
Estate, Boisar, Thane–401501
Fax: 02525-72990
Shri Ambuja 7-C, Surya Towers, 105, Sardar Patel Pthalic anhydride, fumaric acid
Petrochemicals Ltd. Road, Secunderabad–500 003 and maleic anhydride
Works: Nos. 17, 18 and 20 IDA,
Phase-I, Patancheru–502319,
Distt. Medak, AP.
Shriram Fertiliser Shriram Nagar-324004, Kota (Rajasthan) Caustic soda, calcium carbide,
and chemicals Ltd Phone: 01744 423391-98; cement, PVC, ammonia, urea
Fax 91 744-423296
Shubham Aromatics 29, Bank Street, Mumbai–400023 Aromatic and Perfumery
Ltd. Maharashtra Chemicals, benzaldehyde, benzo-
Tel.: 2862453/2863021 trichloride, benzoyl chloride and
Factory: Birla Ram, Nagda, benzyl chloride
MP–456331
SM Dyechem Ltd. S M House, 11, Sahakar Road, Detergents and soaps, oil field
Vile Parle (E), Mumbai-400057 chemicals, petrochemicals, specia­
Maharashtra lity chemicals, surfactants, synthetic
Tel.: 8208445 resins, diethylene glycol, ethylene
Fax: 022-8208451 oxide, glycol ether, monoethylene
glycol and triethylene glycol
Smzschimmer and SM House, 11, Sahakar Road, Ville Parle Emulsions, de-emulsifiers,
Schwarz Chemicals (E), B’bay–400057 Ph.: 83377578 (4 lines) specialty chemicals, organic
Limited Telex: 011-79114 SMDC IN chemicals, fiber and yarn lubricants
Fax: 91-22-8377574 basic for synthetic soap
Southern Synthetics 20/6, Milestone, Mathura Road, Formaldehyde and hexamine
Ltd. (Subsidiary of Faridabad 121006
Nuchem Plastics Ltd.)
Spectrochem Pvt. 1129, Navjivan CHS ldg No. 3, Biochemicals, fine chemicals, lab
Ltd Dr. Bhadamkar Marg, Mumbai–400008 chemicals, solvents, specialty
Tel.: 022-3073317/2016969 chemicals, acetaldehyde,
Fax: 022-2059299 acetamide, acrylamide,
Factory: E-97, MIDC Indl Area, aluminum oxide, adipic acid,
Tarapur, Boisar, Thane, Maharashtra manganese sulfate, etc.
Tel.: 0252-572705
Contd....
Appendices 619

Contd...

Name of Unit Address Product

Sriman Organic Sriman House, BB/12 Veera Indl Est, Dye intermediates, dyes, organic
Chemical Industries New Link Rd, Andheri (W) chemicals, dichloro benzene, mono
Pvt. Ltd. Mumbai–400053 chlorobenzene, nitric acid, sulfuric
Tel.: 022-6316055/56; Fax: 022-6292066 acid, etc.
Factory 1: T-13/14, MIDC Tarapur,
Boisar, Thane, MS
Factory 2: B-50, Phase 1, MIDC Indl
Area, Dombivli (E), Thane, MS
Sriman 710 Dalamal Towers, Nariman Point, Organic intermediates, meta-
Petrochemicals Ltd. Mumbai-400021 chloro aniline, o-anisidine,
Tel.: 022-2844960/2830401 p-anisidine and o-chloroaniline
Fax: 022-2852286
Factory 1: A-171, Phase 1, MIDC,
Dombivli (E), Thane, MS
Factory 2: C-366/376, TTC Indl Area,
Turbhe, Navi Mumbai
Synthetics and Oriental House, 7-Jamshedji Tata Road, Rubber (SBR), nitrile rubber,
Chemicals Ltd. Mumbai–400 020 styrene, butadiene, etc.
Ph.: 220161; Telex: 11-85635 SYNT IN
Fax: 91-22-2870299
Grams: ‘SYNTHACHEM’
Works: PO Bhitaura Rubber Factory,
Bareilly–243501 UP
Ph.: 73371-72, Grams: ‘SYNTHACHEM’;
Telex: 577-212 SYNT IN;
Fax: 0581-76979
SomaiOrganics Regd. Office P and Works. Butyl alcohol, butyl acetate, ethyl
(India) Ltd. O. Somaia Nagar, acetate, acetic acid, paraldehyde,
Distt. Barabanki-2251239 UP dibutyl alcohol, diethyl phathalate
PH: 05248 30322, 30326, 30018, 30391
Fax: 05428 30368
Distellery: Captanganjdistellery,
Captanganj, Dist. Kushi Nagar, UP
Supreme Chemical 6/63, Mittal Tower ‘B’ ariman Point, Inorganic chemicals, leather
Industries Mumbai-400021 chemicals and auxiliaries, organic
Tel.: 022-2872460/61; Fax: 022-2872461 intermediates, dichloro benzene,
Factory: 159/1, GIDC, Nandesari, hydrochloric acid, monochloro-
Baroda, Gujarat Tel.: 338460 benzene, etc.
Supreme Petrochem 17/18, Shah Indl Estate, Petrochemicals, polystyrene
Ltd. Veera Desai Road, Andheri (W),
Mumbai–400053
Tel.: 022-6311829/30/33/39
Fax: 022-6367317/6324830
Factory:
Vill Amdoshi, Wakan-Roha Road,
Tal. Roha, Dist Raigad, MS-402106
Tel.: 0211442-2540-47 Fax: 2537,2617
Contd....
620 Chemical Process Technology

Contd...

Name of Unit Address Product

Supreme Soaps Pvt. Autocare Compound, 178, SV Road, Detergents and Soaps
Ltd. Andheri (W), Mumbai–400058
Tel.: 6211862 Fax: 022-6209777
Factory: E-56, MIDC Tarapur, Boisar,
Thane, MS-401 509,
Tel.: 72650
Tamilnadu 6, Nungambakkam High Road, Linear Alkyl Benzene and heavy
Petroproducts Ltd. Chennai–600034 normal Paraffin
(A joint sector Ph.: 8254545/8252569; Telex: 041-7533
company of TIDCO Fax: 044-863747, 044-8255798
and SPIC) Grams: PETROPRODUCTS
Works: 68, Manali Express Highway,
Manali, Chennai–600008
Ph.: 541350, 541360, 541370, 541380
Telex: 041-8827; Fax: 044-541139
Tata Chemicals Ltd. Mumbai Hse, 24, Homi Mody Street Chlor alkali, Fertilisers, inorganic
Mumbai–400001 chemicals, ammonia, bromine,
Tel.: 022-2049131/2881751 chlorine, ethyl bromide,
Fax: 022-2042947 hydrobromic acid, hydrochloric
Factory 1: Mithapur, Okhamandal, acid, liquid chlorine, sodium
Jamnagar, Gujarat–361345 bicarbonate, sodium carbonate,
Tel.: 02892-222-85/62411 Fax: 22227 sodium hydroxide, urea and zinc
Factory 2 : Indira Dham, PO Box No. chloride
1, Babrala, Dist Baroda–202521
Tel.: 05836-22347/9 Fax: 22357
Thana Acid and 609, Maker Chamber V, 221, Inorganic chemicals, organic
Chemical Co Nariman Point, intermediates, acetic acid, aniline,
Mumbai, Maharashtra–400021 formaldehyde, formic acid,
Tel : 022-2871996/2841133 hydrochloric acid, nitric acid,
Fax : 022-2851680 nitrobenzene, oleum, phosphoric
acid and sulfuric acid
Thirumalai Baldota Bhavan, 117, Maharshi Pthalic anhydride, maleic anhy­
Chemicals Ltd. Kharve Road, Mumbai–400020 dride and plasticisers
Ph.: 290445/251145
Factory: Ranipet, North Arcot Distt.
Tamil Nadu
Ph.: 4441/4442/4045
Telex: 402224, TCL IN/402 201
PTAN IN Fax: 041728-4308
Transpek Industry Kalali Road, Atladra, Sodium hexaphosphate, phosphoric
Ltd. Vadodara–390012, Gujarat acid, trisodium phosphate, sodium
Ph.: 559620/559720 tripolyphosphate, hexachloro cyclo­­
Grams: TRANSPEK pentadiene and allied chemi­cals
UB Petroproducts McDowell House, 3-Second Line Beach, Petrochemical products including
Ltd. Chennai 600001, Ph.: 520025-26-28 propylene oxides, polyols and
Telex: 0418787 UBPL IN propylene glycol
Factory: Sathangadu Village, Manali
Chennai–600066
Contd....
Appendices 621

Contd...

Name of Unit Address Product

United Carbon India NKM International House, Furnace black and various grades
Ltd. Babubhai M, Chinar Marg, of carbon used in tyre production.
178, Backbay Reclamation,
Mumbai–400020
Gram: UNICARBON;
Telex: 011-83107
Ph.: 202-1914, 202-7962, 202-7846,
202-8285, 202-0767; Fax: 2850406
Factory: MIDC Plot No. 3, Trans
Thane Creek Area, Thane,
Belapur Road, Post Ghansoli,
Thane–400701, Maharashtra
Unicorn Organics Thirumala Complex, 2nd Floor, Mannitol and other organic
Ltd. Sarojini Devi Road, chemicals
Secunderabad–500003,
Andhra Pradesh
Grams: UNIAGRO
Ph.: (0842) 8444920, 847351, 847329;
Fax: (0842) 842399
Works: 804, Waddepally village,
Warangal Distt. AP
Telex: 0825-219 VOLW IN
Ph.: (08712) 89156, 89127
Jubliant Organosys Sheetla House, 4th Floor, Adhesives, alcochemicals,
Ltd 73–74 Nehru Place, binders, drug intermediates, dye
New Delhi–110019 intermediates, fertilisers, inorganic
Tel.: 6465772, 6435922; chemicals, organic chemicals and
Fax: 011-6469088 organic inter­mediates, speciality
Factory: Bhartiagram, Gajraula, chemicals, acetaldehyde, acetic
JB Nagar, UP-244223 acid, acetic anhydride, butanol,
Tel.: 05927-52353 to 60 butyl acetate, formaldehyde,
picolinic acid, pyridine, poly vinyl
alcohol, sulfuric acid, etc.
Jubliant Organosys Bhartigram, Gajraula, Vinyl acetate monomer (VAM),
Ltd. Distt. Jyotiba Phooly Nagar, industrial alcohol, polyvinyl
Uttar Pradesh–244223 acetate, acetaldehyde, acetic acid,
Ph.: 05924 52351-52360 pyridine, acetic anhydride and
Fax 05924 523 352; Grams: picoline.
‘VARGONIC’
Web site [Link]
VCM Polyurethanes 329 A/2 Shah and Nahar I E, Leather chemicals and
Pvt. Ltd. S J Marg, Mumbai–400013 auxiliaries, protective coating and
Tel.: 022-4951967/4952408 polyurethane
Fax: 022-4974284
Factory: W-134 MIDC, Phase II,
Dombivli, Thane, MS-421204
622 Chemical Process Technology

APPENDIX 4: MAJOR MANUFACTURING ASSOCIATIONS

Name of firm Address
Adhesive Tape Manufacturers Association 1st Floor, Raj Mahal, 84 Veer Nariman Road,
Churchgate, Mumbai–400020.
Tel:(022) 22048075, 22048878
All India Food Processors Association 206, Aurobindo Place Market Complex
Hauz Khas, New Delhi–110016.
Tel: 011-26510860, 26518848
Fax: 011-26510860
E-mail: aifpa@[Link]
All India Industrial Gases Manufacturers 215, Square One, C-2 District Centre,
Association Saket, New Delhi - 110017, India.
Tel: +91-11-41076159
Fax: +91-11-41076158
All India Instruments Manufacturers and Dealers A/32, Navyug Niwas, 167,
Association Dr D Bhadkamkar Road,
Opp Minerva Theatre, Mumbai–400007
Tel: 022-2307 1868
Fax: 022-2307 1868
All India Rubber Industries Association 601, Pramukh Plaza, B Wing, 485 Cardinal
Gracious Road, Opp. Proctor and Gamble,
Chakala, Andheri (E) Mumbai–400099.
Tel: +91-22-28392095/2107
Fax: +91-22-6710 3211
E-mail: info@[Link]
Alkali Manufacturers’ Association of India 3rd Floor, Pankaj Chambers, Preet Vihar
Commercial Complex, Vikas Marg, Delhi–110092
Tel: 011-2243 2003/2241 0150
Fax: 011-2246 8249
E-mail: [Link]@[Link]
Association of Leasing and Financial Services (Office): Agra Building, 1st Floor, 131, MG Road
Companies Opp. Bombay University, Fort, Mumbai–400023.
Tel: 022-267 5400, 5500 Fax: 022-267 5600
Association of Merchants and Manufacturers of Bhogilia Hargovind Das Building, 18/20,
Textile Stores and Machinery (India) Kaikhushru Dubash Marg, Mumbai–400011.
Tel: 022-2284 4350/2284 4401
Fax: 022-2287 4060
E-mail: ammtsmi@[Link]
Association of Synthetic Fibre Industry 125, Uday Park (First Floor),
New Delhi–110049.
Tel: 011-26964154
Fax: 011-26515462
Cement Manufacturers Association Cement Manufacturers’ Association
CMA Tower
A-2E, Sector 24
Noida–201301 (UP)
Tel: 0120-2411955, 2411957, 2411958
Fax: 0120-2411956
Email : cmand@[Link]
Contd...
Appendices 623

Contd...

Name of firm Address

Confederation of Indian Alcoholic Beverages Z-27, Hauz Khas, New Delhi–110016.
Companies Tel: 011- 26534038
Fax: 011-26967900
Federation of Indian Mineral Industries FIMI House, B-311, Okhla Industrial Area,
Phase-I, New Delhi–110020.
Tel.: +91-11-26814596
Fax: +91-11-26814593/26814594
Email: fimi@[Link]
Fragrance of Flavor Association of India Navin Chandra Ram Chhoddas Shah Hall,
2B, Court Chambers, 35, Sir Vithaldas Thakeray
Marg, Mumbai–400020.
Tel: 022-2090184
Fax: 022-2005875
E-mail: fafia@[Link]
Indian Chemical Manufacturers Association Sir Vithaldas Chambers,
16-Mumbai Samachar Marg,
Mumbai–400023, India,
Ph: +(91)-(22)-4974308/4944624
Fax: +(91)-(22)-4950723
Indian Pump Manufacturers Association Indian Pump Manufacturers Association
406–408, “ATMA House”
Opp. La-Gajjar Chambers, Ashram Road,
Ahmedabad–380009, Gujarat, India.
Ph: +91-79-26583049
Fax: +91-79-26584194
Indian Refractory Makers Association Indian Refractory Makers Association,
5 Lala Lajpat Rai Sarani, 4th Floor,
Kolkata–700020, West Bengal, India.
Ph: 091-33-22810868
Fax: 091-33-22814357
Indian Soap and Toiletries Makers’ aAssociation 614, Raheja Centre, 6th Floor,
Free Press Journal Marg,
Nariman Point, Mumbai–400 021.
Tel: 022-2285 3649/2282 4115
Fax: 022-2285 3649
E-mail: istma@[Link]
Indian Sugar Mills Association Indian Sugar Mills Association (ISMA)
Ansal Plaza, ‘C’ Block, 2nd Floor,
August Kranti Marg, Andrews Ganj,
New Delhi-110049 (India).
Ph: +91-11-2626 2294-98 Fax: +91-11-2626 3231
E-mails: isma@[Link]
Organization of Pharmaceuticals Producers of Peninsula Chambers, Ground Floor
India Ganpatrao Kadam Marg, Lower Parel,
Mumbai–400013.
Ph: +91 22 24918123, 24912486, 66627007
Fax: +91 22 24915168
Contd...
624 Chemical Process Technology

Contd...

Name of firm Address

Organization of Plastics Processors of India 404/5, Golden Chambers, New Link Road,
Andheri (W), Mumbai–400053.
Tel: 022-6326958, 6323644, 6692 3131
Fax: 022-6346975
Process Plant and Machinery Association of India 002 Loha Bhavan, 91/93 , P D’Mello Road
Masjid (East), Mumbai–400009, India
Tel: 91 22 2348 0965, 2348 0405.
Fax: 91 22 2348 0426
Textile Machinery Manufacturers’ Association 53, Mittal Chambers, 5th Floor, Nariman Point
(India) Mumbai–400021.
Tel: 022-2202 3766/2202 4238
Fax: 022-2202 8017
E-mail: mail@[Link]
The All India Plastic Manufacturers’ Association AIPMA House, A-52, Street No. 1
MIDC Moral, Andheri (East)
Mumbai–400093.
Tel: 22 6777 8899 (100 Lines);
Fax: 022-2821 6390
The Asbestos Cement Products Manufacturers’ The Asbestos Cement Products Manufacturers
Association Association, 502, Mansarovar, 90, Nehru Place,
New Delhi 110 019, India.
Tel: + 91 11 46521495
Fax: + 91 11 46521496
The Solvent Extraction’ Association of India 142, Jolly Maker Chamber No. 2
14th Floor, 225 Nariman Point,
Mumbai–400021
Tel: 022-2202 1475/2282 2979/22028911
Fax: 022-2202 1692
E-mail: solvant@[Link]
The Vanaspati Manufacturers Association of 903, Akashdeep Building, 26-A,
India Barakhamba Road, New Delhi–110001
Tel: 011-2331 2640/2331 0758
Fax: 011-2331 5698
E-mail: [Link]@[Link].
[Link]
Boiler and Unfired Pressure Vessels Division Boiler and Unfired Pressure Vessels Division
CII, 23, Institutional Area,
Lodhi Road,
New Delhi–110003
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
Compressed Air Division Compressed Air Division,
CII, 23, Institutional Area,
Lodhi Road, New Delhi–110003
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
E-mail: asr@[Link]
Contd...
Appendices 625

Contd...

Name of firm Address

Industrial Furnace Division Industrial Furnace Division
CII 23, Institutional Area,
Lodhi Road, New Delhi–110 003
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
E-mail: sgr@[Link]
Industrial Valves Division Industrial Valves Division,
CII 23, Institutional Area,
Lodhi Road, New Delhi–110003.
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
Instrumentation Division Instrumentation Division,
CII 23, Institutional Area,
Lodhi Road, New Delhi–110003.
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
E-mail: srg@[Link]
National Committee on Chemicals and National Committee on Chemicals and
Petrochemicals Petrochemicals, CII 23, Institutional Area,
Lodhi Road, New Delhi–110003
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
National Committee on Drugs and National Committee on Drugs and
Pharmaceuticals Pharmaceuticals, CII 23, Institutional Area,
Lodhi Road, New Delhi–110003
Tel: 011-2462 9994 (4 lines)
Fax: 011-2463 3168/2462 6149
E-mail: shalab@[Link]
National Committee on Oil and Gas Exploration- National Committee on Oil and Gas
Production Exploration- Production,
CII, Gate No 31, North Block,
Jawaharlal Nehru Stadium, New Delhi–110003
Tel: 011-2436 6225/2436 6273/2 436 6276/2
436 6281
Fax: 011-2436 6271/2436 7844
National Committee on Petroleum National Committee on Petroleum,
CII, Gate No. 31, North Block,
Jawaharlal Nehru Stadium,
New Delhi-110 003.
Tel: 011-2436 6225/2436 6273/2 436 6276/2
436 6281
Fax: 011-2436 6271 /2436 7844
National Committee on Textiles National Committee on Textiles,
CII 23, Institutional Area,
Lodhi Road, New Delhi–110003
Tel: 011-462 9994 (4 Lines)
Fax: 011-463 3168/462 6149
E-mail: hemant@[Link]
Contd...
626 Chemical Process Technology

Contd...

Name of firm Address

Oil and Gas Equipment Division National Committee on Oil and Gas Equipment
Division, CII, Gate No 31, North Block,
Jawaharlal Nehru Stadium, New Delhi–110003
Tel: 011-436 6225/463 6273/436 6273/436
6376/436 6281
Fax: 011-462 6271/464 7844
Oil and Gas Services Division National Committee on Oil and Gas Services
Division, CII, Gate No. 31, North Block,
Jawaharlal Nehru Stadium, New Delhi–110003
Tel: 011-436 6225/463 6273/436 6273/436
6376/436 6281;
Fax: 011-462 6271/464 7844
Petrotech Society Petrotech Secretrariate
601–603, Tolstoy House, Tolstoy Marg,
Connaught Place, New Delhi – 110 001.
Phones : +91 11 2335 4002-05
Fax : +91 11 2335 4001
email: petrpotechscociety@[Link]
petrotechindia@[Link]
Website: [Link] [Link]
Pollution Monitoring and Control Equipment The Secretary,
Division Pollution Monitoring and Control Equipment
Division CII, 23, Institutional Area, Lodhi Road,
New Delhi –110 003.
Tel: 011-2462 9994 (4 Lines)
Fax: 011-2463 3168/2462 6149
E-mail: shalab@[Link]

APPENDIX 5: COST OF VARIOUS CRUDE OILS AND PETROLEUM PRODUCTS

Various Crudes $ per barrel $43–51
Ethanol $ per barrel $1.52
Fuel oil ` per ton `3800
Ethanol per ton 3900.0
LPG (commercial) 19 kg 1050
LPG (domestic) 14.2 564
Superior kerosene
Diesel (high speed) 56
Diesel (low speed) 54
Aviation fuel 47
Ethanol 39
Bitumen 24,000/metric ton
Cost of various crude oils and petroleum products may vary with time
Appendices 627

Approximate Cost of Some Important Chemicals

Sl. No. Chemicals Cost per ton/kg in Dollars/Rupees
1. Chlorine
2. Ammonia $350
3. Urea $250
4. DAP $420
5. Sulfur $140
6. Potash $310
7. Caustic
8. Soda ash
9. Methanol $250
10. MTBE $650
11. Ethanol
12. Butanol 1300
13. Isobutanol 930
14. Oxoalcohol
15. Ethylene 150
16. Ethylene oxide 1250
17. EDC 350
18. DMT $1160
19. PTA/TPA $650
20. PET resin $980
21. Acetic acid $430
22. Benzene `54000, $725
23. Butadiene 1300
24. p-Xylene $795–820
25. o-Xylene $790
26. Isophtalic acid $ 1850
27. Propylene `74000
28. MEG `52000/$700
29. DEG `45000
30. Phenol $990
31. LAB $1250
32. LAS $1100
33. Polyester `95000–115000
34. Caprolactam $1900–2300
35. Nylon 6 `230/kg
Contd...
628 Chemical Process Technology

Contd...

Sl. No. Chemicals Cost per ton/kg in Dollars/Rupees

36. Nylon 66 `280/kg
37. Polybutadiene $2200
38. Polyethylene `70000, $1200
HDP/LDPELLPDP
39. Polypropylene (PP) $1200
40. PP resin $1200
41. Polystyrene
42. Poly carbonate `210/kg
43. PVC $900
44. TDI $3700
Cost of various crude oils and petroleum products may vary with time

Approximate cost of Utilities

Sl. No. Utility/Product Cost
1. Steam
• SHP • `1700–2380/MT
• HP • `1600–2236/MT
• MP • `1200–2111/MT
• LP • `1988/MT
2. Power, `/Kahr 5.0–6.80
3. Cooling Water, `/m3 1.6–1.65
4. Instrument Air, `/m3 1.0–1.7
5. Plant Air, `/m3 1.0–1.7
6. Nitrogen, `/Nm3 `1.0–3.5/Nm3
7. Service Water, `/m3 11.0–38.0
8. Filter water 6.5
9. DM Water, `/m 3 36–37
10. Service Water, `/m 3 11.0–38.0
Cost of Utilities may vary with time
Index

A Ammonium sulfate from gypsum 131

Acetylene 54 ammonium sulfate as by-product from
Agrochemicals 475 caprolactam plant 131
Alum 91 Argon 55
Ammonia 112 Assesment of coal quality 215
advances in ammonia technology 120 coal as chemical feedstock 215
ammonia manufacture by steam reforming coal as fuel 215
process 116 coal-based power generation 216
adiabatic performing 118 coal carbonization and coal tar distillation 216
ammonia synthesis 119 coal liquefaction by hydrogenation 216
co2 removal 118 coal to methanol technology 217
desulfurization 116 coal to olefin technology 217
methanation 119 coal to plastic technology 217
reforming section 117
C
shift convertor 118
Calcium ammonium nitrate 129
characteristics 113
process technology 130
process steps 115
Carbon dioxide 55
process technology for the manufacture of
Cement industry 148
ammonia 115
different types of portland cement 156
coal gasification 116
blended cements 158
electrolysis process 115
high alumina cement 158
partial oxidation 116
oil well portland cement 158
steam reforming 116
ordinary portland cement 156
raw materials 114 pozzuolana cement 158
Ammonium chloride 131 special or corrosion resistance 158
ammonium chloride by modified solvay sulfate-resisting portland cement 158
process 132
waterproof portland cement 158
ammonium chloride direct neutralization 132
white cement 158
Ammonium nitrate 129 preheater/precalciner 153
process technology 129 process technology 149
Ammonium phosphate 144 for portland slag cement 152
ammonium phosphate sulfate 145 of dry process of portland cement
diammonium phosphate 144 manufacture 150
urea ammonium phosphate 144 profile 148
Ammonium sulfate 130 stepwise environmental impact due to dry
process technology 131 process for cement manufacture 159
629
630 Chemical Process Technology

technological developments in cement Coal-bed methane 213

plant 152 Coal carbonization and coke-oven plant 217
operating principle 155 blast furnace coke 219
preheater/precalciner 153 by-product from coke oven plant 220
roller press 155 coal handling plant and coal preparation
vertical roller mill 153 section 219
vertical shaft kiln technology 156 coal tar distillation 221
vertical roller mill 153 coke-oven gas plant 220
Chemical industry coke-oven plant 218
changing scenario 11 coke oven plant 217
characteristics of the Indian chemical coking coals 218
industry 12 gas condensation section 220
chemical feedstocks 11 Coal origin and composition 210
evolution 6 Coal-production and consumption 213
global and Indian chemical industries 5 Coal reserves 211
Indian chemical industry weaknesses 12 Coal resources 211
major products 2 Coke oven gas 56
revolutionary innovations 4 Common salt 60
role 1 causes which influence the rate of evaporation
structure 2 of water from open surfaces 61
structure 4 design consideration of solar salt works 61
technological development 3 factors affecting solar evaporation 61
technology commercialization 6 main sources 60
typical issues 13 processes for salt manufacture 61
Chlor-alkali industry 57 sea chemicals 61
global caustic soda and chlorine players 59 Corrosion 514
issues and challenges 60 basic methods of combating corrosion for
profile 58 external pipe corrosion 518
Chlor-caustic production 63 classification of corrosion 515
brine purification 64 commonly used terms in corrosion 519
characteristic of charged brine 67 corrosion cells 518
diaphragm cell 65 corrosion monitoring 518
membrane cell process 69 factors affecting corrosion 517
cell house 70 forms of corrosion 515
mercury cell 67 fundamentals of corrosion 515
Chlorosulfonic acid 74 major areas of concerns 514
manufacturing process 75 theory of corrosion 515
product specification 74 corrosion in process industry 519
Classification of polymer 426 corrosion in oil and gas drilling, production and
thermoplastics 426 petroleum refineries 524
thermosetting plastics 426 chloride corrosion and chlorine
Cleaner technology and green chemistry 573 corrosion 527
cleaner technology in pulp and paper co2 corrosion 526
industry 574 corrosion due to moisture/water 527
clean production technologies in chemical corrosion in steam crackers 528
process industries 573 high temperature corrosion 527
clean production technologies in petroleum naphthenic acid corrosion 525
and petrochemical industry 574 steam and water line corrosion 528
principle of green chemistry and cleaner stress corrosion cracking 527
technology 573 sulfide corrosion 525
Index 631

corrosion prevention and control 528 hydrocracking 322

cathodic protection and anodic recent development 323
protection 532 opportunity crude tight oil/shale gas and
coating and lining 532 shale oil 291
corrosion inhibitors 531 rajasthan crude 291
corrosion in inline instrument 532 tight oil/shale oil/shale gas 291
corrosion monitoring 532 origin, occurrence, exploration and
design consideration 531 drilling 289
fertilizer industry 519 processing of petroleum (crude oil) 292
petroleum and petrochemical industries 524 refinery processes 295
pulp and paper industries 523 separation processes 296
Crude oil and natural gas 289 types of petroleum refining processes 296
alkylation, isomerization, and polymerization sulfur recovery unit 342
alkylation 334 merox (mercaptan oxidation unit) 342
C5 alkylate 334 thermal cracking, vis breaking and delayed
isomerization 335 coking 310
lube refinery 338 catalytic cracking 317
polymerization 338 cracking 311
catalytic reforming 326 thermal cracking 312
catalyst in catalytic reforming 332
classification of processes 329 D
octane number of hydrocarbons 327 Dyestuff industry 484
process steps in catalytic reforming 327 anthraquinone-1-sulfonic acid 493, 494
composition of petroleum (crude oil) 292 classification of dyes 486
opportunity oil and shale oil, shale gas 292 dark blue 495
crude oil and refining capacity 297 demand and supply 485
changing scenario in gasoline and diesel gamma acid 490
specifications 299 manufacturing process 490
maximizing value addition to refinery installed capacity and production 485
streams 300
metanillic acid (6-chlorometanillic acid) 492
crude oil blending 305
resorcinol 494
crude oil distillation 305
chemical reaction 495
crude oil distillation 307
manufacturing process 494
pretreatment of crude oils 305
tobias acid 491
crude oil processes in India 294
chemical reactions 491
desulfurization processes and recovery of
sulfur 339 violanthrone 495
future demand in Indian refineries 340 β-naphthol 492
hydrotreatment processes 341 manufacturing process 492
process used to remove sulfur from
E
different products 340
Edible oil industry 176
sulfur output 340
characterization of oil and fats 179
evaluation of crude oil, petroleum products
and petrochemicals 300 classifcation of oil and fats 178
evaluation of feedstocks for based on edible nature 178
petrochemicals 305 based on iodine value 178
product evaluation 304 based on origin 178
sources of indigenous crude, imported edible oil consumption in India 178
crude 300 hydrogenation of oils 183
types of evaluation 301 oilseed production in India 177
632 Chemical Process Technology

processing of oils and fats 179 Environmental pollution from caustic chlorine
processing of soybean oil 182 plant 570
profile of world and India production 177 aluminum industry 572
refining of crude oils 180 coke oven plant 572
bleaching 181 copper and zinc plants 572
degumming: 180 demercurization of waste water 571
deodorization/deacidification 181 sugar and distilleries 572
winterization/dewaxing/crystallization 181 thermal power plant 572
refining of oil 182 Environmental pollution from cement plant 569
Elastomer 428 Environmental pollution from petroleum and
Elastomers 442 petrochemical industry 555
chlorobutyl rubber 448 gasoline benzene reduction 555
ethylene/propylene number 448 pollution caused by petroleum industry 557
hazards in petroleum and petrochemical
ethylene vinyl acetate rubber 448
industry 559
fluorosilicone rubber 448
safety in cracker plant 560
historical development 442
Environmental pollution in pulp and paper
natural rubber 443
industry 560
hypalon 448
air pollution from craft pulping 560
neoprene (polychloroprene) 447
black liquor oxidation 562
nitrile rubber 446 categorization of pulp and paper mills 562
polybutadiene 445 innovation in technology for waste management
polyisobutylene 446 in pulp and paper industry 563
polyisoprene 447 major accident reported in pulping section 564
polysulfide rubber 449 potential health and safety hazards in pulp and
polyurethane rubber 448 paper production 563
silicone rubber (polysiloxanes) 448 Environmental protection acts, rules, and various
spandex 449 amendments 550
styrene butadiene rubber 444 Environment, health and safety management in
synthetic rubber 443 process industries 550
Electrolysis of water 53 categorization of industrial sectors 554
Electrolytic process 63 characteristics of hazardous and toxic
Energy conservation in fertilizer plants 543 wastes 551
Energy conservation measure in cement plant 542 disaster management 552
Energy conservation measures in petroleum Explosive industry 186
refinery and petrochemical industry 544 characteristics 189
energy management system iso 50001 546 classification of explosive 188
energy recovery with compact heat commonly used terms 187
exchangers 546 important explosives 189
Energy consumption and conservation black powder 193
measures 539 high military explosive 192
management of steam 540 lead styphnate 189
Energy consumption in pulp and paper nitrocellulose explosive 193
industry 542 nitrocellulose (gun powder) 190
Enviromental pollution from fertilizer plants 564 nitroglycerine and dynamite 190
environmental impact of fertilizer manufacture pentaerythritol tetranitrate 191
and use 569 research development explosive 192
hazardous waste from fertilizer industry 568 trinitrotoluene 191
pollutants from fertilizer industry 565 properties 189
Index 633

F Hydrochloric acid 72
Fertilizer industry 93 Hydrogen 52
classification 95 raw material 52
elements necessary for plant growth 93
I
structure 94
Industrial gases 46
type 93
gross heating value of some of the industrial
Fluid mechanics 28
fuel gases 48
G carbon monoxide 49
Gasification of coal, petrocoke and biomass 222 profile of global and Indian gas company 46
gasification in petroleum refinery 225 types 47
gasification reactions 227
L
gasifier configurations 225
Leather industries 206
history of gasification 223
leather manufacturing process 207
process steps in gasification 225
chrome tanning 208
surface gasification 224
eco-friendly tanning processes 208
underground coal gasification 224
pertaining process 207
Gibbs–Helmholtz equation 63
post-tanning process 208
Glass industry 162
tanning 208
developments in glass industries 163 vegetable tanning 208
glass raw material and process technology 164 profile 206
fining and fluxing agents 165 Limestone and lime 159
raw materials 164 development in lime processing
recycling of glass 165 equipments 161
process technology of glass manufacture 165 uses of lime 161
refractory in glass industries 168 Linear alkyl benzene 284
status 163 lab application in India 285
types of glasses 166 lab by solid acid catalyst 286
borosilicate glass 166 manufacturing of detergents 287
coated glass 167 process of making powder and liquid
fiber glass 167 detergent 287
fiber reinforced plastic (FRP) 168 process steps in lab manufacture 284
float glass process 167
glass lined steel 168 M
laminated glass 167 Mass transfer 21
lead glass 167 diffusion 21
rolled glass process 167 distillation 22
silica glass 167 drying 25
soda lime glass 166 film theory 22
wired glass 167 humidification 24
leaching 24
H Raoult’s law 23
Heat transfer 17 types of distillation 23
boiling and condensation 18 Metal industries 195
conduction 17 aluminum
convection 17 process of manufacture 200
Fourier’s law 17 raw material for aluminum 200
Planck’s law 18 class of metals 195
radiation 17 alkali and alkali earth 196
634 Chemical Process Technology

ferrous 195 P
nonferrous 195 Paint industries
precious 195 decorative liquid paints 502
refractory 195 glossary of terms 499
copper 202 alkyd resin and modified alkyd resin 501
process of copper manufacture 203 manufacturing process of paints and
iron and steel 196 resins 500
basic oxygen furnace 199 synthetic resins 500
electric arc furnaces 200 profile 498
global per capita consumption 197 major Indian paint industry 498
process of manufacture 197, 200 world’s top 10 paint brands 498
lead 204 raw material 499
trend in world production and use 204 Palm oil 185
world lead resources 204 Per capita energy consumption 536
zinc 201 Pesticides industry 475
Methane and synthesis gas derivatives 52 classification and characteristics of some major
pesticides 479
N pesticide consumption 477
New gasifier designs 227
process technology 481
catalytic coal gasification 228
biopesticides 482
coal gasification in fertilizer industry 228
dichloro diphenyl trichloroethane 482
co-gasification of coal and biomass for
profile 476
methanol synthesis 229
Petrochemical industry 349
ge global/unmixed fuel processor 227
aromatic production 405
KBR transport gasifier 227
catalytic reforming 407
rapid thermal processing process for
conversion of biomass to liquid fuels 228 major units of aromatic complex 407
New generation insecticides 483 process steps in aromatic production 408
insect growth regulators 483 reactions in catalytic reforming process 407
Nitric acid 125 aromatics product profile, ethyl benzene and
nitric acid process technology 126 styrene, cumene and phenol, bisphenol,
aniline 411
strong acid process 126
aniline 416
weak acid processes 126
benzoic acid 417
properties and specification 128
bisphenol 418
uses 125
cumene 415
nitrogenous fertilizer 110
ethyl benzene 413
process flow diagram for manufacture 112
ethyly benzene and styrene 412
Nitrophosphate 146
process flow diagram 146 phenol 416
typical specification 146 phthalic anhydride 414
Nuclear energy 546 composition of feedstock 364
nuclear power generation 547 butadiene 371
first stage 547 dehydrogenation of isobutene 373
fission reaction 548 ethyl tertiary butyl ether 375
second stage 548 fluid catalytic cracking 368
third stage 548 isobutylene 373
profile of nuclear power India 547 methyl tertiary butyl ether 374
product profile of c5 hydrocarbon 368
O recovery of chemicals from fcc and steam
Oleum 91 cracker 367
Oxygen and nitrogen 49 tertiary amyl methyl ether 375
Index 635

trends in technological developments of Petroleum refining 289

Steam crackers for production of Pharmaceutical industry 504
ethylene 367 active pharmaceutical ingredient 508
ethylene derivatives: ethylene oxide, ethylene biologic 508
glycol, ethylene dichloride and vinyl biosimilars 508
chloride 388
branded drug 508
ethylene oxide (eo) 391
diagnostic agents 508
mono-, di-, and tri-ethylene glycols 392
chemicals used in manufacture of API 510
vinyl chloride 392
commonly used terms 508
Indian petrochemical industry 352
exports of medicinal and pharmaceutical
aromatic plant 359 products 507
basic building block process 355 geographical distribution of pharma
basic petrochemicals 355 companies 507
evaluation of feedstock for olefin profile 504
production 358 raw material 512
evaluation of feedstocks for aromatics, olefins role of pharmaceutical industry and paradigm
and surfactant plants 358 shift in drug discovery 512
major end products 355 structure of pharmaceutical industry 509
integration of refinery with petrochemical 360
manufacture of API 509
Indalin process 361
Phosphatic fertilizer 135
Indamax FCC 361
process flow diagram for the manufacture 137
naphtha and gas cracking for production of
raw material 136
olefins 361
Phosphoric acid 138
petrochemicals feedstock 356
technological development 141
propylene, propylene oxide, and
types 138
isopropanol 398
electric furnace acid 140
oxidation route using peroxide
compounds 402 wet phosphoric acid 139
propylene 398 Phosphorus 133
propylene oxide, propylene glycol, and composition of rock phosphate 133
polyols 401 Phosphorus 134
structure of petrochemical complexes 351 compounds 135
synthesis gas and its derivatives: hydrogen, baking powder 135
CO, methanol, formaldehyde, methanol to forms 134
olefin technology 375 red 135
acetic acid (CH3COOH) 382 yellow 135
acetylene 387 Plastic consumption 423
chloromethanes (methyl chloride, types of polymer 424
methylene dichloride, chloroform, Plastic industry in India 425
carbon tetrachloride) 385 Polyaluminum chloride 73
dimethylformamide 386 manufacturing process 73
formaldehyde 382 polymers 435
methanol 379 catalyst for polyolefin 436
methanol process technology 380 polyethylene 437
raw materials for synthesis gas 377 DuPont Sclairtech process 439
synthesis gas 377 Unipol process 438
vinyl acetate 394 polyolefins 435
acetaldehyde 397 polypropylene 439
acetone 398 process technology 439
ethanol 395 unipol process 440
636 Chemical Process Technology

polystyrene 441 problems in utilization of hardwood 244

process technology 442 quality of good newsprint 244
Profile of fertilizer industry 95 process steps in the manufacture 236
Fertilizer (Control) Order 1985 106 kraft pulping process 237
fertilizer demand 100 pulping and bleaching 236
global fertilizer consumption 96 pulping of agricultural residue 238
global fertilizer industry 95 profile of Indian paper mills 232
Indian fertilizer industry 96 raw material 234
installed capacity and production 99 recovery of chemicals 247
landmarks 98 black liquor oxidation 248
natural gas demand 102 kraft recovery 247
coal and lignite 103 recovery of chemicals in agro-based mill 250
coal-bed methane 102 secondary fiber in paper making 236
coke-oven gas 103 stock preparation and paper making 251
fuel oil 103 beating and refining process in stock
naphtha 102 preparation 252
shale gas 102 Fourdrinier machine 255
problems and prospects 104 paper machine 255
environmental issues 104 sulfite process 245
imbalance use 105 technological turning point 234
impact of energy 104 various grades of paper 259
policy-related issues 105
biofertilizer 105 R
nitrogen fixer bacteria 105 Reaction engineering 26
organic fertilizer 105 Refractories 169
price volatility 104 application of refractory in various
raw material availability 104 industries 173
production and consumption 98 classification 170
raw material 100 important properties 171
natural gas 101 important refractory materials 170
sector-wise and nutrient-wise installed Indian refractory industry 169
capacity 99 process technology 174
specification straight nitrogenous fertilizers 107 refractories consumption 174
Pulp and paper industry 231 type of refractories 171
advances in Indian paper industry 232 Renewable energy in India 538
advances in pulp and paper industry 258 Risk and hazard in chlorine handling and
biotechnology application 259 processing 564
forest management 258
bagasse pulping 239 S
commonly used terms in pulping 246 Sea water 60
innovating technologies in paper industry 236 Single superphosphate 141
major challenges and shortcomings 234 process flow 142
mechanical pulping 240 Soap 277
bleaching of mechanical pulp 243 categorization 277
refinery mechanical pulping 242 continuous saponification process 280
stone groundwood 240 glycerine purification 281
newsprint 243 glycerine recovery 280
advantage of groundwood pulp 244 raw material 277
newsprints pulp 244 salt removal 281
Index 637

soap making process 277 Synthetic fiber 428

soap removal 281 acrylonitrile, acrylic fiber, modified acrylic fiber,
Soda ash 75 polyurethane 462
consumption pattern 76 cellulosic fibers (viscose rayon and acetate
global overview 76 rayon, cuprammonium rayon) 466
Indian scenario 76 cuprammonium rayon 472
modified solvay process (dual process) 80 dimethyl terephthalate and terephathalic
plants in India 77 acid 454
solvay process 79 acrylonitrile 463
steps involved in soda ash process 80 acrylonitrile by ammoxidation of
propylene 463
Stable bleaching powder 75
dimetyl terephthalate 455
Sugar and alcohol industry 262
mobil process 458
ethanol 264
paraxylene 455
alcohol from biomass 266
polybutene terephthalate 460
ethanol as biofuel 270
polyethylene terephthalate 460
ethanol as biofuel and chemical
polyethylene terephthlate (polyester) 459
feedstock 269
polyurethane 466
Indian alcohol industry 269
sn man-made textile industry 432
ethanol as chemical feedstock 271
nylon 6, nylon 6,6, cyclohexane, caprolactam,
fermentation of molasses 265
adipic acid and hexamethylene diamine 449
process technology 267
adipic acid 451
technological barriers 268
caprolactam 450
integration of sugar, paper, distillery and
cyclohexane 449
chemical plant 273
nylon 6 453
process steps in sugar manufacture 263
nylon 6,6 454
processing sugar beet 264
raw materials 434
Sulfur 82
mining process 83 T
properties 83 Thermodynamics 19
recovery from h2s 84 common terms
sources 82 enthalpy 20
Sulfuric acid 85 entropy 20
catalyst in sulfuric acid manufacture 88 fugacity 21
double contact double absorption system 87 Gibbs free energy 21
manufacture 86 Hselmholtz free energy 21
process steps involved 87 Joule Thomson effect 21
reaction in pyrite roasting 91 humidification 24
sulfuric acid from pyrite roaster gases 89 properties of system 19
technological development 86 types 19
uses 86 adiabatic 20
Synthetic detergent and linear alkyl benzene cyclic 20
detergent 281 isobaric 20
basic components 283 isochoric 20
classification of detergent 282 isothermal 19
anionic 282 Zeroth law 20
cationic 283 Triple superphosphate 142
ethoxylates 283 potassic fertilizer and mixed fertilizers 143
nonionic or zwitterionic 283 process 142
fatty alcohols 282 specifications various npk fertilizer 144
638 Chemical Process Technology

Types of coal 214 prilling 125

Types of polymer 424 purification and low pressure recovery 124
U synthesis and high pressure recovery 123
Unit processes and unit operations in chemical production technologies 122
process technology 34 raw material 123
Urea 121
W
process description 123
World total polymer demand 422
concentration 124