1

DECLARATION

We hereby declare that the work in this report of the integrated project is our own except for
quotations and summaries which have been fully acknowledged.

14 MARCH 2011 NURUL HAZWANI

(A127192)

NG GAIK HOON
(A130113)

LEE PAK HOE

(A130132)

MOHD AZIZAN BIN RAZAL @ ABD RAZI

(A130463)
2

ACKNOWLEDGEMENT

First of all, thank to god for giving us enough time and energy to finish our integrated
project – Production of phenol on time. Here, we wish to show our appreciation to those
who help and contribute in accomplishing our project.

We would like to take this opportunity to state our appreciation to our lecturers Dr.
Manal Ismail, Assoc. Prof. Dr. Zahira Yaakob and Prof. Dr. Abdul Amir Hassan Kadhum by
providing guidance and help based on the format and issues of this integrated project in
detail. Without their guidance, it is impossible to finish this project.

Then, we would like to thank the Chemical and Process Engineering Department for
conducting this integrated project to let us have an exposure toward our working field in the
future. Other than that, throughout this project, we are able to improved our learning skills,
identify current issues and apply basic knowledge of our 3 courses, Transportation
Phenomenon I, Reactor I and Organic Chemistry for Engineers.

Thirdly, we would like to thank each other as a group member. All of us had given
very best cooperation during the progress of completing our project. We worked as a team in
order to complete our project successfully. Also thanks to our course mates for sharing
information and knowledge on this project.

Next, we would also like to express our appreciation to the other groups which are
our classmates as well because of their selfless sharing of knowledge and suggestions in
solving the questions. Group discussions are always the most efficient way.

Lastly, we also wish to thank to those whom we did not mention here but had helped
us directly or indirectly in accomplishing our project. Thank you.
3

ABSTRACT

We are assigning to do a research on how to produce the phenol. The main objective of our
report is to design the production plant for phenol in industry. Besides, in this report we had
include information on the product usage, demand, supply and production, future marketing
potential, sources of raw materials, process description, process flow diagram, waste
generation, environmental issues and safety precaution for the production process. We have
also performed material balance and energy balance calculation at selected reactor, which is
oxidation vessel. Phenol is also known as carbolic acid. Phenol can be form from cumene
peroxidation process. The raw material in this process is cumene and oxygen. In this
peroxidation process cumene is oxidizing first with present of oxygen into cumene peroxide
and then decomposition process to form phenol and acetone. A process flow diagrams
(PFD) which is for production of phenol had been included to provide clearer picture of the
process. It is done by using engineering design software, Microsoft Visio. Based on
research, phenol is supply from all over the world such as Asia, Western Europe, North
America and others. In global market, phenol production and consumption increases year by
year. This is because in future world the development of technology growth rapidly. Many
engineering equipments are made from phenol such as electrical and electronic equipment,
automobiles, sports safety equipment and reusable food. Hence, increases the demand of
phenol. From the calculation of mass balance, we obtain F1, mass flow rate in for cumene
(66239.76 kg/h ), F2 mass flow rate in for oxygen (5930.65 kg / h),F3 mass flowrate out for
mixture of cumene,oxygen and cumene hydroperoxide (73722.26 kg / h). From calculation
of energy balance we obtain Q heat transfer (-6710.005 kJ/s ). As a conclusion we can
assume that the phenol production per year is 165.6 kmole / year. During the process with
Q=-6710.005 kJ/s heat is being released during the process.
4

CONTENTS
Pages
ACKNOWLEDGEMENT 2
ABSTRACT 3
CONTENT 4
LIST OF TABLE 7
LIST OF ILLUSTRATION 8
LIST OF SYMBOL 9
GLOSSARY 11

CHAPTER I INTRODUCTION 13
1.1 Phenol 13
1.2 Chemical Reaction Involved 13
1.3 Physical properties 14

CHAPTER II RAW MATERIAL 15

2.1 Source of raw material 15

CHAPTER III PRODUCT USAGE AND APPLICATION 17

3.1 Product usage for Phenol 17

CHAPTER IV ECONOMIC ISSUES 19

4.1 Supply and demand for Phenol 19
4.2 Future Marketing potential of Phenol 23

CHAPTER V ENVIRONMENTAL ISSUE 24

5.1 Waste Generation 24
5.2 Environmental Issues 26
5.3 Relevant Environmental Act 27
5.4 Exposure limit 28
5.5 Safety Precaution 29
5

CHAPTER VI PROCESS FLOW DIAGRAM 30

6.1 Process Description 30
6.2 Process flow diagram 31
6.3 Block diagram 31

CHAPTER VII MATERIAL AND ENERGY BALANCE 32

7.1 Material balance 32
7.2 Energy balance 35
7.3 iCON simulation of Material and Energy Balance 38
7.4 Error calculation of Material Balance 39
7.5 Error calculation of Energy Balance 40

CHAPTER VIII REACTOR 41

8.1 Reactor Determination 41
8.2 General mole balance equation 42
8.3 Kinematic rate Expression 43
8.4 Stoichiometry Table for CSTR 45
8.5 Catalyst 46

CHAPTER IX ORGANIC CHEMISTRY 47

9.1 Balance Stoichiometry equatiom 47
9.2 By product process and separation method 47
9.3 Quality and standard 48

CHAPTER X TRANSPORT PHENOMENON 1 50

10.1 Introduction 50
10.2 Friction loss calculation 51
10.3 Performance rates of pump 54
10.4 iCON simulation 59
6

10.5 Computational Fluid Dynamic 61

CHAPTER XI CONCLUSION 62

REFFERENCE 63

APPENDIX 66
7

LIST OF TABLES

No. Table:

Table 1.1: Properties of phenol

Table 2.1: The physical and chemical properties of oxygen
Table 2.2: The physical and chemical properties of cumene
Table 4.1: Demand of Phenol in Global Market
Table 4.2: Capacity of Phenol in Global Market
Table 5.1: The physical and chemical properties for acetophenone
Table 5.2: The physical and chemical properties for acidified wash water
Table 5.3: The physical and chemical properties for acetone
Table 5.4: Parameter limits of effluent
Table 5.5: Exposure limits of raw materials
Table 7.1: Coefficient of Heat Capacity for the Components
Table 7.2: Heat of Formation for the Components
Table 7.3: Comparison of material balance between manual and iCON® calculation
Table 7.4: Comparison of energy balance between manual and iCON® calculation
Table 9.1: Percentage of composition of phenol production
Table 10.1: Vapour pressure of components in stream 5
Table 10.2: Data-data calculated by HYSYS in plotting pump performance curve
Table 10.3: Comparison of Manual Calculation and iCON Calculation of Pump
8

LIST OF ILLUSTRATION

No.Figure:

Figure 1.1: Structural Formula of phenol

Figure 1.2: Reaction of the manufacture of phenol
Figure 3.1: The uses of phenol
Figure 4.1: Pie chart of worldwide demand of phenol
Figure 4.2: Pie chart of world consumption of phenol
Figure 4.3: Supply and demand of phenol from 2009 to 2015
Figure 4.4: Future Marketing Potential Of Phenol
Figure 6.2: Block diagram for the process of Phenol.
Figure 7.1: Diagram drawn in iCON®
Figure 8.1: Continuously-Stirred tank reactor
Figure 9.1: Short path vacuum distillation apparatus with vertical condenser
Figure 10.1: Unit operation involves pump at the second reactor
Figure 10.2: Pump performance curve plot using data from iCON
Figure 10.3: iCON simulator to the unit operation of pump
Figure 10.4: Typical CFD presentation for heat exchanger
9

LIST OF SYMBOL

A Area
Cj Concentration of component j
Specific heat capacity constant pressure
Cp
D Diameter
F Friction force
Ff Friction loss in pipe due to the flow

f Fanning factor
Fi Total mass flow rate at inlet

Fo Total mass flow rate at outlet

Fi j Mass flow rate of component j at inlet

Fo j Mass flow rate of component j at outlet

g Gravitational force
H Head
 Enthalpy change of component j
Hj

hc Friction loss due to sudden contraction

h ex Friction loss due to sudden enlargement

hf Friction loss for fittings and valves

kc Contraction-loss coefficient

k ex Expansion-loss coefficient

kf Loss factor for the fitting or valve

kj Specific reaction rate of component j

L Length of pipe
m Mass flow rate (kg/s)
Mj Molecular weight of component j
10

Ni Total molar flow rate at inlet

N Re Reynolds Number

No Total molar flow rate at outlet

Nij Mole flow rate of component j at inlet

Noj Mole flow rate of component j in outlet

ND Degree of freedom

NV Number of unknown

NE Number of independent equation

P Pressure
Pvp Vapour pressure

Q Energy
r Rate of reaction
r' j Rate of reaction of component j in heterogeneous reaction

υ Velocity
W Weight of catalyst
Wp Shaft work delivered to pump

Ws Mechanical work

w oj Mass fraction of component j at outlet

X Conversion
x ij Mole fraction of component j at inlet

x oj Mole fraction of component j at outlet

Z Elevation
x Stoichiometric coefficient of component j
ρ Density
μ Viscosity
ε Equivalent roughness for new pipes
11

GLOSSARY

Aromatic compound A Hydrocarbon characterized by general alternating double and single

bonds between carbons

Bond Cleavage Process of splitting the chemical bonds

Catalyst A substance that causes or accelerates a chemical reaction without

itself being affected
Caprolactam An organic compound with the formula (CH2)5C(O)NH and used in
synthetic polymer

Cumene Systematic name for isopropylbenzene

Distillation A method of separating mixtures based on differences in their

volatilities in a boiling liquid mixture

Effluent An out flowing of water or gas from a natural body of water, or from
a human-made structure

Enthalpy A measure of the total energy of a thermodynamic system

Epoxy resin Thermosetting polymer formed from the reaction of an epoxide with
polyamine

Fluid Mechanics The study of fluids and the forces on them. (Fluids include liquids,
gases, and plasmas.)
12

Heterogeneous Having more than one type represented

Homogeneous Having the same uniform appearance and composition throughout

Limiting Reactant The substance which is totally consumed when the chemical reaction
is complete

Polycarbonate A particular group of thermoplastic polymers. They are worked,

moulded and themoformed

Stoichiometry A branch of chemistry that deals with the quantitative relationships

that exist between the reactants and products in chemical reactions

Synthesis The combining of the constituent elements of separate material or

abstract entities into a single or unified entity (opposed to analysis).

Viscosity Measure of the resistance of a fluid which is beig deformed by either

shear stress or tensile stress
13

CHAPTER I

INTRODUCTION

1.1 PHENOL
Phenol, is an aromatic compound with an OH group bonded to the phenyl ring
with chemical formula C6H5OH. Phenol is used in the production of disinfectants, dyes,
pharmaceuticals, plastics, germicides, preservatives, synthetic resin, antiseptic, detergent
and drug.
Molecular structure:

Figure 1.1: Structural Formula of phenol

(Sources: Wikipedia, ChemBlink, Wikimedia Commons)

1.2 CHEMICAL REACTION INVOLVE

Phenol is form initially from the basic raw material; benzene and propylene which in turn to
produce cumene or the systematic name is isopropylbenzene. The cumene is further oxidised
to become a cumene hydroperoxide before it is split into phenol and acetone as the product.
The sulphonation route produced large quantities of waste, and more and thus being
replaced by oxidation of cumene process.
The reaction between phenol and acetone would yield to the production of
Bisphenol-A (BPA). It is used to manufacture polycarbonate and epoxy resin.
However, the process that we studied for the project is oxidation of cumene. The chemical
reactions are shown by below.
14

C6H5CH(CH3)2 (l) + O2 (g) C6H5C(CH3)2OOH (l) ---------------------- (1)

C6H5C(CH3)2OOH (l) C6H5OH + CH3COCH3 -------------------------- (2)
Figure 1.2: Reaction of the manufacture of phenol

 Reaction of
benzene
sulfonic acid
with base

 Reaction of
chlorobenzene
with base

 Acidic
oxidation of
cumene

 Hydrolysis of
diazonium
salts

1.3 PHYSICAL PROPERTIES

Phenol is a caustic, poisonous, white crystalline solid at room temperature. The molecular
weight and density of phenol are 94.11g/mole and 1.07g/cm3 respectively. Phenol is soluble
in water is due to its ability to form hydrogen bonds with water.
Table 1.1: Properties of phenol
Properties
Molecular formula C6H6O
Molar mass 94.11 g mol−1
Appearance White Crystalline Solid
Density 1.07 g/cm³
Melting point 40.5 °C, 314 K
Boiling point 181.7 °C, 455 K
Solibility in water 8.3g/100ml
Dipole moment 1.7 D

(Source: http://en.wikipedia.org/wiki/Phenol , Wikipedia)

15

CHAPTER II

RAW MATERIAL

2.1. SOURCES OF RAW MATERIAL

Cumene peroxidation process is a process involves the liquid phase air oxidation of cumene
to cumene peroxide, which in turn is decomposed to phenol and acetone by the action of
acid.During the cumene peroxidation process, there are two main raw materials used in this
process which are cumene and oxygen.

Oxygen is a gas form fluid. Oxygen is colourless gas that can be found in the air. In
the air there is 21% of oxygen contains while another 79% is nitrogen gas. Oxygen acts as
an oxidizer. Table 2.1 shown the physical and chemical properties of oxygen.

Table 2.1: The physical and chemical properties of oxygen

Physical Properties Data
Synonyms Oxygen
Chemical Formula o2
Physical State at room temperature gas
Odor Odourless
Appearance Colorless gas
Melting Point 219 °C
Boiling Point 183°C
Critical Temperature 118°C
Relative Density 1.1 g/cm3
16

Molar mass 32.00 g/mol

Solubility mg/L water 39 mg/L

Source: LINDE Industrial Gases (Malaysia) Sdn. Bhd. MSDS (Material Safety Data Sheet)
Information.

Cumene is an aromatic hydrocarbon. Cumene can be form from the alkylation of

benzene with the addition of propylene. Cumene is a liquid form fluid. Cumene is a
colourless liquid. The systematic name for cumene is isopropyl benzene.

Table 2.2: The physical and chemical properties of cumene

Physical Properties Data
Synonyms Isopropyl benzene
Chemical Formula C6H5CH(CH3)2
Physical State at room temperature Liquid
Odor Aromatic
Appearance Colorless liquid
Melting Point -
Boiling Point 152°C
Critical Temperature -
3
Relative Density 4.1 g/cm (vapour)
Molar mass 120.00 g/mol
Solubility mg/L water Negligible solubility in cold water
Vicosity 0.7
Source: CITGO Petroleum Corporation MSDS (Material Safety Data Sheet) Information.
17

CHAPTER III

PRODUCT USAGE AND APPLICATION

3.1 PRODUCT USAGE FOR PHENOL

Uses for Phenol

18%

Bisphenol
40%
PF Resins
8%
Alkyl Phenol
4% Caprolactam
Other

30%

Figure 3.1: The uses of phenol

Source: Dow Phenol: Properties, Usage, Storage and Handling, The Dow Chemical
Company

Based on the chart most of the phenol is used as a Bisphenol A (BPA). Bisphenol A
is an industrial chemical used in the production of epoxy and polycarbonate plastic resins.
Polycarbonate plastic resins are a lightweight, high-performance plastic that possesses a
unique balance of toughness, high heat resistance, and very good electrical resistance.
18

Because of these features, polycarbonate is used in a wide variety of common products

including digital media for example CDs and DVDs, sports safety equipment and reusable
food. Epoxy resins have many uses including engineering applications such as electrical
laminates for printed circuit boards, composites, paints and adhesives, as well as in a variety
of protective coatings.

Second large usage of phenol is Phenol-formaldehyde (PF) resins which is 30%. A

PF resin is commonly used as molding powders, laminates, adhesives, and coating resins. PF
resins in powder form are molded into products such as telephone housings and electrical
outlets or plugs. The other application of PF resins are high and low pressure laminates are
used in the manufacture of panel boards,chemically resistant containers, boat hulls, airplane
parts, luggage, brake linings and many others.

Next, the usage of phenol is caprolactam which contribute 8% of product usage.

Caprolactam used in nylon 6 production to make carpet and rug yarns. Besides, caprolactam
also used in resins. Caprolactam based resins are used in automotive and truck parts
including rear-end license panels, louvers, mirror housings, and wheel covers. Others usage
also contribute 18%. Lastly, alkyl phenol is one of the usages. The examples of alkylphenol
are p-nonylphenol and p-dodecylphenol. Alkyl phenols are used as stabilizers or
antioxidants in motor oil.
19

CHAPTER IV

ECONOMIC ISSUE

4.1. SUPPLY AND DEMAND OF PHENOL

4.1.1. DEMAND OF PHENOL
The phenol/acetone capacity expansion in the world has been brisk in recent years due to the
strong demand for its derivatives such as Bisphenol A and phenolic resins. The largest single
market for phenol is in the production of Bisphenol A (BPA), which is manufactured from
phenol and acetone. About 40% of BPA is made up from phenol. According to SRI
Consulting, world consumption of phenol for BPA is estimated to grow at a good average
annual rate during 2009–2014. Increased demand and capacity for BPA will result in strong
demand for phenol in these regions. Bisphenol A of Asian demand is expected to increase
by 13% this year. The second-largest derivative market for phenol is phenol resins which are
used in the moulding of heat-resistant components for household appliances, counter-top
and flooring laminates, and foundry castings. From ICIS news, the global phenol market has
been growing at an average of 5%/year and total demand will recover from 7.9m tonnes in
2009 to reach 10.6m tonnes by 2015. The phenol markets look especially promising in
China since 2000.
20

World demand of Phenol in 2010

others
North
10%
America
Weatern 32%
Europe
27%
Asia
31%

Figure 4.1: Pie chart of worldwide demand of phenol

World Consumption of Phenol in

2010
Others
North
9%
America
30%
Western
Europe
31%

Asia
30%

Figure 4.2 : Pie chart of world consumption of phenol

(Source: HighBeam Research)

*the data is translated from words to pie chart form

21

Table 4.1: Demand of Phenol in Global Market

Supplied quantity
Year
(million tones / year)
2009 7.9
2010 8.3
2011 8.7
2012 9.1
2013 9.6
2014 10.1
2015 10.6

(Source: ICIS Market News)

*the data for 2011 to 2015 is the estimation data while the other is the data published by
ICIS market research and some other site.

4.1.2 SUPPLY OF PHENOL

Shell, Sunoco, Georgia Gulf, Dow, JLM and INEOS are the major producer in United State.
Shell Chemical LP have a facility that is fully integrated from raw materials to end products
gives Shell Chemical LP a significant advantage in operating as a low cost producer of
phenol. However, INEOS Chemical is the world largest phenol producer. INEOS Chemical
produce 540 kilo tonne per year to USA and 1330 kilo tonne per year to Europe while
Sunoco produces over 590,000 t/a of phenol in its facility in Philadelphia, Penn, USA.
Sunoco/UOP phenol technology is currently used in 11 plants worldwide having a total
phenol capacity of more than 1,500,000 t/a. The capacity of phenol in China still cannot
meet the demand thus many enterprises are plan to expand or construct the new units.
22

Table 4.2: Capacity of Phenol in Global Market

Supplied quantity
Year
(million tones / year)
2009 8.58
2010 9.09
2011 9.55
2012 10.12
2013 10.73
2014 11.37
2015 11.37

(Source: ICIS Market News)

Supply and demand of phenol

12.00
million tonnes/year

10.00
8.00
6.00
4.00 Production
2.00 Consumption
0.00
2009 2010 2011 2012 2013 2014 2015
year

Figure 4.3: Supply and demand of phenol from 2009 to 2015

(Source: ICIS Market News)

23

4.2. FUTURE MARKETING POTENTIAL OF PHENOL

30

25

20

15 SUPPLY
DEMAND
10

0
2009 2010 2011 2012 2013 2014 2015 2016 2017 2018 2019 2020

Figure 4.4: Future Marketing Potential Of Phenol

Source: ICIS Market News for year (2009-20015)
x-axis: production per year(millions tones/year)
y-axis: year

From the figure 4.4 we have made a prediction for future market potential of phenol
from years 2016 until 2020. We have made an extrapolation from the previous data for
supply and demand of phenol from 2009 until 2015. From the graph we can see that, the
demand and supply of phenol will increase by year. The supply graph is slightly higher than
demand graph. Moreover the supply graph showed that steeper increase year by year. While
the demand graph increases less steeper.
24

CHAPTER V

ENVIRONMENT ISSUE

5.1. WASTE GENERATION

Waste generation is quantity of materials or products that enter a waste stream before land
filling, or recycling. In this process acetophenon is the side product while phenol is the major
product. Sometimes the company sells their side product or uses it for another purpose. Next
is Acidified wash water can be harmful to environment if we release it in the exceed limit.
The table below shows the physical and chemical properties for acetophenone.

Table 5.1: The physical and chemical properties for acetophenone

Physical Properties Data
Synonyms Ketone methyl phenyl
Chemical Formula C6H5COCH
Physical State at room temperature Liquid
Melting Point 19.7°C
Boiling Point 201.7°C
Critical Temperature -
Relative Density 4.1 g/cm3 (vapour)
Molar mass 120.16 g/mol
Solubility mg/L water soluble in water, methanol, diethyl ether
Vicousity -

Source: http://www.sciencelab.com/xMSDS-Acetophenone-9922778 MSDS (Material

Safety Data Sheet) Information.
25

Acidified wash water is released from the separation process. The acidified water
form is removed from the process. Table below shows the physical and chemical properties
for acidified wash water.

Table 5.2: The physical and chemical properties for acidified wash water
Physical Properties Data
Synonyms Water
Chemical Formula H2O
Physical State at room temperature Liquid
Odor -
Appearance Colourless liquid
Melting Point 0°C
Boiling Point 100°C
Critical Temperature -
Relative Density 1 g/cm3 (vapour)
Molar mass 18.00 g/mol
Solubility mg/L water Infinite
Vicousity 8.90 × 10−4 Pa·s
pH 3.0

Source :GE Power & Water MSDS (Material Safety Data Sheet) Information.

Lastly, acetone is also one of the waste generations in this process. Acetone is form
during acetone fractionation process. Acetone is a colorless liquid with pungent smell. The
table below shows the physical and chemical properties for acetone.

Table 5.3: The physical and chemical properties for acetone

Physical Properties Data
Synonyms 2-propanone
Chemical Formula C3H6O
Physical State at room temperature Liquid
Odor Pungent smell
26

Appearance Colourless liquid

Melting Point -95.3°C
Boiling Point 56.2°C
Critical Temperature 235°C
Relative Density 0.7925 g/cm3
Molar mass 58.08g/mol
Solubility mg/L water soluble in cold water and hot water
Vicousity 0.4013 mPa·s at 0°C
0.3311 mPa·s at 20°C
0.2562 mPa·s at 50°C

Source : http://www.sciencelab.com/xMSDS-Acetone-9927062 MSDS (Material Safety

Data Sheet) Information.

5.2 ENVIRONMENTAL ISSUES

Leading to the phenol production plant, there is acidified wash water has been eliminate
during the process. This waste generation will lower water pH due to acid precipitation and
deposition usually through precipitation. This process disrupts ecosystem nutrient flows and
may kill freshwater fish and plants dependent on more neutral or alkaline conditions.

Next, the air pollution cause by emission of hazardous substance such as

acetophenon from this plant has been one of the issues. Air pollution happen when there is
emission of hazardous substance in exceed limit. Air pollution can cause the possibility of
children living within them to develop asthma, pneumonia and other lower respiratory
infections.

Lastly, the latest issues in Malaysian government banned the use of milk
bottles containing bisphenol A. Bisphenol A contains toxic substance that use to made milk
bottles for babies. Bisphenol A is one of phenol’s product usages. Bisphenol A is
27

an endocrine disruptor, which can mimic the body's own hormones and may lead to negative
health effects

5.3 RELEVANT ENVIRONMENTAL ACT

Environmental act that is related to this process is Environmental Quality Act 1974. These
environmental quality acts have their regulation to make sure the plant will not discharge or
use harmful or hazardous materials. The waste generation discharges for this pulp mill are
following the environmental quality (sewage and industrial effluents) regulations 1979.
There are list of environmental quality (sewage and industrial effluents) regulations:-
1. Prohibition against new and altered sources of effluent discharge
2. Requirement and approval of plans.
3. Prohibition of discharge of effluent containing certain substances.
4. Standard methods of analysis of effluents.
5. Parameter limits of effluent to be discharged into inland waters.
6. Restrictions on the discharge of effluents.

Table 5.4 showed parameter limits of effluent to be discharged into inland waters. It
is also one of the regulations for environmental quality (sewage and industrial effluents).

Table 5.4: Parameter limits of effluent

Parameter Standard
pH value 5.5 - 9.0
COD (mg/L) 100
BOD5@20°C (mg/L) 50
Suspended Solids (mg/L) 100

Source : Anon. 2006. MSDS (Material Safety Data Sheet) Information.

28

5.4. EXPOSURE LIMIT

Exposure limit is a legal limit for exposure to a chemical substance. These limits are
generally discretionary and every country defines its own limits, resulting in a lack of widely
accepted standards. The exposure limits of raw materials and waste are stated in table 5.5.

Table 5.5: Exposure limits of raw materials

Chemical Substance Exposure limit
Cumene 0.2 ppm
Oxygen >21% concentration of air

Source : MSDS (Material Safety Data Sheet) Information.

5.5 SAFETY PRECAUTION

In this cumene process the raw materials are oxygen and cumene. Oxygen will become a
hazardous substance if we are exposed to it in the exceeded limit around more than 21% air
in atmosphere. The plant must use only properly specified equipment, which is suitable for
this product, its supply pressure and temperature. Keep away from ignition sources
(including static discharges). Apart from that, peoples that working with oxygen are advise
not to smoke while handling product.

Cumene is also listed as a hazardous chemical substance. It is a flammable liquid

because it release vapour at or below ambient temperature. Its vapour can cause a flash fire
when mixed with air in certain proportions and exposed to an ignition source. Therefore,
when handling this material, if there is spill or leak of pipe people work in this plant must
keep the containers closed and do not handle or store near heat. Those

Acetophenon is very hazardous in case of eye contact (irritant). It is also hazardous

in case of skin contact (irritant). It is slightly hazardous in case of ingestion, of inhalation.
29

Inflammation of the eye is characterized by redness, watering, and itching. Peoples that have
been in charge for handling this material should keep it away from heat and sources of
ignition. They also should not ingest the materials. If ingested, seek medical advice
immediately and show the container or the label.
30

CHAPTER VI

PROCESS FLOW DIAGRAM

6.1. PROCESS DESCRIPTION

In this production process, purified cumene is used as raw material input and is mixed with
recycle Cumene in the main feed stream. It is feed to the oxidation vessel which the
condition is maintained at 110-115 oC and pH range of 6.0 to 8.0. In the vessel, the mixture
from the feed is exposed to compressed air until 20-25% of the Cumene has converted into
Cumene Hydroperoxide. This is the stoichiometry equation of the reaction.

C6H5CH(CH3)2 + O2 C6H5C(CH3)2OOH

The crude mixture from the oxidizer is concentrated up to 80% before entering the
reactor where the Cumene Hydroperoxide is cleavage to phenol and acetone. The reaction is
carried out in mild temperature and pressure around 70 oC and atmospheric pressure. Small
amount of sulphuric acid is added to the reactor as the reaction takes place.

C6H5C(CH3)2OOH C6H5OH + CH3COCH3

After that, the stream is directed to the separation processes. First of all, the stream is
washed with water and Acetone is removed overhead in the first column. The mixture is
then further purified by going through steps of distillation. For the first distillation column,
the unreacted Cumene is transferred to the recycle stream. The Cumene is purified before it
is sent back to the feed stream. The purification of Cumene is done by catalytic
hydrogenation of Methyl Styrene to Cumene, by careful fractionation where methyl styrene
is available as by-product of the reaction.
31

The reaction of Phenol required 2 step of reaction. The first reaction is the
production of Cumene Hydroperoxide by two raw materials, which is Cumene and Oxygen.
The reaction occurs at tank T101, which is oxidizing tower. The reactions occur in the
condition of temperature 110-115 oC and pH is at range of 6.0 to 8.0. Then, the intermediate
product; Cumene Hydroperoxide will be used as the reactant in second reactor, R101. Type
of reactor that will be used is Continuous Stirred Tank Reactor (CSTR). It about 90%
conversions occurs in the cleavage process to form Phenol and Acetone. The next unit
operation is the separation process where all of the side product and waste will be separate
to get the main product: Phenol.

6.2. PROCESS FLOW DIAGRAM

Process flow diagram for the production of Phenol in figure 6.1

6.3. BLOCK DIAGRAM

Figure 6.2 below show the block diagram for the production of phenol.

Figure 6.2: Block diagram for the process of Phenol

32

CHAPTER VII

MATERIAL AND ENERGY BALANCE

7.1. MATERIAL BALANCE

The first reactor is choose for the calculation of the mass balance. The reactor 1 involve the
reaction between Cumene and Oxygen to produce Cumene Peroxide. These are the reaction
that involves in the first reactor.
In this reaction it shows that 1 kmole of C6H5CH(CH3)2 and 1 kmole of O2 will
produce 1 kmole of C6H5C(CH3)2OOH. After that, the Cumene Hydroperoxide make a
cleavage process by a reaction with catalyst Sulphuric Acids (H2SO4) and produce Phenol
and Acetone in reactor number 2. Based on the reaction equation, 1 kmole of
C6H5C(CH3)2OOH will cleavage 1 kmole of C6H5OH and 1 kmole of CH3COCH3.

Based on the principles of mass balance equation, mass is neither created nor
destroyed but it can change in physical and chemical state. Total mass of feed into the
reactor are equal to the mass of product out of reactor with the total accumulation of mass
inside the reactor.
Rate of mass input = Rate of mass output + Rate of mass accumulation
Since that the reaction is steady flow process, so total mass in is equal to total mass out of
the reactor.
Rate of mass input = Rate of mass output
These are the given data from the literature review:-
1. Phenol production per year =136363.64 tonnes / year
= 15.56663 tonnes / h
= 15566.63 kg / h
= 165.6 kmole / h
33

2. Fraction composition for the product mixture of Cumene hydroperoxide acids in

reactor 1.
X3cumene = 0.6
X3cumene hydroperoxide = 0.3
X3oxygen = 0.1
3. Conversion factor:
X reactor 2 = 90%
To find the total number of molar flow rate to the feed in reactor 1, firstly find the total flow
rate output of the reactor by calculate the total flow rate of reactor 2 (reaction between
Cumene Hydroperoxide and Sulphuric Acids to produce Phenol and Acetone).
 Molecule Balance on reactor 2 (acidifier).

1. Phenol Balance:
N3X3phenol = N4X4phenol – ar2
N4X4phenol = 165.6 kmole / h
a=1
0 = N4X4phenol – r2
r2 = 165.6 Kmole / h
2. Acetone Balance:
N3X3acetone = N4X4acetone–ar2
N4X4acetone = 165.6 kmole / h
3. Cumene Peroxide Balance:
N3X3cumene hydroperoxide= -ar2 / Xreactor2
= - (-1) (165.6) / (0.9)
= 184 kmole / h
4. Total number of mole in feed reactor 2, N3
N3X3cumene hydroperoxide= 184 kmole / h
X3cumene hydroperoxide= 0.3
N3 (0.3) = 184 kmole / h
N3 = 613.3 kmole / h
34

5. Finding mass flow rate for feed in reactor 2.

F3 = N3X3cumene (Mrcumene) + N3X3cumene hydroperoxide (Mrcumene hydroperoxide) + N3X3oxygen
(Mroxygen)
= (613.33) (0.6) (120) + (613.33) (0.3) (150) + (613.33) (0.1) (32)
= 73722.26 kg / h

From this value, it shows that the reactor 2 required 73722.26 kg / h feed mixture of
Cumene hydroperoxide, Cumene and Oxygen to produce 15566.63 kg / h of Phenol at the
conversion of 90% of Cumene Peroxide at reactor 2.

 Molecule Balance on reactor 1:

1. Cumene hydroperoxide Balance:
N1X1cumene hydroperoxide = N3X3cumene hydroperoxide – ar1
0 = 184 kmole / h –ar1
r1= 184 kmole / h
2. Cumene Balance:
N1X1cumene = N3X3cumene –ar1
X1cumene = 1 (100% purity feed of Cumene)
N1X1cumene = (613.33) (0.6) – (-1) (184)
= 551.998 kmole / h
3. Oxygen Balance:
N2X2oxygen = N3X3oxygen–ar1
X2oxygen = 1 (100% purity feed of Oxygen)
N2X2oxygen = (613.33) (0.1) – (-1) (184)
= 185.33 kmole / h
4. Finding Mass flow rate for feed at stream 1 and stream 2.
F1 = (N1X1cumene) (Mrcumene) = (551.998) (120) = 66239.76 kg / h
F2 = (N2X2oxygen) (Mroxygen) = (245.33) (32) = 5930.65 kg / h
Total mass flow rate = F1 + F2
= 66239.76 + 5930.65
= 74090.42 kg / h
35

Based on the calculation above, the total mass flow rate required in the feed stream of
Cumene and Oxygen is about 74090.42 kg / h to produce 74200 kg / h.

7.2. ENERGY BALANCE

Cumene Peroxidation Process is the process where the raw material, cumene and oxygen gas
that is 100% purity is react. The product form is cumene hydroperoxide. The calculation of
the energy balance is done in the first reactor.

C6H5CH(CH3)2 (l) + O2 (g) C6H5C (CH3)2OOH (l)

Cp= A + BT + CT2 + DT3(J/mol.K)

Table 7.1: Coefficient of Heat Capacity for the Components

A B C D
C6H5CH(CH3)2 139.2×10-3 53.76×10-5 -39.79×10-8 120.5×10-12
O2 29.1×10-3 1.158×10-5 -0.6706×10-8 1.311×10-12
C6H5C (CH3)2OOH 1.345×105 3.8060×102 - -

Source: Perry’s Chemical Engineer’s Handbook, Perry, R.H. and Elementary Chemical
Process

Table 7.2: Heat of Formation for the Components

∆Hof(kJ/mol)
C6H5CH(CH3)2 -41.1
O2 0
C6H5C (CH3)2OOH -149.67
Source: National Institute of Standards and Technology

Equation for Energy Balance:

Q = ∆Hout - ∆Hin + r∆Hof
36

Where,
Q = Heat absorbed or heat released in the reactor
∆Hout = Change of enthalpy in the system out
∆Hin = Change of enthalpy in the system in
r = Rate of reaction
∆Hof = Heat of formation at 298.15 K

Enthalpy change for the component

T2
∆H = T1
C p dT

∆H = A( T2 - T1 ) + B( T22 - T12 )/2 + C( T23 - T13 )/3+D( T24 - T14)/4

where, T1 = Reference Temperature (298.15 K)

T2 = Input / Output Temperature

Enthalpy change for the inflow,

T1 = 110oC = 383.15 K

For Cumene:-
383.15
∆H =
298.15
𝐶𝑝 𝑑𝑇
= (139.2×10-3)(383.15-298.15) + (53.76×10-5)( 383.152-298.152) /2 + (-
39.79×10-8)( 383.153-298.153)/3 + (120.5×10-12)( 383.154-298.154)/4
= 11.832 + 15.566 + (-3.945) + 0.411
= 23.864 kJ/mol
For Oxygen:
383.15
∆H =
298.15
𝐶𝑝 𝑑𝑇
= (29.1×10-3)(383.15-298.15) + (1.158×10-5)( 383.152-298.152) /2 +(-
0.6076×10-8)( 383.153-298.153)/3 + (1.311×10-12)( 383.154-298.154)/4
= 2.4735+ 0.3353 + (-0.06024) + 0.0044736
= 2.75303 kJ/mol
37

Enthalphy change for outflow,

T2 = 115oC = 388.15 K
For Cumene Hydroperoxide,
388.15
∆H =
298.15
𝐶𝑝 𝑑𝑇
= (1.345×105)(388.15-298.15) + (3.8060×102)( 388.152-298.152) /2
= 12105000 + 11754260.1
= 23859260.1 J/mol
For Cumene:-
388.15
∆H =
298.15
𝐶𝑝 𝑑𝑇
= (139.2×10-3)(388.15-298.15) + (53.76×10-5)( 388.152-298.152) /2 + (-
39.79×10-8)( 388.153-298.153)/3 + (120.5×10-12)( 388.154-298.154)/4
= 12.528 + 16.603 + (-4.241) + 0.446
= 25.336 kJ/mol
For Oxygen:
388.15
∆H =
298.15
𝐶𝑝 𝑑𝑇
= (29.1×10-3)(388.15-298.15) + (1.158×10-5)( 388.152-298.152) /2 +(-
0.6076×10-8)( 388.153-298.153)/3 + (1.311×10-12)( 388.154-298.154)/4
= 2.619+ 0.358 + (-0.06024) + (-0.065) + (4.85×10-3)
= 2.917 kJ/mol

For overall enthalpy at inflow, ∆Hin,

∆Hin = (∆HiCumene × NiCumene ) + (∆HiOxygen × NiOxygen)
= (23.864 kJ/mol × 551998 mol/h) + (2.75303 kJ/mol × 185333 mol/h)
= 13683099.32 kJ/h

For overall enthalpy at outflow, ∆Hin,

∆Hout= (∆HoCumene Hydroperoxide × NoCumene hydroperoxide ) + (∆HoCumene × NiCumene ) +
(∆HoOxygen × NiOxygen)
38

= (23859.2601kJ/kmol × 613330 mol/h) + (25.336 kJ/mol × 367998 mol/h) +

(2.917 kJ/mol × 61333 mol/h)
= 9503960.298 kJ/h
For Heat of formation, Hof
Hof = ∑∆Hofproduct - ∑ ∆Hofreactant
= [-149.67kJ/mol] – [ (-41.1kJ/mol) + 0 kJ/mol]
= -108.57kJ/mol
From the overall energy balance equation,
Q = ∆Hout - ∆Hin + r∆Hof
= 69753.978kJ/h – 66.011kJ/h + (184000 mol/h × -108.57kJ/mol)
= -24156019.02 kJ/hr
= 24156019.02 kJ/h × (1h/3600s)
= -6710.005 kJ/s

7.3 iCON® SIMULATION ON MATERIAL AND ENERGY BALANCES

In order to perform material and energy balance using iCON®, we have draw conversion
reactor and the respective input and output streams using standard symbols in the software. .
Figure 5.7 shows the diagram we have drawn in iCON®.

Stream 2

Stream 1 Stream 3

Figure 7.1 Diagram drawn in iCON®

39

7.4 ERROR CALCULATION OF MATERIAL BALANCE

The table 7.3 below shows the comparison of material balance calculation between manual
calculation and iCON®.

Table 7.3: Comparison of material balance between manual and iCON® calculation
Manual calculation iCON® Percentage
Mass flow rate
(kmole hr-1) (kmole hr-1) error(%)
Stream 1 551.998 551.12 0.16
Stream 2 185.330 185.34 0.0054
Stream 3 613.33 614.00 0.11

Error calculation of mass flow rate of stream 1

551.998 − 551.12
Error = ⃒ ⃒ × 100%
551.98
= 0.16 %

Error calculation of mass flow rate of stream 2

185.330 − 185.340
Error = ⃒ ⃒ × 100%
185.330
= 0.0054 %

Error calculation of mass flow rate of stream 3

613.33 − 614.00
Error = ⃒ ⃒ × 100%
613.33
= 0.11 %

7.5 ERROR CALCULATION OF ENERGY BALANCE

The table 7.4 shows the results comparison of energy balance between manual calculation
and iCON®.
40

Table 7.4 : Comparison of energy balance between manual and iCON® calculation
Manual calculation iCON® Percentage error
Heat flow
(kJ/s) (kJ/s) (%)
Reactor 1 -6710.005 -6855.608

Error calculation of reactor 1 energy balance

−6710.005 − −6855.608
Error = ⃒ ⃒ × 100%
−6710.005
=2.17 %
41

CHAPTER VIII

REACTOR 1

8.1 REACTOR DETERMINATION

Choosing a suitable reactor is the most important part before the reaction will be done in the
real plant. It is important, especially in designing an industrial process. Furthermore, factor
such as reaction conversion rate, phase reaction, and the condition of the process should be
taken in selecting type of reactor as well as designing the reactors.

The production of phenol required a multiple reaction, that is called a series reaction.
Series reaction is reaction where the reactant forms an intermediate product, which will react
further to form another product. The first reactor (oxidation column) consist of the reaction
between Cumene and Oxygen gas to form Cumene Hydroperoxide. In this reaction, reactor
that will be chosen is Plug Flow Reactor (PFR) because the reaction consists of the gas-
liquid phase reaction.

For the second reactor, that is the place where the main product is being produce,
which is Phenol. This process consist the reaction between Cumene Hydroperoxide with
Sulphuric acids. Sulphuric acids act as catalyst of this reaction. Since that reaction is in the
liquid phase and the catalyst involve also at liquid phase so that the reactor that have been
choose for the second process is Continuous-Stirred Tank Reactor (CSTR). CSTR or called
as vat, backmix reactor is usually primarily used for liquid phase reactions. It is normally
operates at steady state and is assumed to be a perfectly mixed. Consequently, there is no
time dependence or position dependence of the temperature, the concentration, or the
reaction inside the CSTR.
42

Thus, the temperature and the concentration in the exit stream are modelled as being
the same as those inside to the CSTR.

Figure 8.1: Continuously-Stirred tank reactor.

8.2. GENERAL MOLE BALANCE EQUATIONS.

This is the equation for the general mole balance for the CSTR. Since that this is the
continuously flow reaction, so this balance equation will used molar flow rate as the
parameter.
 Molar rate of   Molar rate of 
 Molar flow   Molar flow  
rate of species    Generation   Accumulati on 
 j   rate of species j   
of species j  of species j 
 In at V  Out at V  V      
 within V   within V 

Molar flow rate in – Molar flow rate out + Molar Generation = Molar Accumulation
The general molar flow rate for the continuous reaction:
𝑉
𝑑𝑁𝑗
𝐹𝑗𝑜 − 𝐹𝑗 + 𝑟𝑗 𝑑𝑉 = 𝑑𝑡
0

It is applied to the second reactor, CSTR. For this overall reaction, we assumed that
the first step reaction is very fast such that the overall reaction rate is not affected to the
overall reaction. It just considered the second reaction, which is CSTR.
43

The reaction applied to a CSTR operated at steady state, that is the condition do not change
with time:
𝑑𝑁𝑗
𝑑𝑡 = 0

For CSTR, it assumed that the condition inlet is equal to the exit of the reactor. It
means that there are no spatial variation in the rate of the reaction or perfectly mixing.
𝑉
0 𝑗
𝑟 𝑑𝑉 = 𝑟𝑗 𝑉
So, it takes the familiar form known as the design equation for a CSTR for a species A:
𝐹𝐴𝑜 − 𝐹𝐴 = −𝑟𝐴 𝑉
The volume necessary for CSTR to reduce the entering flow rate of species A from 𝐹𝐴𝑜 to 𝐹𝐴
when species A is disappearing at a rate,−𝑟𝐴 .

𝐹𝐴𝑜 − 𝐹𝐴
𝑉𝐶𝑆𝑇𝑅 =
−𝑟𝐴

8.3. KINEMATIC RATE EXPRESSION

The rate law is defined as the product of the concentration of the individual species to the
raise of power of the species. This is the example for the rate law expression in term of
concentration.
𝛽
−𝑟𝐴 = 𝑘𝐴 𝐶𝐴𝛼 𝐶𝐵

The rate of reaction, −𝑟𝐴 is the number of moles of A reacting or disappearing per
unit time per unit volume. −𝑟𝐴 is always determined based on the experimental observation.

The rate law also depend on the power law. The power law is related with the
reaction order. Again, the order of reaction depend to the experimental observation. The
order of reaction is the power index to which the concentration are raised based onn the
kinetic rate laws. The reaction is 𝛼 order with respect to reactant A and 𝛽 order with respect
to the reactant B. The overall order of the reaction rate, n, is
44

𝑛= 𝛼+ 𝛽

For the second reaction at CSTR, the overall stoichiometric reaction involved to the
production of phenol and acetone.
C6H5C(CH3)2OOH → C6H5OH + CH3COCH3
1 Kmole of cumeneperoxide ≡ 1kmole of phenol ≡ 1kmole of acetone
Let:
C6H5C(CH3)2OOH = A
C6H5OH = B
CH3COCH3 = C
Therefore, the chemical equation in term of alphabetical form:
A→ B + C
Net rates of reaction:
rA  rA
rB  rB
rC  rC

The reaction stoichiometric form is:

rA rB rC
 
1 1 1
The rate of reaction of each of the species:
Cumene Hydroperoxide:
rA  k A C A

Phenol:
1
rB  rA  rA  k AC A
1
Acetone:
1
rC  rA  rA  k AC A
1
So, the design equation for the CSTR to produce Phenol:
FAO  FA
V
k A C A
45

8.4. STOICHIOMETRY TABLE FOR CSTR.

Let species A stand for Cumene Hydroperoxide, B for Phenol and C for Acetone.

Feed Rate To Change Within Effluent Rate From

Species
reactor Reactor Reactor
Cumene Peroxide -FAOX
FAO FA=FAO (1-X)
(A)
-FAOX
Phenol (B) FBO = ΘBFAO FB=FAO (ΘB-X)
FAOX
Acetone (C) FCO = ΘCFAO FC=FAO (ΘC+X)

Total FTO FT=FTO - FAO X

FBO Fco
Where ΘB =FAO , ΘC =FAo
For liquids, volume change with the reaction is negligible when no phase changes are taking
place. Consequently, we can take

𝜐 = 𝜐ₒ
Then, the concentration in term of conversion is:
FA 0
CA= (1-X) = CAO (1-X)
𝜐ₒ

Species In term of flow rate In term of concentration

CA= CAO (1-X)

Cumene Hydroperoxide FA=FAO (1-X)

CB= CAO (ΘB-X)

Phenol FB=FAO (ΘB-X)

CC= CAO (ΘC+X)

Acetone FC=FAO (ΘC+X)
46

8.5. CATALYST
A catalysts is a substance that affets the rate of a reaction but emerges from the process
unchanged. A catalysts usually changes a reaction rate by promoting a different molecular
path for the reaaction. A catalyst can either accelerate or slow down the formation of the
particular product species. A catalyst change only the rate of a reaction and it does not affect
the equilibrium.

In this process, Sulphuric Acids are used as the catalyst for the cleavage of Cumene
Hydroperoxide into Phenol and Acetone. It is homogeneous catalysis that concern process in
which a catalysts is in solution with at least one of the reactants .
47

CHAPTER IX

ORGANIC CHEMSITRY

9.1 BALANCED STOICHIOMETRY EQUATION

The balanced stoichiometric equations of the production of phenol process are shown as
below:

C6H5CH(CH3)2 (l) + O2 (g) C6H5C(CH3)2OOH (l) ---------------------- (1)

C6H5C(CH3)2OOH (l) C6H5OH + CH3COCH3 -------------------------- (2)

9.2 BY-PRODUCT OF THE PROCESS AND SEPARATION METHOD

9.2.1 Introduction

Distillation is a purification technique in which compounds with different boiling points can
be separated by controlled heating. The performance of the distillation column is based on
feed condition, state of feed, composition of feed and internal liquid and fluid flow condition.
During the reaction to produce phenol, the byproducts, acetone and acetophenone are
produced and a few of separation methods are used to get rid of the byproduct.

9.2.2 Separation method

Fractional distillation is used for the mixture whose boiling points are similar. Acetone is
passed through the fractional distillation column which operated at 65oC. The boiling point
of acetone is 56.7oC thus it will be volatile. Vacuum distillation is distillation at a reduced
pressure. It is used to distill compounds that have a high boiling point or any compound
48

which might undergo decomposition on heating at atmospheric pressure. Since the boiling
point of a compound is lower at a lower external pressure, the compound will not have to be
heated to high temperature in order for it to boil. The vacuum is provided either by a water
aspirator or by a mechanical pump. The unreacted cumene is discharged to the purifying
column after pass through the vacuum distillation column. The methylstyene is distilled off
from the distillation column 1. Cumene can be purified by catalytic hydrogenation of
methylstyene. The cumene stream which contains methylstyene can be supplied to a
hydrogenation reactor, hydrogenated over a two-bed nickel and noble metal catalyst system
to produce pure cumene. The cumene stream can be recycled as a feed stream. The
extracting agent, diethylene, is fed to the extraction distillation column. The pure phenol is
coming off from the head of the extraction column and acetophenone is drawn out as a side
stream.

Figure 9.1: Short path vacuum distillation apparatus with vertical condenser
9.3 QUALITY AND STANDARD

Phenol also known as carbolic acid is a caustic, poisonous, white crystalline compound,
C6H5OH, derived from benzene. It is widely used in resins, plastics, and pharmaceuticals
and in dilute form as a disinfectant and antiseptic. The molecular weight and density of
phenol are 94.11g/mole and 1.07g/cm3 respectively.

By using the process we studied, 21.3% of phenol, 47.2 % of cumene, 33.1% of

acetone, 7.9% of oxygen and 2.3% of cumene peroxide will be produced. Table 9.1 show
the percentage of composition of the product.
49

Table 9.1 Percentage of composition of phenol production

COMPOUND (wt %) %COMPOSITION

Phenol 21.3
Cumene 47.2
Oxygen 7.9
Acetone 21.3
Cumene peroxide 2.3
50

CHAPTER X

TRANSPORT PHENOMENON 1

10.1 Introduction
From the process flow diagram of the production of phenol, the pump which delivers the
products from the cleavage reactor (R-101) along stream 5 to the washing tower (T-102) is
chosen to be analyzed.
Here is some data acquired from the previous streams which is needed for our calculation:

Assumptions made:
1. We are taking the properties of the component with highest composition, cumene
properties as the properties of the stream in our calculations.

Density of fluid in stream 5:   845 kg m3

Viscosity of fluid in stream 5:   0.621  103 Pa.s
m
Volumetric flow rate along stream 5: V 

20.58 kg s
V 
845 kg m 3

V  0.024 m 3 s
2
D
Given V  A f  v f ; where A    
2
We choose to use 8 inch nominal pipe size, schedule 40 for this section, hence, the inside
diameter, D  0.2027 m . The cross-sectional area,
0.2027 2
A  ( )
2
51

A  0.0323 m 2

We know that,
V  0.024 m 3 s ; where V  A  v

V
Hence, v 
A
0.024 m 3 s
v 
0.0323 m 2
v  0.743m s

D v
Hence, Reynolds Number of the flow: N Re 

0.2027 m  0.743 m s  845 kg m 3
N Re 
0.621  10  3 kg ms

N Re  204931

Since N Re  4000 , it is a turbulent flow.

10.2 Friction loss calculation

Figure 10.1: unit operation involves pump at the second reactor

Assumptions made:
1. The friction produced by the pump is negligible.
2. The pipe size is exactly the same along the pipe.
3. The volumetric flow rate is constant along the flow.
52

4. Pump efficiency is assumed as 80%.

10.2.1 Mechanical Energy Balance

The mechanical energy balance equation:
1 2 P  P1
(v2 av  v12av )  g ( z 2  z1 )  2   F  Ws  0
2 
Eliminating kinetic energy, since the flow rate is assumed constant, v22av  v12av  0 ;

Hence,
P2  P1
g ( z 2  z1 )    F  Ws  0 (1)

L v2
where  F  (4 f D
 K ex  K c  K f )
2
So, we need to calculate total friction losses,  F in order to perform mechanical energy
balance calculation.

10.2.2 Friction losses along pipe of stream 5

i. Contraction loss at reactor exit;
A5
is assumed zero as the diameter of the reactor is large compared to diameter
AR 101
of the pipe.
For turbulent flow,   1.0

 A5 
K C  0.55 1  
 AR 101 

K C  0.55 1  0  0.55

v2
hC  KC
2

0.7432
 0.55   0.152 J kg
2 (1.0)
ii. Friction in the straight pipe;
53

Same pipe size from the reactor to the washing tower;

N Re  204931
D  0.2027 m
v  0.743 m s

Using commercial steel pipe roughness;   0.000046m

 0.000046
Relative roughness,   0.000227
D 0.2027
From Moody chart, fanning friction factor, f  0.00375
Total length of pipe connecting reactor and washing tower;
 L  1  2  5  1  9m

 L v2
Ff  4 f
D 2
9 0.7432
 4  0.00375  
0.2027 2
 0.184 J kg

iii. Friction in 3 elbows (90o);

Numbers of velocity heads, K f  0.75

v2
h f 3Kf
2

0.7432
 3  0.75   0.621 J kg
2
iv. Expansion loss at washing tower inlet;
A5
is assumed zero as the diameter of the reactor is large compared to diameter
AR 101
of the pipe.
For turbulent flow,   1.0
2
 A 
K ex  1  4   1  0  1.0
2

 AE1 
54

v2 0.743 2
hex  K ex  1.0   0.276 J kg
2 2

Hence, total friction loss;

L v2
 F  (4 f D  K ex  K c  K f ) 2
 F  0.152  0.184  0.621  0.276
=1.233 J/kg

Substituting  F  1.233J / kg into material balance equation (1) in section 10.2.1;

P2  P1
g ( z 2  z1 )    F  Ws  0

(151.988  101.325)  10 3
9.81(5  1)   1.233  Ws  0
845

Ws = -100.43 J/kg
We know that Ws  W p ;

Assuming the efficiency of the pump is 80%,

Ws 100.43
Wp     125.54 J / kg
 0.8
Hence, pump power, P  m W p

 20.58 kg s  125.54 J / kg

 2.584 kW
10.3 Performance rating of pump
55

Figure 10.1: unit operation involves pump at the second reactor

Assumptions made:
1. The position of the pump is taken as the reference point.
2. Z1 is the reference height from the reactor to the pump.
3. Z2 is the reference height from the washing tower to the pump.
4. Pump efficiency is assumed as 80%.

10.3.1 Suction Head Calculation

Let A denote the outlet from the reactor,
ZA  1m PA  101325 Pa

  1.0   845 kg m 3
u A  v  0.743 m s

PA  u A2
HA   g ZA 
 2

1.0  0.743
2
101325
HA   9.81  1 
845 2
 130 m 2 s 2

10.3.2 Discharge Head Calculation

Let B denotes the inlet stream of the washing tower,
ZB   5 m PB  151988 Pa

  1.0   845 kg m 3
u B  v  0.743 m s

PB  uB 2
HB   g ZB 
 2

151.988  10 3 1.0  0.743

2
HB   9.81  5 
845 2
56

 229.19 m 2 s 2

10.3.3 Pump Fluid Power Calculation

Total Head, H  H B  H A
 229.19  130

H  99.19 m 2 s 2

H 99.19 m 2 s 2
Total Head in unit length, 
g 9.81 m s 2
 10.1 m
We know that;
Total Head, H  99.19 m 2 s 2
  20.58 kg s
Mass flow rate, m
Fluid Power, Pf  m
 H

 20.58 kg s  99.19 m 2 s 2
 2.041 kW
10.3.4 Net Positive Suction Head (NPSH) Calculation

Figure 10.1: unit operation involves pump at the second reactor

p1  101325 Pa   845 kg m 3
57

Z1   1 m v  0.743 m s

Friction loss in suction line to the pump, F :

i. Contraction loss at reactor exit;
  1.0
K C  0.55 1  0  0.55

v2
hC  K C
2

0.743 2
hC  0.55   0.152 J kg
2 (1.0)
ii. Friction along straight pipe of suction line;
 L  1 2  3 m

 L v2
Ff  4 f
D 2
3 0.7432
 4  0.00375  
0.2027 2
 0.0613 J kg
iii. Friction in elbow (90o);
Numbers of velocity heads, K f  0.75

v2
h f  Kf
2

0.743 2
 0.75   0.207 J kg
2
Hence, total friction loss in suction line,  F is,

 F  hC + F f + h f

 F  0.152  0.0613  0.207

 F  0.4203 J kg
58

Table 10.1 vapour pressure of components in stream 5

Components Mole fraction Vapour pressure Partial pressure
(kPa) (kPa)
Cumene 0.472 4.667 2.203
Phenol 0.213 0.467 0.099
Acetone 0.213 24.000 5.112
Oxygen 0.079 - -
Cumene hydroperoxide 0.023 18.665 0.429

pv p  2.203  0.099  5.112  0.429

 7.843kPa

Net Positive Suction Head that will be available, NPSH  A at the pump suction:

p1 pv p v2
g NPSH  A    g z1   F
  2

101325 7.843  10 3 0.7432

   9.81 5   0.4203
845 845 2
 158.98 m 2 s 2

158.98 m 2 s 2
NPSH  A 
9.81 m s 2

NPSH A  16.21m

10.3.5 Pump Performance Curve

Table 10.2 Data-data calculated by HYSYS in plotting pump performance curve

Volumetric Flow Rate Total Head m  NPSH A m  Efficiency (%)
m h 3

0.00 10.1122 16.23 0

3.38 10.1083 16.55 20
59

7.82 10.1055 16.78 37

12.07 10.1017 17.27 53
16.02 10.0974 17.88 69
19.57 10.0929 18.35 80
23.71 10.0892 18.72 85
27.16 10.0869 19.26 82
31.20 10.0828 19.68 65
35.01 10.0791 19.75 40

Figure 10.2 Pump performance curve plot using data from iCON
10.4 iCON calculation
10.4.1 Introduction
For analysis of the pump, iCON calculation is carried out to compare the results with our
manual calculation. By using iCON, the total head, fluid power and NPSH  A of the

pump are determined. Consequently, comparison results between manual and iCON
calculation is used to confirm the consistency and accuracy of our manual calculation.
10.4.2 Calculation of Pump
For this analysis, the inlet temperature is same with the reaction temperature, which is 70 oC.
Meanwhile, the inlet pressure is at atmospheric pressure, P  101325Pa and the outlet
60

pressure is assumed to be 151988Pa . After the efficiency of the pump is set to 80%, iCON
calculation of the pump is then run. We are interested in the results of total head and pump
power. Finally, the result of iCON calculation is compared with the result of manual
calculation.

Figure 7.2 iCON® Calculation of Pump

Figure 10.3: iCON simulator to the unit operation of pump

Table 10.3 Comparison of Manual Calculation and iCON Calculation of Pump

Manual iCON
Error (%)
Calculation Calculation
Total Head,  H m 10.11 5.47 46
Pump Power, Pf kW  2.584 1.380 47

According to table 10.3, we found out that the percentages of error of total head and
pump power are quite significance. However, the occurrence of errors is due to some
mistakes and difference between the data sources. Firstly, assumptions are made in order to
simplify our manual calculation. For instance, the relative height of the reactor in the suction
line to the pump, Z 1 and the relative height of the evaporator in the discharge line from the
pump, Z 2 is assumed to be at 1m and 5m respectively. This may contribute to error because
the values of Z 1 and Z 2 in the iCON calculation cannot be set accordingly. Furthermore,

the efficiency of the pump is set to be 80% in iCON calculation which is an approximate
61

assumption. It is because the actual efficiency of the pump may not be ideally have 80%
efficiency. Besides that, the error percentage of the total head is partly contributed by the
liquid density of components in stream 5. The density in manual calculation is assumed
same as the major component, cumene but the density used in iCON is based on the data
input in iCON.

10.5 COMPUTATIONAL FLUID DYNAMIC (CFD)

Computational Fluid Dynamics (CFD) is the science of predicting fluid flow, heat transfer,
mass transfer, chemical reactions and related phenomena by solving the mathematical
equations which govern these processes using a numerical process. The main application of
CFD is as an engineering method, to provide data that is complementary to theoretical and
experimental data. The result of CFD analyses is also used in conceptual studies of new
designs, detailed product development, troubleshooting and redesign.

Figure 10.4: Typical CFD presentation for heat exchanger

62

CHAPTER XI

CONCLUSION

The process that we studied for the production of phenol is oxidation of cumene process.
Cumene is used as the raw material for this process. First of all, cumene is feed into the
oxidation vessel and some dilute soda ash solution is added to maintain the pH. The mixer is
exposed to compressed air until the cumene has converted into cumene peroxide. The
cumene peroxide is cleaved to phenol and acetone. Sulphuric acid as the catalyst has been
added to the reactor while reactions take place. In order to separate the main product which
is the phenol and the by-product which is the acetone, we have to use the method of
distillation. Distillation is a method of separating mixtures based on differences in their
volatilities in a boiling liquid mixture. Besides, the friction losses and performance rating of
a pump and a compressor also apply in this project.

After analysis properties of phenol, we found that there are many side effects if we
expose to phenol such as irritation, corneal damage or blindness in humans. It is not only
hazardous to our health but also harmful to the environment. A good management of the by-
products and waste that produced is needed to make sure the environment is being protected.

Demand of the phenol is increasing year by year from 2009 to 2015. From last year
data, estimation had been made until year 2015 which shown an increase quantity from 7.9m
tonnes in 2009 to reach 10.6m tonnes by 2015.
63

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65

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66

APPENDIX

APPENDIX A MSDS ACIDIFIED WATER

APPENDIX B MSDS ACETONE
APPENDIX C MSDS ACETOPHENONE
APPENDIX D CUMENE
APPENDIX E CUMENE HYDROPEROXIDE
APPENDIX F PHENOL
APPENDIX G MALAYSIA ENVIRONMENTAL LAW
APPENDIX H ICON SIMULATION
67