1.

INTRODUCTION

Methanol is the simplest alcohol compound, comprised of one carbon atom, one oxygen
atom, and four hydrogen atoms (CH3OH). It is also referred to as wood alcohol, carbonyl
alcohol, methyl alcohol, wood naphtha and wood spirits.

The ancient Egyptians are considered to be the first to discover Methanol. They obtained
it from the Pyrolysis of wood and utilized it, along with mixture of other substances. But pure
methanol was first isolated in 1661 by Irish chemist- Robert Boyle, who called it spirit of box,
because he produced it via the distillation of box wood.

Methanol can be manufactured from a variety of carbon-based feedstock such as natural

gas, coal, and biomass (e.g., wood). Use of methanol would diversify the countrys fuel supply
and reduce its dependence on imported petroleum. Methanol is much less flammable than
gasoline and results in less severe fires when it does ignite.

Large scale production of methanol from natural gas and coal is a well-developed
technology. Methanol prices today are competitive with hydrocarbon fuels (on an energy basis).
There is progress on the economic conversion of biomass to methanol using thermo-chemical
processes. Sufficient feedstock of natural gas and coal exists to enable the use of non-renewable
methanol as a transition fuel to renewable methanol from biomass. A variety of renewable
feedstock is available in the US for sustainable transportation with bio-methanol.

Global production:

The methanol industry spans the entire globe, with production in Asia, North and South
America, Europe, Africa and the Middle East. Worldwide, over 90 methanol plants have a
combined production capacity of about 75 million metric tons (almost 24 billion gallons or 90
billion litres), and each day more than 100,000 tons of methanol is used as a chemical feedstock
or as a feedstock additive (33 million gallons or 125 million litres). The global methanol
industry generates $36 billion in economic activity each year, while creating over 100,000 jobs
around the globe.

Page 1
2. PHYSICAL AND CHEMICAL PROPERTIES AND USES

This chapter includes the study of various physical and chemical properties of methanol along
with its industrial uses and applications.

2.1. PHYSICAL PROPERTIES:

Molecular weight : 32.04 gm/mol

Boiling point : 64.6oC

Freezing point : -97.6oC

Heat of formation : -201.3 MJ/kmol

Gibbs free energy : -162.62 MJ/kmol

Relative density : 0.79

Refractive index (200c : 1.32840

Reid vapour pressure : 32kpa

Flash point (closed cup) : 120C

(Open cup) : 15.60C

Water Solubility : greater than or equal to 100 mg/mL at 70 F

Lower Explosive Limit (LEL) : 6 %

Upper Explosive Limit (UEL) : 36.5 %

Auto ignition Temperature : 867 F

2.1.1. Heat of combustion:

Heating value (at 250c and 101.325 kpa) = 726.1kJ/mol

2.1.2. Critical properties:

Page 2
Critical temperature : 512.6 K

Critical pressure : 81 bar

Critical volume : 0.118 m/kmol

Critical density : 0.2715 gm/cm3

Critical compressibility : 0.224 factors

2.1.3. Liquid Properties:

Density : 791 kg/m at 20 C

Heat of Vaporization : 35278 kJ/kmol

2.1.4. Viscosity: a

= 555.3, b = 260.6

Where log (viscosity) = a * (1/T - 1/b)

viscosity: mNs/m T: Kelvin

2.1.5. Vapor Properties:

Heat capacity (Cp):

a = 21.152, b = 0.07092, c = 2.59E-05, d = -2.85E-08

Where Cp = a + bT + cT + dT

Cp: kJ/kmol temp (T) : Kelvin

Vapor pressure (P):

a = 18.5875, b = 3626.55, c = -34.29

Where ln (P) = a - b/ (T+c)

P: mmHg T: Kelvin

2.2. CHEMICAL PROPERTIES:

Page 3
2.2.1. Combustion of Methanol:

When Methanol burns in the presence of air, it burns with a pale-blue, non-luminous flame
to form carbon dioxide and steam.

2CH3OH + 3O2 2CO2 + 4H2O R2.1

. Methanol

2.2.2. Oxidation of Methanol:

Methanol is oxidized with acidified Potassium Dichromate (K2Cr2O7 ) or with acidified

Sodium Dichromate( Na2Cr2O7 ) or with acidified Potassium Permanganate( KMnO 4 ) to form
formaldehyde.

CH3OH + (O) HCHO + H2 R2.2

. Methanol formaldehyde

2H2 + O2 2H2O R2.3

If the oxidizing agent is in excess, the formaldehyde is further oxidized to formic acid and then
to carbon dioxide and water.
(O) (O)

HCHO HCOOH CO2 + H2O R2.4

Formaldehyde Formic Acid

2.2.3. Dehydrogenation of Methanol:

Methanol can also be oxidized to formaldehyde by passing its vapor over copper heated to
300 C. Two atoms of hydrogen are eliminated from each molecule to form hydrogen gas and
hence this process is termed dehydrogenation.

o
300 c

CH3OH HCHO + H2 R2.5

Methanol cu formaldehyde

2.2.4. Catalytic Oxidation of Methanol:

Page 4
The catalytic oxidation of methanol using platinum wire is of interest as it is used in model
aircraft engines to replace the sparking plug arrangement of the conventional petrol engine. The
heat of reaction is sufficient to spark the engine.

2.2.5. Dehydration of Methanol:

Methanol does not undergo dehydration reactions. Instead, in reaction with sulphuric acid
the ester, dimethyl sulphate is formed.

conc. H2SO4
2 CH3OH (CH 3)2SO4 + H2O R2.6 Methanol
Dimethyl Sulphate Water

2.2.6. Esterification of Methanol:

Methanol reacts with organic acids to form esters.

H(+)
CH3OH + HCOOH HCOOCH3 + H2O R2.7
Methanol Formic Methyl Water
Acid Formate

2.2.7. Substitution of Methanol with Sodium:

Methanol reacts with sodium at room temperature to liberate hydrogen. This reaction is
similar to the reaction of sodium with ethanol.

2 CH3OH + 2 Na 2CH3ONa + H2 R2.8

Methanol Sodium Sodium Hydrogen
Methoxide

2.2.8. Substitution of Methanol with Hydrogen Chloride:

Page 5
Methanol reacts with hydrogen chloride to form methyl chloride (i.e. chloromethane)
and water. A dehydrating agent (e.g. zinc chloride) is used.

ZnCl2
CH3OH + HCl CH3Cl + H2O R2.9
Methanol Hydrogen Methyl chloride Water
Chloride

2.3. USES OF METHANOL:

2.3.1. Chemical Intermediate and Fuel:

The primary uses for methanol are the production of chemical products and use as a fuel. It
is also being used increasingly for waste water treatment and for producing biodiesel.

Methanol is used in the production of formaldehyde, acetic acid and a variety of other
chemical intermediates which form the foundation of a large number of secondary derivatives.
These secondary derivatives are used in the manufacture of a wide range of products including
plywood, particleboard, foams, resins and plastics.

Much of the remaining methanol demand is in the fuel sector, principally in the production
of MTBE, which is blended with gasoline to reduce the amount of harmful exhaust emissions
from motor vehicles. Methanol is also being used on a small scale as a direct fuel and it is fuel
for fuel cells.

2.3.2. Fuel Cell Applications:

Methanol is widely considered to be one of the most promising fuels for fuel cell
applications currently being developed for cell phones, portable computers and small scale
transportation such as commuter scooters. Several distinct attributes of methanol make it an
ideal hydrogen source for future fuel cell vehicles and may one day provide an alternate source
of energy in homes.

2.3.3. Waste Water Treatment:

Page 6
Methanol is a simple molecule that serves as an ideal carbon source for the bacteria used in
denitrification. Accelerated by the addition of methanol, anaerobic bacteria will rapidly convert
the nitrate (NO3) to harmless nitrogen gas (N2), which is vented into the atmosphere.

2.3.4. Biodiesel Production:

Biodiesel is made by chemically reacting fats and oils are with an alcohol, typically
methanol, to produce an ester, or biodiesel. Although most any alcohol can be used, methanol is
preferred because it is relatively inexpensive and allows for the most thorough reaction process.
This process is known as trans-esterification. For each 10 volumes of biodiesel produced, one
volume of methanol is used in the process.

2.3.5. Miscellaneous Uses of Methanol:

Methanol is also used in the following applications:

Crystallization, precipitation and washing of alkali metal halide salts

Precipitation of polystyrene and chloroprene resins

Washing and drying of powdered coal fractions

Paint stripping

Metal surface washing

Cleaning of ion exchange resins

Moisture and resin removal from lumber

Extraction agent in the oil, chemical and food industries

Fondue fuel

Fuel for picnic stoves and soldering torches De-icer and windshield washer fluid

for automobiles

Antifreeze for pipeline dehydration.

Page 7
3. DIFFERENT PROCESSES FOR MANUFACTURE OF METHANOL

This chapter includes the brief study of various process and technologies required for the
production of methanol based on feed stock used and operating conditions.

Methanol was first produced as a by-product in the manufacture of charcoal through the
destructive distillation of wood, with yields of 12-24 litres per ton of wood. Most of methanol
today is produced from natural gas. In principle, many carbon-containing materials may be
substituted for natural gas as starting materials. These include (in addition to wood) coal, lignite,
and even municipal wastes. Each of these raw materials, however, must first be converted to
syngas; for this step, each alternative feedstock requires process modifications that increase
capital investment costs over those required for natural gas. The feed stocks are

Wood
Coal
Natural gas
Crop residues
Grass
Forest residues
Cellulosic parts of municipal solid wastes

3.1. METHANOL FROM NATURAL GAS:

The production of methanol through the conversion of natural gas to syngas is used in
conventional methanol plants throughout the world. Typically natural gas-primarily methane-is
catalytically reacted with steam and carbon dioxide to yield hydrogen and carbon monoxide in a
ratio of 2:1.

3CH4 + 2H2O + CO2 8H2 + 4CO R3.1

This gas mixture (syngas) is then compressed and converted to methanol:

8H2 + 4CO 4CH3OH R3.2

3.2. METHANOL FROM WOOD:

Page 8
The production of methanol through the conversion of wood to syngas is being examined
in several countries. In terms of converting carbon to methanol, wood is inherently less efficient
than natural gas. The initial gasification step in producing syngas from wood yields a mixture of
CO and H2 deficient in hydrogen; to bring the ratio of H2 to CO to 2:1, part of the CO is reacted
with steam to yield additional hydrogen:

CO + H2O CO2 + H2 R3.3

This carbon dioxide is then removed from the process stream and discarded.
Approximately 50 percent of the carbon in the wood entering the process is non-productively
released to the atmosphere.

3.2.1. Suggested Steps for Wood Conversion Gasification:

In the first step, wood is charged at the top of the reactor and ash discharged from the
bottom.
Air and steam are charged near the base of the reactor.

The sequences of reactions occurring in wood gasification are as follows:

Drying (100 - 200C):

Moist wood and heat Dry wood and water vapor

Pyrolysis (200-500C):

Dry wood and heat Char + CO + CO2 + H2 + CH4 + tars and pyroligenous acids

Gasification (500C+):

Char + O2 + H2O CO + H2 + CO2 R3.4

The raw gas typically contains hydrogen (18%), carbon monoxide (22.8%), carbon
dioxide (9.2%), methane (2.5%), other hydrocarbons (0.9%), oxygen (0.5%), and nitrogen
(45.8%).

Page 9
3.2.2. Gas Purification and Shift Conversion:

The raw gas is then purified to remove all but hydrogen and carbon monoxide. This mixture
is reacted to convert part of the CO to H 2 So that the final mixture contains a 2:1 ratio of H 2 to
CO. In this conversion, additional CO2 is formed and must be removed before methanol
synthesis.

In detail, the raw gas from the reactor passes through a scrubber for cooling the gas to
about 32 C and removing tars and acid.

The gas is then compressed to about 100 psig and treated in two stages to remove carbon
dioxide. In the first stage, a hot potassium carbonate solution reduces the CO 2 content to about
300 ppm. In the second stage, monoethanolamine (MEA) is used to reduce the CO 2 content to
about 50 ppm.

The gas then passes through a cryogenic system, which removes the residual CO 2 and
water vapor, plus methane and other hydrocarbons and finally nitrogen.

The purified gas is a mixture of hydrogen (approximately 44%) and carbon monoxide
(approximately 56%). It requires further processing to provide the 2:1 ratio of H 2 to CO needed
to produce methanol.

Following cryogenic purification, the gas is compressed to 400 psig for shift conversion.
Part of the CO reacts with water vapour in the presence of an iron catalyst to form additional
hydrogen so that the exit gas contains a 2:1 ratio of H2 to CO.

Since the shift reaction also produces CO 2 it is necessary to rescrub the gas with a
potassium carbonate absorption system.

3.2.3. Methanol synthesis:

The syngas is then compressed to 2,000-4,000 psig and passed into the methanol synthesis
reactor. In the reactor, approximately 95% of the gas is converted to methanol over a
zincchromium catalyst. The Unreacted gasses are separated and recycled and the methanol is
purified by distillation.

3.3. PRODUCTION TECHNOLOGIES:

Page
10
All commercial methanol technologies is made up of three process sections as listed below:

Synthetic gas preparation

Methanol synthesis
Methanol purification

Synthesis gas (syngas) is a general term used in describing a mixture of hydrogen and carbon
monoxide (CO) in different ratios and can be generated from any hydrocarbon feedstock.
Synthesis gas can be produced from a large variety of materials which includes natural gas,
naphtha, residual oil, petroleum coke, biomass and coal. The most material applicable in the
production of methanol is natural gas. The conventional process for synthesis gas production is
steam reforming, but partial oxidation, CO2 reforming, auto thermal reforming or combinations
are also used which are shown in Figure 3.1. Typical inerts in the methanol synthesis are
methane, argon and nitrogen.

Fig.3.1. Steps involved in Methanol production from Natural gas

The first technology, the high pressure synthesis, was commercialized in 1923. It operated
at 300oC -400oC and above 300 bar and the catalysts used were based on ZnO-Cr 2O3. The zinc-
chromite catalyst had a very high resistance to catalyst poisoning, especially towards sculpture,
which was quite abundant in the early coal-based synthesis gases. Later ICI developed the low-
pressure methanol synthesis which replaced the high-pressure methanol synthesis in the
60s. It had become possible to produce large amounts of pure synthesis gas, essentially free of
poisons like sulphur and chlorine and a better catalyst was discovered: the combination Cu/ZnO
which was clearly much more active. The low-pressure synthesis operates between 50 and 100
bar and at 220oC -2800C. Two low-pressure methanol processes dominate the market; the ICI
Page
11
process uses multi-bed synthesis reactors with feed-gas quench cooling and the Lurgi process
uses multitubular synthesis reactors with internal cooling. Different process technologies are

1. Lurgi low pressure methanol synthesis process

2. ICI low pressure methanol process
3. Haldor Topsoe methanol process
4. The MGC low pressure process

3.3.1. Lurgi low pressure methanol synthesis process:

Lurgis low pressure methanol process is an advanced technology for natural gas to
methanol at low cost in large quantities which is shown in Figure 3.2.

The natural gas is first desulphurized and saturated with process steam, then reformed in
three steps; pre reforming, steam reforming, and auto thermal reforming. A Ni-based catalyst is
used in all reformer steps.

Lurgi reactor, the catalyst is packed in vertical tubes surrounded by boiling water. The
reaction heat is transferred to the boiling water and steam is produced. Efficient heat transfer
gives small temperature gradients along the reactor. Typical operating conditions are 523 K and
80 bars. The reactor temperature is controlled by the pressure of the boiling water, because of the
quasi-isothermal reaction conditions and high catalyst selectivity, only small amounts of
byproducts are formed. Methanol conversion is limited by equilibrium.

Unreacted synthesis gas is separated from crude methanol, then compressed and
recycled. A portion of recycle gas is purged to remove inerts. The H 2-rich purge stream is partly
used as fuel in the steam reformer, and partly recycled to the synthesis gas section. The methanol
synthesis loop consists of two parallel reactors with a common steam drum, a feed effluent
interchanger, a cooler, a methanol separator and a recycle compressor. Part of the MP steam
produced in the steam drum is utilized in the recycle compressor.

The crude methanol is purified by distillation. Only small amounts of by-products are
present. Ethanol is the most difficult component to remove. Dissolved gases are first removed by
flashing at low pressure. Low- and high- boiling by-products are removed in a energy-integrated

Page
12
three column distillation sequence. In the stabilizer column, low-boiling by-products are removed
from the top. The second and third columns separate pure methanol from water and low boiling
by-products. Ethanol is removed in a side-stream in the third column. The second column
operates at elevated pressure and the third operates at ambient pressure. The condenser in the
high-pressure column is integrated with the reboiler in the low-pressure.

Fig.3.2. Flow sheet for lurgis low pressure methanol synthesis

3.3.2. ICI low pressure methanol process:

The process showed in Figure 3.3. utilizes the use of an adiabatic reactor and a single
catalyst bed. The heat of reaction is removed or quenched by introducing cold reactants at

Page
13
different heights of the catalyst bed. The whole process includes two sections: methanol synthesis
section, and distillation section.

The Synthesis Section:

The synthesis section consists of reactor and heat exchangers and flashers. The Syngas
stream comes out of the reforming section and is compressed to 1500 psia. After exchanging heat
with the synthesis reactor product in heat exchangers, the syngas reacts in reactor to produce
crude methanol, and then uncondensed gases are separated. The impure methanol synthesized
and flows to the distillation section for purification.

The Distillation Section:

The distillation section includes two distillation towers. The overhead vapor from 1 st
distillation column is cooled in heat exchanger, and the condensate, mainly methanol with some
light ends, is returned as reflux. The uncondensed vapor mainly consisting of dimethyl ether is
removed from reflux drum to blend with the synthesis section purge. The bottom product from 1 st
distillation column is fed to 2nd distillation column, the refining column, which is operated at 100
psia at the base. Most of the water is separated in the bottom, and the wet methanol is obtained as
the top product which is having purity of 99.85 mol%.

Fig.3.3. Flow diagram for ICI low pressure process

3.3.3. Haldor Topsoe methanol process:

A typical Topsoe methanol design includes the following main process steps and is shown
in Figure 3.4.

Feed purification:
Page
14
It is imperative to remove impurities like sulphur and chlorine efficiently from the
hydrocarbon feed in order to prevent poisoning of nickel-based catalyst used in the various
reforming technologies and other downstream catalysts. Topsoes range of feed purification
catalysts provides an effective and economical removal of sulphur and chlorine compounds from
hydrocarbon feedstocks ranging from natural gas to naphtha.

Reforming:

In the adiabatic reformer, all higher hydrocarbons are converted into a mixture of carbon
oxides, hydrogen and methane at equilibrium. This results in stable and mild operating conditions
for the downstream tubular reformer.

Methanol synthesis:

In the methanol synthesis section the synthesis gas is converted to raw methanol containing
small amounts of water and by-products. In Topsoes methanol technology. The boiling water
reactor is most widely used due to its efficiency and ease of temperature control. Adiabatic
reactors in series or combinations of boiling water reactor (BWR) and adiabatic reactors may
also be considered. Two methanol synthesis catalysts are today included in the
Topsoe product portfolio MK-121 and MK-151 FENCE. Water and by-products are removed
from the raw methanol in the distillation section, which is most commonly designed for
production of methanol.

Fig.3.4. Flow sheet for Haldor Topsoe methanol synthesis

3.3.4. Mitsubishi Gas Chemical low-pressure methanol synthesis process:

The Flow Scheme showed in Figure 3.5. is the process developed by Mitsubishi Gas
Chemical Company. It uses copper-based methanol synthesis catalyst. It operates at temperatures
ranging from 200 - 280C over a pressure range of 50 150 atm. The temperature of the catalyst
bed is kept under control by using quench type converter design, and also some of the heat of
Page
15
reaction is recovered in an intermediate stage boiler. This process utilizes hydrocarbon as
feedstock. The raw material is desulphurized and then fed into a steam reformer at 500C. The
exit stream from the reformer contains hydrogen, carbon monoxide and carbon dioxide at 800 -
850C. The gases are compressed in a centrifugal compressor and mixed with the recycle stream
before being fed into the converter. From the mixture is sent to the distillation column for
separating methanol.

Fig.3.5. Flow sheet for MGC pressure methanol synthesis process

4. SELECTION OF THE PROCESS

This chapter includes the criteria for the selection of I.C.I Low Pressure Process Technology
with the comparison of other process technologies used in the manufacture of methanol which is
shown in Table 4.1.

The I.C.I process utilizes the use of an adiabatic quench reactor. The heat of reaction is
removed or quenched by introducing cold reactants at different heights of the catalyst bed. First

Page
16
of all fresh synthesis gas which is compressed and mixed with recycled gas is heated by heat
exchange with the reactor effluent. Then the stream is sent to the reactor after undergoing
supplementary preheating also by the reactor effluent. Then the rest is used as a quench gas for
removing the heat of reaction. The products emanating from the reactor is cooled by heat
exchanged with the feed and water for the generation of high pressure steam. It is further cooled
with an air-cool heat exchanger in which methanol and water are condensed. The separation of
gas/liquid takes place in a flash drum under pressure. The gas is recycled after purging small part
to keep the inerts level in the loop within limits. Purification of the methanol is done in two
different columns. The first column removes Di methyl ether and other light impurities whiles
the second separates methanol from water residue

4.1. FEATURES OF THE ADIABATIC QUENCH REACTOR:

Simple vessel structure

Ease of catalyst loading and unloading
Large single reactor capacity with capabilities over 3000 tonnes of methanol per day
Complex heat recovery
High rate of recycle gas
High catalyst volume

4.2. ADVANTAGES OF THE PROCESS TECHNOLOGY:

Major advantages of the ICI low pressure methanol process are:

1. Excellent selectivity of the converter catalyst (CuO-ZnO-Al2O3) and the consequent low level of
organic impurities.

2. The simple distillation column can achieve high efficiency with requiring high reboil heat loads

3. To prevent corrosion a pre mixed aqueous solution of 1% NaOH is metered into the crude feed at
a rate sufficient to neutralize any organic acids present.

Due to the above reasons, the I.C.I Low Pressure Process Technology is used for the
manufacture of methanol.

4.3. COMPARISON OF DIFFERENT PROCESS TECHNOLOGIES:

Table.4.1. Comparison of different process technologies based on various parameters

Page
17
Properties ICI low pressure Haldor Topsoe Lurgi low The MGC
technology methanol methanol methanol process
process process
Feed stock Synthesis gas Natural gas Natural gas Natural gas

Reforming No Auto-reforming Steam-reforming Steam-reforming

Catalyst CuO-ZnO-Al2O3 MK-121 & MK- Cu-ZnO-Al2O3 Cu-based catalyst

151
Temperature(K) 500 483-518 523 473-553

Pressure(bar) 10 15-50 80 50-150

Reactor Quench-type Boiling water Tubular Quench-type

type
Conversion per 15-25 30 35 40
pass (%)
Heat recovery More Less Less Less

Design Simple Complex Complex Complex

4.4. INDUSTRIES USING THIS PROCESS TECHNOLOGY:

1. Gujarat Narmada Valley Fertilizers Company Limited

2. Deepak Fertilizers and Petrochemicals Corporation Limited
3. Rashtriya Chemicals and Fertilizers Limited
4. Assam Petrochemicals Limited

5. PROCESS DETAILS

This chapter includes the study of various steps which are taking place in the process
technology used along with the reactions, operating temperatures and pressures of streams used
including the Process flow diagram which is shown in Figure 5.1. and Block flow diagram in
Figure 5.2.

Feed stock: Synthesis gas which is entering the mixer at a temperature of 423 K and 10 atm.
Main processes involving in this terminology:

Mixing of synthesis gas and recycle gas.

Conversion of mixed gas into methanol.

Page
18
Passing the product mixture into a heat exchanger.
Cooling of the product mixture.
Separation of product mixture into top separated gas and bottom separated liquid.
Separations of top separated gas into purge gas and recycle gas.
Compression of recycle gas.
Distillation of bottom separated liquid to get dimethyl ether as light end product.
Purification of bottom distilled product-1to get high purified methanol.

5.1. Mixing of synthesis gas and recycle gas:

The synthesis gas which is at 423 K and 10 atm is mixed with recycle gas of temperature
333oK and pressure 10 atm. Then the mixed gas is formed which is at a pressure of 10 atm and
348oK temperature.

5.2. Conversion of mixed gas into product mixture:

The mixed gas which is at temperature 348 K passes through the heat exchanger and
reaches temperature around 370 K and at pressure of 10 atm. The main reaction which takes
place in the reactor is

CO + 2H2 CH3OH H298 = -90.5 kJ/mol. R5.1

Set of side reactions which takes place are
CO + 3H2 CH4 + H2O R5.2
CO + H2O CO2 + H2 R5.3
2CH3OH CH3OCH3 R5.4

The conversion in the quench reactor is in the range of 15-25% per pass until it reaches the
thermodynamic equilibrium. The product mixture leaves the reactor at the temperature 470 K and
5 atm.

5.3. Passing the product mixture into a heat exchanger:

The product mixture which is at a temperature 455 K and pressure 5 atm is cooled by mixed
gas in the heat exchanger. The product mixture is cooled to temperature 420 K and the pressure 5
atm.

5.4. Cooling of the product mixture:

Page
19
The product mixture must be cooled before it enters the separator. It is cooled from 420 K to
330 K with the help of air entering at 298 K and leaving at 308 K.

5.5. Separation of product stream into top separated gas and bottom separated liquid:

The product mixture enters the separator which is maintained at a temperature of the product
mixture (330 K) and pressure of 5 atm. The top separated gas and bottom separated liquid are
obtained at the same temperature and pressure which are maintained at 330 K and 5 atm
pressure.

5.6. Separation of top separated gas into purge gas and recycled gas:

The top separated gas is sent into a purge separator in which the purge gas and recycle gas are
separated under the same conditions of temperature and pressure (330 K and 5 atm).

5.7. Compression of recycle gas:

The recycle gas which is at temperature of 330 K and pressure 5 atm is sent into the
compressor which is compressed to a pressure of 10 atm. The recycle gas leaves at a temperature
of 333 K and pressure of 10 atm.

5.8. Distillation of bottom separated liquid to get dimethyl ether as light end product:

The bottom separated liquid is sent into the light end column in which the distillation takes
place. The dimethyl ether leaves the distillation column at 308 K and bottom product leaves the
column at 358 K.

5.9. Purification of bottom product column-1 to get high purified methanol:

The bottom product column-1 enters the purification column at temperature of 358 K and
pressure 5 atm. The purification of bottom product coumn-1 takes place and methanol is obtained
as top product at 328 K with the purity of 99.85 mol % leaving the water residue at 368K and 5
atm pressure.

Page
20
FLOW DIAGRAMS

Page
21
Page
22
. Block diagram with equipment in the process

.2

Page
23
6. MATERIAL AND ENERGY BALANCES

This chapter includes the detailed study of material balance & energy balance of all the streams
present the process and details of all the streams are tabulated accordingly.

6.1. MATERIAL BALANCE:

BASIS:

Assume methanol plant capacity as

The product capacity is 900,000 tonnes/year

Production per hour: 3,906.25 kmol/hr

Decomposition of methanol to dimethyl ether can happen and the range of fraction is given as

Product % fraction of methanol decomposition

Di methyl ether 0-5

Assume 4% fraction of methanol is decomposed to Di methyl ether. Therefore the methanol

required to form is

(104/100) * 3,906.25 = 4,062.5 kmol/hr

CO balance:

Set of reactions required for the formation of methanol from components in the synthesis gas:

(1) CO + 2H2 CH3OH R6.1

(2) CO + H2O CO2 + H2 R6.2

(3) CO + 3H2 CH4 + H2O R6.3

(4) 2CH3OH CH3OCH3 + H2O R6.4

Selectivity of the reaction (1) is 90%

Selectivity = (amount of desired product / amount of undesired product)

Therefore total CO required: 4062.5 / 0.9 = 4,513.89 kmol/hr

Page
24
In total CO required the amount of CO required for other unwanted reactions is

=> 4,513.89 4,062.5 = 451.39 kmol/hr.

This amount is used in the formation of methane.

In reactions (2) and (3) CH4 is being from CO.

About 25% of CO is consumed in reactions (2) and remaining in (3)

The amount of CO is consumed in (2) = 451.39 * (25 / 100)

= 112.848 kmol/hr

The amount of CO consumed in (3) = 451.39 * (75 / 100)

= 338.542 kmol/hr

CO consumed here = CO consumed in (2) + CO consumed in (3)

= 112.848 + 338.542

= 451.39 kmol/hr

Di methyl ether balance:

Ether produced by decomposition of methanol.

=> (4,062.5 3,096.25) / 2

=> 78.125 kmol/hr.

Methane balance:

Methane is formed in reaction (3)

Methane formed in (3) = amount of CO formed in (3) = 338.542 kmol/hr

Then total methane = 338.542 kmol/hr.

Water balance:

Water is formed in reactions (3) and (4) and consumed in (2)

Water consumed in (2) = 112.847 kmol/hr

Water formed in (3) = 338.542 kmol/hr

Page
25
Water formed in (4) = 78.125 kmol/hr

Then total water formed = 338.542 + 78.125 - 112.847

= 303.82 kmol/hr.

CO2 balance:

CO2 is formed in (2)

Then CO2 = 112.847 kmol/hr

Hydrogen balance:

Hydrogen is being consumed in reactions (1), (2), (3)

Hydrogen consumed in (1) = 2 * 4062.5 = 8,125 kmol/hr

Hydrogen produced in (2) = 112.847 kmol/hr

Hydrogen consumed in (3) = 3 * 338.542 = 1,015.626 kmol/hr

Total H2 consumed = 8125 - 112.847 + 1015.626

= 9,027.779 kmol/hr

But synthesis gas contains CO and H2 present in feed gas in the ratio of 1:6

H2 in feed gas = 6 * 4,513.89 = 27,083.34 kmol/hr

Excess hydrogen in reaction = 27,083.34 - 9,027.779 = 18,055.561 kmol/hr

Amount of CO in recycle gas:

In single pass only about 25% of the synthesis gas is converted because of
thermodynamic equilibrium is reached.

A part of the product stream is purged and rest is recycled. Since CO is the limiting reactant, we
find recycle gas.

Unreacted CO = purged CO + recycled CO

0.75(CO + X) = 0.05 * 0.75(CO+X) + X

Amount of CO converted to methanol = 4513.89 kmol/hr

=> 0.75(4513.89 + X) = 0.05 * 0.75(4513.89 + X) + X

Page
26
=> 3385.4175 + 0.75X = 1.0375 X + 169.27

=> X = 3216.14625 / (1.0375 - 0.75) = 11,186.596 kmol/hr

The amount of CO in the recycle gas = 11,186.596 kmol/hr.

Amount of H2 in recycle gas:

The amount of CO converted in single pass conversion = 3,925.1217 kmol/hr

The amount of H2 required in single pass conversion = 7,856.2426 kmol/hr

The excess amount of H2 recycled for one pass = 27,083.34 7,856.2426

= 19,227.094 kmol/hr

For obtaining the giving capacity and purity the required amount of H 2 in the recycle gas to be 4
times the actual amount of H2 gas for single pass = 4 * 19,227.094

= 76,908.3896 kmol/hr

6.1.1. Mixer:

Inlet streams of mixer are recycle gas and synthesis gas and the outlet stream of mixer is mixed
gas are shown in Figure 6.1. & detailed conditions of mixer are shown in Table.6.1. and
individual component flow rates are shown in Table.6.2.

Fig.6.1.Synthetis gas and recycle gas Mixer

Table.6.1. Details and process conditions in mixer
INPUT OUTPUT
Variable Synthesis gas Recycle gas Mixed gas
Mass flow rate(kg/hr) 1.8963* 105 4.8087*105 6.705*105

Page
27
Temperature(K) 423 333 338
Pressure (atm) 10 10 10
Molar flow rate (kmol/hr) 31597.23 102948.53 134545.76
Mole fraction:
CO 0.142 0.126 0.13
H2 0.857 0.868 0.865
CO2 0 0.001 0.0008
CH3OH 0 0 0
CH3OCH3 0 0 0
H2O 0 0 0
CH4 0 0.003 0.002

Table.6.2. Mass balance for mixer

INPUT(kg/hr) OUTPUT(kg/hr)
component Synthesis gas Recycle gas Mixed gas
CO 135,427.37 303,202.41 429,746.56
H2 54,157.65 168,718.65 231,734.16
CO2 0 4,716.01 4,716.01
CH3OH 0 0 0
CH3OCH3 0 0 0
H2O 0 0 0
CH4 0 4,305.46 4,305.46
TOTAL 189,630.02 480,872.32
670,502.34 670,502.19

6.1.2. Reactor:

The inlet stream of reactor is mixed gas and the outlet stream is product mixture is shown in
Figure 6.2 and detailed conditions of reactor streams are shown in Table.6.3. and individual
component flow rates in Table.6.4.

Page
28
Fig.6.2. Quench reactor

Table.6.3. Details and process conditions in reactor

INPUT OUTPUT
Variable Mixed gas Product mixture
Mass flow rate(kg/hr) 6.705 *105 6.705*105
Temperature(K) 370 455
Pressure (atm) 10 5
Molar flow rate (kmol/hr) 134545.76 112811.32
Mole fraction:
CO 0.13 0.10
H2 0.865 0.85
CO2 0.0008 0.001
CH3OH 0 0.036
CH3OCH3 0 0.0006
H2O 0 0.002
CH4 0.002 0.003

Table.6.4. Mass balance for reactor

INPUT(kg/hr) OUTPUT(kg/hr)
component Mixed gas Product mixture
CO 429,746.56 325,871.69
H2 231,734.16 196,179.34

Page
29
CO2 4,716.01 4,936.69
CH3OH 0 129,958.64
CH3OCH3 0 3,383.59
H2O 0 4,767.25
CH4 4,305.46 5,404.94
TOTAL 670,502.19 670,502.14

6.1.3. Separator:

The inlet stream of separator is product mixture and the outlet streams of separator are top
separated gas and bottom separated liquid is shown in Figure 6.3. & detailed conditions of
separator streams are shown in Table.6.5. and individual component flow rates are shown in
Table.6.6.

Fig.6.3. Main Separator

Table.6.5. Details and process conditions in main separator

INPUT OUTPUT
Variable Product mixture Top separated gas Bottom separate
Mass flow rate(kg/hr) 6.705*105 5.323*105 1.38*105
Temperature(K) 330 330 330
Pressure (atm) 5 5 5
Molar flow rate (kmol/hr) 112811.32 108366.88 4288.19

Page
30
Mole fraction:
CO 0.10 0.12 0
H2 0.85 0.86 0
CO2 0.001 0.001 0
CH3OH 0.036 0 0.911
CH3OCH3 0.0006 0 0.018
H2O 0.002 0 0.071
CH4 0.003 0.002 0

Table.6.6. Mass balance for separator

INPUT(kg/hr) OUTPUT(kg/hr)
component Product mixture Top separated gas Bottom separate
CO 325,871.69 325,871.69 0
H2 196,179.34 196,179.34 0
CO2 4,936.69 4,936.69 0
CH3OH 129,958.64 0 129,958.64
CH3OCH3 3,383.59 0 3,383.59
H2O 4,767.25 0 4,767.25
CH4 5,404.94 5,404.94 0
TOTAL 532,392.66 138,109.48
670,502.14 670,502.14
6.1.4. Purge separator:

The inlet stream is Top separated liquid and outlet streams leaving the purge separator are purge
gas and recycle gas is shown in Figure 6.4. & detailed conditions of purge separator streams are
shown in Table.6.7. and individual component flow rates in Table.6.8.

Page
31
Fig.6.4.Purge separator

Table.6.7. Details and process conditions in purge separator

INPUT OUTPUT
Variable Top separated gas Recycle gas Purge gas
Mass flow rate(kg/hr) 5.323*105 4.808*105 5.15*104
Temperature(K) 330 330 330
Pressure (atm) 5 5 5
Molar flow rate (kmol/hr) 108366.88 102948.54 5418.34
Mole fraction:
CO 0.12 0.12 0.12
H2 0.86 0.86 0.86
CO2 0.001 0.001 0.001
CH3OH 0 0 0
CH3OCH3 0 0 0
H2O 0 0 0
CH4 0.002 0.002 0.002

Table.6.8. Mass balance for purge separator

INPUT(kg/hr) OUTPUT(kg/hr)
component Top separated gas Recycle gas Purge gas
CO 325,871.69 303,202.41 22,669.28
H2 196,179.34 168,718.65 27,460.69
CO2 4,936.69 4,716.01 606.955

Page
32
CH3OH 0 0 0
CH3OCH3 0 0 0
H2O 0 0 0
CH4 5,404.94 4,305.46 783.41
TOTAL 480,872.32 51,520.335
532,392.66 532,392.66

6.1.5. Distillation column (): (light end column):

The bottom product liquid is the inlet for light end column and from this distillation column
dimethyl ether is obtained as top product is shown in Figure 6.5 & detailed conditions of light-
end column streams are shown in Table.6.9 and individual component flow rates in Table.6.10.

Fig.6.5. Light-ends distillation column

In this distillation only dimethyl ether is being distilled as no other reactions occur, no other
products are formed as top products.

Feed entering: methanol + water + ether

= 3906.25 + 303.82 + 78.125

= 4288.195 kmol/hr

Page
33
Ether is the component to be separated, assume that xd = 0.998 and xb = 0.005

xf = 78.125/4288.195 = 0.0182 F=B+D xf F =

xd D + xb B

=> 0.182F = 0.005 B + 0.998 D

=> 0.005 B + 0.998 D = 78.125 (a)

B + D = 4288.195 (b)

Solve (a) and (b) we get

B = 4231.191 kmol/hr ; D = 57.003 kmol/hr

Table.6.9. Details and process conditions in light-end column

FEED DISTILLATE BOTTOM
Variable Bottom separate Di-methyl ether Bottom column-1
Mass flow rate(kg/hr) 1.38*105 2,618.8 1.355*105
Temperature(K) 330 308 358
Pressure (atm) 5 4.8 5.2
Molar flow rate (kmol/hr) 4288.19 57.00 4231.19
Mole fraction:
CO 0 0 0
H2 0 0 0
CO2 0 0 0
CH3OH 0.92 0.002 0.924
CH3OCH3 0.01 0.998 0.006
H2O 0.07 0 0.07
CH4 0 0 0

Table.6.10. Mass balance for light end column

FEED(kg/hr) DISTILLATE(kg/hr) BOTTOM(kg/hr)
component Bottom separate Di-methyl ether Bottom column-1
CO 0 0 0
H2 0 0 0
CO2 0 0 0

Page
34
CH3OH 129,958.64 3.648 129,954.99
CH3OCH3 3,383.59 2,616.75 766.84
H2O 4,767.25 0 4767.25
CH4 0 0 0
TOTAL 2,620.39 135,489.09
138,109.48 138,109.48

6.1.6. Distillation column (2): Purification column:

Bottom product column-1 is the inlet for purification column and in this distillation column
methanol is obtained as top product and water as bottom product is shown in Figure 6.6. &
detailed conditions of purification column streams are shown in Table.6.11 and individual
component flow rates in Table.6.12.

Fig.6.6. Purification distillation column

Here no other components are present except methanol and water

Here methanol is key component

F = 4231.191 kmol/hr xf =

3909.56 / 4231.191

= 0.924

Specific grade A methanol is 99.85 mol%

Page
35
Then xd = 99.85 / 100 = 0.9985

Assume xb = 0.001

F= D+B xf

F = xd D + xb B

0.924 * 4231.191 = 0.9985D + 0.001 B (a)

We know that F = D + B

4231.191 = D + B (b)

Solve (a) and (b) we get D =

3,915.18 kmol/hr (99.85 mol %)

B = 316.01 kmol/hr = water.

Table.6.11. Details and process conditions in Purification column

FEED DISTILLATE BOTTOM
Variable Bottom Column-1 Methanol Water
Mass flow rate(kg/hr) 1.355*105 1.3*105 5,436.63
Temperature(K) 358 328 368
Pressure (atm) 5.2 5 5.4
Molar flow rate (kmol/hr) 4231.19 3915.18 316.01
Mole fraction:
CO 0 0 0
H2 0 0 0

Page
36
CO2 0 0 0
CH3OH 0.924 0.9985 0.001
CH3OCH3 0.006 0.0015 0.039
H2O 0.07 0 0.96
CH4 0 0 0
Table.6.12. Mass balance for Purification column
FEED(kg/hr) DISTILLATE(kg/hr) BOTTOM(kg/hr)
component Bottom Column-1 Methanol Water
CO 0 0 0
H2 0 0 0
CO2 0 0 0
CH3OH 129,958.64 129,948.42 10.22
CH3OCH3 766.84 272.91 493.93
H2O 4765.19 0 4,765.19
CH4 0 0 0
130,221.33 5,269.35
TOTAL 135,490.68 135,490.68

6.2. ENERGY BALANCE:

This part deals with the energy balance of equipment present in the process and for streams
passing through them.

6.2.1. Energy balance for the reactor:

BASIS: 1 hour operation (only for reactor)

The mixed gas coming from the mixture enters reactor at 370K and is shown in Figure 6.7
Reactants from the reactor:
CO : 17490.95 kmol

H2 : 116382.1 kmol

CO2 : 107.64 kmol

CH4 : 269.1 kmol

Page
37
Base temperature = 45oC = Tb Temperature
of inlet = 97oC = 370 K Products from the
reactor:
CO : 11281.13 kmol

H2 : 96889.63 kmol

CO2 : 112.847 kmol

CH3OH : 4061.84 kmol

CH4 : 338.542 kmol

H2O : 304.96 kmol

CH3OCH3 : 78.125 kmol

Temperature of the outlet = Tre = 300 K

Main reaction:

CO + 2H2 CH3OH R6.5

Side reactions:

2CO + 2H2 CH4 + CO2 R6.6

CO + H2O CO2+H2 R6.7

2CH3OH CH3OCH3 + H2O R6.8

Page
38
Fig.6.7. Heat flow from the reactor

Energy balance equation for the reactor:

The specific heats of components at 370K and 500K are shown in Table.6.13 and Table.6.14
respectively.

(m*Cp*T) reactants + HR + Q = (m*Cp*T) products Where

Q = heat released by exothermic reaction.

(m*Cp*T) reactants = [(m1*Cp1) CO + (m2*Cp2) H2 + (m3*Cp3) CO2 + (m4*Cp4) CH4]* Treactants

Treactants = Tr - Tb => 97 - 45 = 52oC

Table.6.13. Specific heats of components at 370K and total heat from reactants mixture
Component Cp (kJ/Kmol K) mCpT(kJ)

CO 29.28 26812942.04

H2 29.071 175933889.5

CO2 40.166 224820.348

CH4 39.825 557279.19

Total 20352891.8

(m*Cp*T) reactants = [26812942.04 + 175933889.5 + 224820.348 + 557279.19]

= 203,528,915.8 kJ = 20.35* 1010 J.

(m*Cp*T) products = [(m1*Cp1) CH3OH + (m2*Cp2) CH4 + (m3*Cp3) CO2 + (m4*Cp4) H2O+
(m5*Cp5)CH3OCH3 + (m6*Cp6) H2 + (m1*Cp1) CO)] * (TProducts - Treference)

TR = reaction temperature = 500 K

Tproducts = 500 - 370 K = 130 K

Table.6.14. Specific heats of components at 500K and total heat from product mixture
Component Cp (kJ/kmol K) mCpT(kJ)
Page
39
CH3OH 59.5165 31583282.36

CH4 47.1925 2076963.634

CO2 44.652 655196.452

H2O 35.394 1403188.051

CH3OCH3 93.24 946968.75

H2 29.283 365031646.5

CO 29.8135 43768992.79

Total 445268769.3
(m*Cp*T) products = [31583282.36 + 2076963.634 + 655196.452 + 1403188.051 + 946968.75

+ 365031646.5 + 43768992.79]

= 445,268,769.3 kJ

= 44.526 *1010 Joule.

From the literature the heat of reaction for both main and side reactions is

HR = heat of reaction (actual) + heat of reaction (side reactions)

HR = 4.65*108 J (for methanol) + 1.762*1011 J (for other side reactions)

= 1.766*1011 J

Heat to be removed = (m*Cp*T)products - HR - (m*Cp*T)reactants

= 44.526 *1010 - 17.66*1010 - 20.35* 1010

= 6.516*1010 J

Heat from the reactor = Q = 6.516*`1010 J

This heat is being removed by the boiling water at 180oC (483K)

6.516*108 = mo * 34.946 * (500 - 483)

Page
40
=> mo = 39,672,150.71 kmol of boiling water

= 7.14*1010 kg of boiling water is required.

Note: The boiling point of water at 5 atm is 2640C (537K). Therefore only sensible heat is
considered and no latent heat is considered.

6.2.2. Energy balance for the heat exchanger:

In this heat exchanger the product mixture (hot stream) enters at tube side and the mixed gas
enters at shell side (cold stream) which is shown in Figure 6.8. & their inlet and outlet
temperatures are shown in Table.6.15.

The temperatures of inlet and outlet stream of products are Th,in= 455K ,Th,out = 420K

The molar flow rates of cold stream = 134548.76 kmol/hr

The molar flow rates of hot stream = 112811.32 kmol/hr

Cp of hot stream calculated on molar basis at inlet temperature 455K = 30.12 kJ/kmol

Cp of cold stream calculated on molar basis at inlet temperature 338 K = 27.62 kJ/kmolK

The heat of cold stream = 134548.76 * 27.622 * (370 - 338) = 118,925,588.1 kJ/hr

The heat of hot stream = 112811.32 * 30.12 * (455 - 420) = 118,925,588.16 kJ/hr

Page
41
Fig.6.8. Product mixture and mixed gas flowing in the heat exchanger

Table.6.15. Temperature for hot and cold streams in the heat exchanger
Hot Stream (Kelvin) Product mixture Cold Stream Mixed gas
(from reactor) (to reactor)

Tin 455 T(in)(deg K) 338

Tout 420 T(out)(deg K) 370

The log mean temperature difference:

LMTD = [(Th,in Tc,out) (Th,out Tc,in)] / ln[(Th,in Tc,out)/(Th,out Tc,in)]

= (85 82) / ln (85 / 82)

= 83.491K

6.2.3. Energy balance for cooler:

Cooler inlet temperature = 420 K

Cooler outlet temperature = 330 K

Air entering temperature = 298 K

Air leaving temperature = 308 K

The specific heats of components at 330K and the heat from the products leaving the cooler are
shown in Table.6.16

T = 330 308 = 22 K

Page
42
Table.6.16.Specific heats of components at 330K and heat from products leaving the cooler
Compound mo (kmol/hr) CP (kJ/kmol K) mCpT(kJ/hr)

CH3OH 4061.54 46.349 4141462.98

CH4 338.542 37.547 279647.2024

CO2 112.847 38.545 95693.127

H2O 304.96 33.898 227425.74

CH3OCH3 78.125 70.340 120896.875

H2 95889.62 28.974 61122728.7

CO 11281.13 29.2 7246997.912

Total 73234852.55

(H) products leaving the reactor = (mCpT)

(H) products leaving the reactor = [(4141462.98 + 279647.2024 + 95693.127 + 227425.74 + 120896.87

+ 61122728.7 + 7246997.912)

= 73,234,852.55 kJ/hr

(m*Cp*T) products entering cooler = 118,925,588.16 kJ/hr

Heat removed in the cooler = 118,925,588.16 73,234,852.55

= 45,690,735.55 kJ/hr

6.2.4. Energy balance for separator:

The product mixture from the cooler enters the separator and in separator the product mixture
separated into two streams (liquid stream, gas stream). The liquid stream leaves the separator
from the bottom and gas stream leaves from the top. The enthalpies of both streams are
calculated and tabulated in Table.6.17.

We take the constant temperature (330 K) separating with the calculated L/G ratio.
Page
43
L/G = 4288.195 / 107622.159

= 0.04

Amount of heat present in the liquid stream = 0.04 * 73,234,852.55

= 2,929,394.12 kJ/hr

Top separated gas = 70,305,458.43 kJ/hr

Table.6.17. Enthalpies of streams entering and leaving the separator

Stream Enthalpy(kJ/hr)

Product mixture from cooler 73,234,852.55

Bottom separated liquid 29,29,394.12

Top separated gas 70,305,458.43

6.2.5. Energy balance for compressor:

The recycle gas from the purge separator enters the compressor which is shown in Figure.6.9. &
the calculated enthalpies of inlet and outlet streams are tabulated in Table.6.18.

Temperature inlet for the compressor = 330 K

F = 102948.53 kmol/hr

Rg = 8.314 kJ/ kmol K Cp = 29 kJ/kmol K

= Cp / (Cp Rg) = 1.3989 = adiabatic factor

Polytrophic efficiency = 0.78 = p

Mechanic efficiency = 0.98 = m

Page
44
Pressure increases from 5 atm to 10 atm

Pout = 10atm ; Pin = 5atm ;

Qcompressor = F * *Rg * Tin * [(Pout /Pin) ( )/ (-1 *p) -1] / (1 - * )m

= 102948.53 *1.3989* 8.314*330 *[(10/5) (1.3989-1)/ (1.3989*0.78) -1] / (1.3989-1) *0.98

= 2,914,979.75 kJ/hr

This work will be added to enthalpy. so the increase in enthalpy =

= (0.948 * 70,305,458.43) 2,914,979.75

= 66,790,185.51 2,914,979.75 kJ/hr

= 63,875,205.76 kJ/hr

Therefore the energy leaving the compressor = 63,875,205.76 kJ/hr.

Fig.6.9. Heat supplied to the compressor

Table.6.18. Enthalpies of streams entering and leaving the compressor

Stream Heat(kJ/hr)

Qcompressor 2,914,979.75
Page
45
Recycle gas entering 66,790,185.51
the compressor

Recycle gas leaving 63,875,205.76

the compressor
6.2.6. Energy balance for distillation column-1(light-ends column):

The bottom separated liquid from the separator is sent to light-ends column shown in Figure
6.10.

F = 4288.195 kmol/hr

D = 57.003 kmol/hr

B = 4231.194 kmol/hr

Assume reflux ratio (R) = 4

Liquid flow rate = L = R * D

= 4 * 57.003

= 228.012

Vapour flow rate = (R+1) D

= (4+1) *57.003

= 285.015 kmol/hr

Page
46
Fig.6.10. Condenser and Reboiler duty in light-end column

Energy balance for condenser:

The equation used for energy balance for condenser:

> VHV = Qcondensor + LHL + DHD avg

of mixture at 330K = 22515.02 kJ/mol Cpavg of

mixture at 308 = 67.103kJ/molK

VHV = V [avg + Cpavg (Tfeed Ttop )

= 285.015 [22515.02 + 67.102 (330 - 308)]

= 6,837,875.99 kJ/hr

DHD = D [Cpavg (Tfeed Ttop)]

= 57.003 * 67.102 * (330 - 308)

= 84,150.33 kJ/hr

LHL = L [Cpavg (Tfeed Ttop)]

= 228.012 * 67.102 * (330 - 308)

= 336,601.347 kJ/hr
Page
47
Qcondensor = VHV - DHD - LHL

= 6,837.875.99 84150.33 336,601.347

= 6.417*106 kg/hr

Cooling water requirement = 6.417 *106 / [4.187 * (55 - 24)]

= 4.944*104 kg/hr

Energy balance for reboiler:

The equation used for energy balance for reboiler:

FHF + Qreboiler = QC + DHD + BHB

FHF calculated from separator = 2,929,394.12 kJ/hr

DHD = 84,150.33 kJ/hr

Cpavg of mixture at 358K = 47.694 kJ/molK

BHB = B [CPavg (Tbottom - Tfeed)

= 4231.191 *47.694 * (358 - 330)

= 5650,467.86 kJ/hr

Qreboiler = QC + DHD + BHB - FHF

= 6,417,000 + 84,150.33 + 5,650.467 2,929,394.12

= 9.22*106 kJ/hr

The calculated enthalpies of entering and leaving streams of light-end column are tabulated in
Table.6.19

Steam requirement:

Steam available at 5 atm pressure and temperature of 410K

Steam requirement = 9.22*106 / 2143.4

Page
48
= 4301.57 kg/hr

Table.6.19. Enthalpies of streams entering and leaving the light-end column

Stream Heat rate(kJ/hr)
FHf 2,929,394.12
DHd 84,150.33
BHb 5650,467.86
Qcondensor 6.417*106
Qreboiler 9.22*106
6.2.7. Energy balance for distillation column-2(purification column):

The bottom distilled product from the bottom of the light end column is sent to the purification
column where it is separated into methanol and water as shown in Figure 6.11

F = 4231.191 kmol/hr

D = 3915.18 kmol/hr

B = 316.01 kmol/hr

Assume reflux ratio (R) = 1.6

Liquid flow rate = L = R * D

= 1.6 * 3915.18

= 6264.288 kmol/hr

Vapour flow rate V = (R+1) D

= (4+1) * 57.003

= 10179.468 kmol/hr

Page
49
Fig.6.11. Condenser and Reboiler duty in purification column

Energy balance for condenser:

The equation used for energy balance for condenser:

> VH V = Qcondensor + LHL + DHD avg

of mixture at 358K = 33482.55 kJ/mol

Cpavg of mixture at 328K = 46.225 kJ/molK

VHV = V [avg + Cpavg (Tfeed Ttop)

= 10179.468 [33482.55 + 46.225 (358 328)]

= 35,495,092.85 kJ/hr

DHD = D [Cpavg (Tfeed Ttop)]

= 3918.18 * 46.225*(358 328)

= 5,429,375.86 kJ/hr

LHL = L [Cpavg (Tfeed Ttop)]

= 6264.288 * 46.225 * (358 328)

Page
50
= 8,687,001.38 kJ/hr

Qcondensor = VHV - DHD - LHL

= 35,495,092.85 + 5,429,375.86 + 8,687,001.38

= 21,378,715.11 kJ/hr = 21.378*106 kJ/hr

Cooling water requirement = 21.378*106/ [4.187*(26 - 20)]

= 85.096*104 kg/hr

Energy balance for reboiler:

The equation used for energy balance for reboiler:

FHF + Qreboiler = QC + DHD + BHB

FHF = BHB from previous column = 5,650,467.86 kJ/hr

DHD = 5,429,375.86 kJ/hr

Qcondenser = 21.378*106 kJ/hr

Cpavg of mixture at 368K = 45.835 kJ/mol

BHB = B [CPavg (Tbottom - Tfeed)

= 316.01 * 35.835 * (368 - 358)

= 113,344.59 kJ/hr

Qreboiler = Qcondenser + DHD + BHB - FHF

= 21.378*106 + 5,429,375.86 + 113,344.59 5,560,467.86

= 21.27*106 kJ/hr

The calculated enthalpies of entering and leaving streams of purification column are tabulated in
Table.6.20

Steam requirement:
Page
51
Steam available at 5 atm pressure and temperature of 410K

Steam requirement = 21.27*106 / 2143.4 = 9,923 kg/hr

Table.6.20. Enthalpies of streams entering and leaving the purification column

Stream Heat rate(kJ/hr)
FHf 5,650,467.56
DHd 5,429,375.86
BHb 113,344.59
Qcondensor 21.378*106
Qreboiler 21.27*106

7. SPECIFIC EQUIPMENT DESIGN

PURIFICATION COLUMN, CONDENSER AND REBOILER

This chapter includes detailed design of main equipment used in this process technology which
is purification column and its condenser & reboiler.

7.1. Calculation of theoretical stages:

Composition of bottom product column-1 = Feed Composition = 92.32 mol% of methanol

xf = 0.9232

Composition of methanol stream = Distillate Composition = 99.85 mol% of methanol

xd = 0.9985

Composition of water residue stream = Bottom composition = 0.1 mol% of methanol

xb = 0.001

Feed Pressure = 5.2 atm, the equilibrium data for methanol-water at this pressure is as shown in
Table.7.1

Feed temperature = 358 K

Page
52
Table.7.1. Equilibrium data of methanol-water mixture at 5.2 atm

T (K) x y
369.65 0.0084 0.1030
365.45 0.0258 0.227
360.65 0.068 0.391
353.25 0.137 0.568
349.05 0.24 0.68
343.75 0.48 0.79
341.85 0.572 0.82
339.55 0.741 0.906
329.35 1 1
Thermal condition of the feed stream:

Feed is in saturated liquid form, so the value of q = 1

Now the rectifying line and feed line intersect on the equilibrium line and make the intercept
which is given by min

min = xd/ (Rmin +1)

From the below graph-Figure 7.1, the value of min is found out to be 0.71

Page
53
Fig.7.1. Minimum Reflux Graph

=> xd/ (Rmin +1) = 0.71

0.9985/ (Rmin +1) = 0.71

Rmin = 0.4006

Assume the operating reflux to be 4 times the minimum reflux, which implies

R = 4*Rmin

R = 4*0.4006 = 1.6

Intercept for the rectifying operating line = = xd/(R+1)

= 0.9985/ (1.6+1) = 0.38

Fig.7.2. Theoretical construction of stages

From the above graph- Figure 7.2, stages are plotted between the rectifying operating line,
stripping operating line and the equilibrium line using the McCabe-Thiele method.

Number of theoretical stages obtained from the graph = 7

7.2. Design Data:

Page
54
Number of theoretical stages =7

Slope of bottom operating line = 1.03

Slope of top operating line = 0.6154

Top composition (mol %) = 99.85

Bottom composition (mol %) = 0.1

Reflux ratio = 1.6

Molar flow rate of feed = F = 4231.9 kmol/hr

Molar balance on methanol gives distillate flow rate

D = 3911.79 kmol/hr

Vapor rate = V = D (1+R)

= 3911.79 * (1+1.6) = 10170.654 kmol/hr

Liquid rate = L = D * R

= 3911.79 * 1.6 = 6258.86 kmol/hr

In the stripping section, the bottom flow rate can be found out by overall mass balance

B = F-D = 4231.19 3911.79 = 319.79 kmol/hr

L1 = L+F = 6258.86 + 4231.19 = 10490.05 kmol/hr

V1 = V = 10170.654 kmol/hr

7.3. Physical properties:

The column efficiency to be 60% as it is validated by OConnells correlation (given in

Appendix) and consider reboiler as an equivalent stage.

Total number of real stages = (number of theoretical stages -1)/fractional efficiency

= (7-1) / 0.60 = 10

Page
55
Consider the pressure drop per plate to be 300 m.m of water (liquid)

Column pressure drop = Pressure drop per plate * number of real stages

= 300 * 10-3 * 1000 * 9.81 *10 = 29430 Pa

Top pressure of the column = 5 atm = 506600 Pa

Estimated bottom pressure of the column = 506600 + 29430 = 536030 Pa = 5.4 atm (nearly)

From steam tables, densities of liquid and vapor with surface tension of bottom mixture at base

temperature = 950C = 3680K L = 961.54 kg/m3 V = 0.594 kg/m3

Surface tension = 59.87*10-2N/m

From standard data, top product contains 99.85 mol% of methanol which contain densities of

liquid and vapor with surface tension of mixture at top temperature = 55 0C = 3280K L = 759.5

kg/m3 V = 0.945 kg/m3

Surface tension = 20.6*10-2N/m

7.4. Column diameter:

Calculation of flow-parameters at bottom and top portions of the column

FLV bottom = (L

FLV top = (L/V)*

From these FLV bottom and FLV top values we can calculate K- values from the Figure 7.3

Page
56
Fig.7.3. Flow-parameter vs. K-value for particular plate spacing
Consider the plate spacing to be 1 meter then k-values for the obtained flow-parameters are as

Base K1 = 15.75*10-2

Top K2 = 35.08*10-2

These K1 , K2 values are obtained at the surface tension of 20*10 -2 N/m so there must be
correction of values obtained inorder to get required K1,K2 values at given surface tension values.

Corrected K1 = K1 * (/20)0.2

= 15.75 *10-2 * (59.87/20)0.2 = 19.61*10-2

Corrected K2 = K2*(/20)0.2

= 35.08*10-2 *(20.6/20)0.2 = 35.29*10-2

Flooding Velocity at base and top of the column should be found to find the area of the column

Base Uf

= 7.89 m/s

Top Uf

= 35.29*10-2* = 10 m/s

Designing the column for 80% of the flooding velocity

Page
57
Base Uv = 0.8 * 7.89 = 6.313 m/s

Top Uv = 0.8 * 10 = 8 m/s

Maximum Volumetric vapor flow rate at the base and top of the column

Base = V1 * Mol.Wt / (V * 3600)

= 10170.654 *18.2 / (0.594 * 3600) = 85.61 m3/s

Top = V*Mol.Wt/ (V *3600)

= 10170.654 * 32.1 / (0.945 * 3600) = 95.66 m3/s

Net area required at the bottom and top portion of the column

Bottom net area = base vol.rate / base Uv = 85.61 / 6.313 =13.56 m2

Top net area = top vol.rate/ top Uv = 95.66 / 8 = 11.95 m2

Consider the downcomer area to be 12 per cent of the total net area in both sections. So the
column cross-sectional areas in both sections are

Bottom = 13.56 / (1- 0.12) = 15.413 m2

Top = 11.95 / (1-0.12) = 13.59 m2

Base diameter = = 4.43 m

Top diameter = = 4.16 m

Therefore the construction of the distillation column must be uniform either in the outer diameter
and inner diameter. Consider the column of standard outer diameter of O.D = 4.5116m and
thickness of 9.52 m.m, thus having the inner diameter of I.D = 4.5 m

7.5. Liquid flow pattern:

Maximum volumetric bottom liquid flow rate = L1 *Mol.Wt / (L*3600)

= 10490.05 *18 / (961.54*3600) = 0.0545 m3/s

Page
58
Fig.7.4.Type of flow according to column diameter and liquid flow rate
From the above graph Figure 7.4, the region for the considered diameter and liquid flow rate has
been specified as the cross-flow arrangement which is known as single pass plate arrangement

Therefore the single pass plate can be used in this purification column with column internal
diameter 4.5 m

7.6. Provisional plate design:

Inner diameter of the column = Dc = 4.5 m

Area of the column = Ac = 3.14*(4.5)2 = 15.9 m2

Downcomer area on each plate = Ad = 0.12 * Ac = 0.12 * 15.9 =1.91 m2

Net area of the column = An = Ac - Ad = 15.9 - 1.91 = 13.99 m2

Active area of the column = Aa = Ac-2 *Ad = 15.9 - ( 2 *1.91) = 12.08 m2

Consider hole area on the each plate = Ah = 10% of Aa = 1.208 m2

From the above plot Figure 7.5, the weir length can be found with the help of % of downcomer
area on total area.

Page
59
Fig.7.5.Relation between downcomer area and weir length

Percent of downcomer area is 12%, then from the graph lw / Dc is equal to 0.76

Weir length = lw = 0.76 * Dc = 0.76 * 4.5 = 3.42 m

Take weir height = hw = 50 m.m

Hole diameter = dh = 5 m.m

Plate thickness = 5 m.m

7.7. Check weeping:

Maximum liquid mass flow rate = L1 *Mol.Wt / 3600

= 10490.05 * 18 / 3600 = 52.45 kg/s

Minimum liquid mass flow rate = 75% of the maximum = 0.75 *52.45 = 39.38 kg/s

Maximum over-weir height = how = 750 (max mass.flow rate/ L*lw) 2/3

= 750 * (52.45 / 961.54 *3.42) = 47.52 m.m of liquid

Minimum over-weir height = how = 750(min mass.flow rate/ L*lw) 2/3

Page
60
= 750 * (39.38 / 961.54 *3.42) = 39.26 m.m of liquid At

minimum mass flow rate = hw + how = 50 + 39.26 = 89.26 m.m of liquid

Fig.7.6. Weep point correlation plot

From the above plot Figure 7.6 the corresponding K 2 value for the obtained hw+how value is 30.8
Minimum design vapor velocity = Uhmin = (K2 0.90 (25.4 dh )) / V0.5

= (30.8 0.9 ( 25.4-5 )) / 0.5940.5 =16.1408 m/s

Actual minimum vapor velocity = min.vapor rate /Ah = 0.75 *85.61 / 1.208 = 53.15 m/s

So the minimum operating rate will be well above the weep point

7.8. Plate pressure drop:

Maximum vapor velocity through holes = Uh = max.vapor volumetric flow rate/Ah

= 85.61 / 1.208 = 70.86 m/s

Page
61
Fig.7.7. Discharge coefficient, sieve plate in relation with Percent perforated area
From considerations Plate thickness/hole diameter =1

Ah / Ap = Ah / Aa =0.1

From the above graph Figure 7.7. the orifice coefficient obtained is Co = 0.84

Dry plate pressure drop = hd = 51( Uh / Co) 2(V / L)

= 51( 70.86 / 0.84 )2 (0.594/961.5)

= 224.22 m.m of liquid

Residual head = hr = 12.5 *103 / 961.54 = 12.99 m.m of liquid

Total pressure drop = ht = hd + ( hw + how ) + hr

= 224 + ( 50 + 39 ) +12 = 325 m.m of liquid

Page
62
It was assumed that 300 m.m of liquid of pressure drop per plate inorder to calculate the base
pressure. The calculation could be the repeated estimate but the small change in physical
properties will have effect on the plate design. 325 m.m of liquid pressure drop per plate is
considered acceptable.

7.9. Downcomer liquid back-up:

Calculating the downcomer pressure loss

Take hap = hw-10 = 40 m.m

Area under apron = Aap = lw * hap =3.42 * 40 *10-3 m2 = 0.1368 m2

As this value is less than Ad = 1.208 m2, the above area is substituted in the equation

hdc = 166 ( Lw / L* Aap )2

= 166 ( 52.45 / 961.54 * 0.1368 ) 2 = 4.2 m.m say

5 m.m of liquid

Back-up in downcomer = hb = ht + ( hw + how ) + hdc

= 325 + ( 50 + 39 ) + 5 = 419 m.m of liquid = 0.42 m of liquid

Plate spacing = 1m

Weir height = 0.05 m

(Plate spacing + weir height) / 2 = (1+0.05) / 2 = 0.52 m

0.42 m < (Plate spacing + weir height) / 2; So the plate spacing is acceptable.

7.10. Check residence time:

Residence time is calculated by using the equation = tr = Ad*hb* L/Lw

= 1.91*0.42*961.54/52.45 = 14.75 s
> 3 s (satisfactory)
7.11. Check entrainment:

Vapor velocity = Uv = Vapor Vol.Flow rate/net area = 85.61 / 13.99 = 6.1 m/s

Page
63
Percent flooding = Uv / base flooding velocity = 6.1 / 7.89 = 77%

Fig.7.8. Entrainment correlation for sieve plates in accordance of flow parameter

The percent of flooding is 77% and flow parameter at the bottom of distillation column is F LV =
0.0256. From the above graph Figure 7.8, by using the above two parameters, the fractional
entrainment is found out to be = 0.056 which is well below the value = 0.1

As the percent flooding is well below the design figure of 80 percent, the column diameter could
be reduced, but this would increase the pressure drop.

7.12. Trial layout:

We use the cartridge type construction; consider 50 m.m of unperforated strip round plate edge;
50 m.m wide calming zones as shown in Figure 7.9. and the relation between weir length, chord
height and angle subtended by weir length are shown in Figure 7.10.

Page
64
Fig.7.9.Trial layout of sieve plate

Fig.7.10.Relation between weir length, chord height and angle subtended by weir length

The value lw / Dc = 3.42 / 4.5 = 0.76

From the above graph Fig 8.10 the angle subtended by the weir chord is c = 990

Angle subtended by the edge of the plate =1800 - 990 = 810

Mean length of unperforated edge strips = (4.5-0.05) *3.141* 81 / 100 = 11.32 m

Area of unperforated edge strips = 0.05 * 11.32 = 0.566 m2

Mean length of calming zone = weir length + width of unperforated strip

= 3.42 + 0.05 = 3.47 m

Page
65
Area of calming zones = 2 * 3.47 * 0.05 = 0.347 m2

Total area of perforations = Ap = Aa-Auhp-Acz = 12.08 - 0.566 - 0.347 = 11.167 m2

Fig.7.11.Relation between hole area and pitch

The ratio Ah/Ap = 1.208/11.167 = 0.108

From the above Figure 7.11, the corresponding value of lp/dh =2.8

= which lies between 2.5 and 4.0 Hole

pitch = 2.8 *dh =2.8 * 5 = 14 m.m

8.13. Number of holes:

Area of one hole = 1.964*10-5 m2

Number of holes = Total hole area / Area of one hole

= 1.208 / (1.964*10-5) = 61507 holes

8.14. Plate specification:

Page
66
All plate specifications are tabulated in Table.7.2 and sieve plate specifications are shown in
Figure 7.12. and Figure 7.13

Table.7.2.All plate specifications

Plate: No 1

Plate I.D 4.5 m

Hole size 5 m.m

Hole pitch 14 m.m

Active holes 61507

Turn down(% of maximum) 70

Plate material Mild Steel

Downcomer material Mild steel

Plate spacing 1m

Plate thickness 5 m.m

Plate pressure drop 325 m.m of liquid = 3.2 Kpa

Page
67
Fig.7.12.Sieve plate specifications

Fig.7.13.Weir height and apron height

7.15. Condenser design:

The molar flow rate of vapor into the condenser of a purification column is

Page
68
V = 10,179.468 Kmol /hr
Entering temperature of the condensate = 350C = 308 K

Leaving temperature of the condensate = 250C = 298 K

The enthalpy of the vapor = 3,480.93 kJ/kmol

The enthalpy of the condensate = 2,773.5 kJ/kmol

Entering temperature of the cooling water = 200C = 293 K

Leaving temperature of the cooling water = 260C = 299 K

Standard plant requires the tubes of each having outer diameter 20 m.m and inner diameter

16.8 m.m and tube length of 4.88 m long made of admiralty brass

Thermal condition of vapor: Totally condensed and no sub-cooling occurs

Here only the thermal design of the condenser is considered

The physical properties of the mixture will be taken as mean of those for methanol (M.W=32)

and di-methyl ether (M.W=46) at the average temperature.

Heat transferred from vapor = 10179.468 * (3486.93 - 2773.5) / 3600

= 2,016.325 kW

Cooling water mass flow rate = 2016.325 / 4.187 * (26-20)

= 80.26 kg/s

Assume the overall heat coefficient = 800 W/m2 K as it is methanol-water system the

overall heat transfer coefficient lies in the range of

700-1200 W/m2 K .

Mean temperature difference:

The condensation range is small and the change in the saturation temperature will be linear. So
the corrected logarithmic mean temperature is used.

R = ( Tcon.in Tcon.out ) / ( Tw.out Tw.in )

= ( 35-25 ) / ( 26-20 ) = 1.6

Page
69
S = ( Tw.out Tw.in ) / ( Tcon.in Tw.in)

= ( 26-20 ) / ( 35-20 ) = 0.4

Take a horizontal exchanger with condensation in the shell, four tube passes. For one shell and
four tube passes Ft = 0.78 from the below Figure 7.14.

Fig.7.14.Ft parameter versus S correlation

Tlh = (( 35-26 ) - ( 25-20 )) / ln (( 35 - 26 ) / ( 25-20) )

= 70C
Tm = 0.78 * 7 = 5.460C

Trial area = 2016.325 *103/ 800 *5.46 = 461 m2

Surface area of one tube = * 20 * 10-3 * 4.88 = 0.305m2

Number of tubes = 461 / 0.305 = 1,512

Using square pitch = Pt = 1.25 * 20 = 25 m.m

Tube bundle diameter = Db = do (Nt / K1)1/n1

K1 for 4 pass and square pitch is 0.158 and n1 is 2.263

Db = 20 (1.512 / 0.158 )1/2.263

= 1,148 m.m
Page
70
Number of tubes in the center row = Nr = Db / Pt = 1148 / 25 = 46

Shell-side coefficient:

Estimate tube wall temperature by assuming the condensing heat transfer coefficient as

1400 W/m2 0K

Shell side mean temperature = (35 + 25) / 2 = 300C

Tube side mean temperature = (26 + 20) / 2 = 230C

Balancing the heat energy on both sides

=> (30-Tw) *1400 = (30-23) * 800

=> Tw = 260C

Mean temperature condensate = ( 30 + 26 ) / 2 = 56/2 = 280C

Physical properties at 280C

L = 0.5354 mNs/m2 L =

785 kg/m3

KL = 0.1981 W/m0C

Vapor density at mean vapor temperature = V

= (32 / 22.4) * (273 / (273 + 30)) *10 = 12.87 kg/m3

h = Wc / L*Nt = (325529.2 / 3600) * (1 /4.88 *1512) = 12.25*10-3 kg/s.m

Nr = 2 *46 / 3 = 30

(hc)b = 0.95 * KL (L ( L-V ) g / L * h )1/3 *Nr-1/6

= 0.95 * 0.1981 (785 * ( 785 - 12.87 ) * 9.81) / 0.5324*10-3*12.25*10-3)-1/3* (30)-1/6

= 1327.859 W/m2 0C

Close enough to assumed value of 1400 W/m2 0C. So no correction to Tw needed.

Tube-side coefficient:

Page
71
Tube cross-sectional area = (/4) * (16.8*10-2)2 * 1512 / 4 = 0.084 m2

Density of water at 230C = 998 kg/m3

Tube velocity = (80.26 / 998) * (1 / 0.084) = 0.957m/s

Inner heat transfer coefficient = hi = 4200 (1.35 + 0.02t ) Ut0.8 / di0.2

= 4200 (1.35 + 0.02 * 23) * 0.9570.8 / 16.80.2

= 4374 W/m2 0C

Fouling factors: As neither fluid is heavily fouling, use 6500 W/m 2 0C for each side and Kw = 50
W/m0C

Overall coefficient:

1/U = 1/1327.859 + 1/6500 + 20*10-3ln (20/16.8)/2*50 + 20/(16.8*6500) + 20/(16.8*4374)

= 12.39*10-4

U = 807 W/m2 0CClose enough to the estimate, firm up design.

Shell-side pressure drop:

Use pull through floating head, no need for close clearance

Select baffle spacing = shell diameter, 45 percent cut

Page
72
Fig.7.15. Shell bundle clearance

For calculated bundle diameter Db = 1148 m.m the clearance from the above graph Figure 7.15 is
97 m.m

Shell inner diameter = shell bundle diameter + clearance = 1148 + 97 = 1245 m.m

Using kerns method to make an approximate estimate

Cross-flow area = As = ( Pt do ) * Ds * lb / Pt

= ( 25-20 ) * 1245 *1245 *10-6 / 25 = 0.31 m2

Mass flow rate based on inlet conditions = Gs = (325529.2 / 3600) * (1 / 0.31)

= 291.69 kg/s.m2

Equivalent diameter = de = 1.27( Pt2 0.785do2 ) / do

= 1.27( 252 0.785*202 ) / 20

= 19.8 m.m

Vapor viscosity = 0.056 mNs/m2

Reynolds number = Re = 291.69 * 19.8 *10-3 / 0.056*10-3

= 103,133

From this Reynolds number we can calculate shell side friction factors, and segmental baffles
from the below graph in Figure 7.16

Page
73
Fig.7.16. Shell-side friction factors, segmental baffles

From the above figure, the friction factor = jf = 2.2*10-2

Us = Gs / V = 291.69 / 12.87 = 22.6 m/s

Take the pressure drop as 40 % of that calculated using the inlet flow, neglect viscosity correction

Ps = 8 * jf ( Ds / de ) ( L / lb) ( V * Us2 / 2) ( / w )-0.14

= (2/5) * (8 * 2.2 *10-2) (1245 / 19.8) (4.88 / 1245) (12.87 * (22.6)2 / 2)

= 6425 N/m2

= 6.4 kPa

Negligible, more sophisticated method of calculation not justified.

Tube-side pressure drop:

Viscosity of water = 0.6 mNs/m2

Reynolds number = 0.957*993*16.8*10-3/(0.6*10-3) = 26,608

Page
74
By using this Reynolds number we can calculate tube side friction factors from the below graph
in Figure 7.17.

Fig.7.17. Tube-side friction factors

From the above graph, the friction factor jf = 3.8*10-3

Neglect viscosity correction factor

Pt = Np (8*jf (L/di) (/w)-m + 2.5)**Ut2/2

= 4 (8*3.8*10-3(4.88/13.8*10-3) +2.5)*993*0.9572/2

= 20,608.73 N/m2 = 20.61 KPa which

is an acceptable value.

7.16. Reboiler design:

Consider a kettle type reboiler is used in purification column

Physical properties of methanol at 5.4 atm

Page
75
Vaporization rate of methanol : 10179.468 kmol/hr

Boiling point at 5.4 atm : 125.440C

Latent heat of the stream : 35,278 kJ/kmol

Critical pressure (Pc) : 80 atm

Mean specific heat liquid : 51.463 kJ/kmol0C

Calculation of heat loads:

Sensible heat load (maximum) = ( 125.44 - 0) * 51.463 = 6,455.52 kJ/kmol

Total heat load = (6455.52 + 35,278) *10179.418 / 3600 = 1180 kW

For methanol-water mixture, we use steam to vaporize the mixture. The range of overall heat
transfer coefficient is in the range of 900 1200 W/m2 0C

Assume U = 1200 W/ m2 0C

Mean temperature difference:

Steam saturation temperature at 5 atm = 4100K = 1370C

Tm = 137 125.44 = 11.560C

Area required (outside) = Total head load / U *Tm

= 1180 *1000 / 1200 *11.56 = 85 m2

Select 56 m.m of inner diameter and 60 m.m of outer diameter plain U-tubes of nominal length =
9.6 m

Number of U-tubes = Area required (outside)/Area of each pipe

= 85 / (60*10-3) * 3.14 * 9.6 = 46 tubes

Use square pitch arrangement, pitch = 1.5 * tube outer diameter

= 1.5 * 60 = 90 m.m

Page
76
Draw a tube layout diagram as shown in Figure 7.18, take minimum bend radius = 1.5 * tube
outer diameter

=> 1.5 * 60 = 90 m.m

Process layout gives 48 tubes; tube outer limit diameter is 1440 m.m

Fig.7.18. Tube sheet layout

Use mostinskis equation

Heat flux, based on estimated area = Q = Total heat load / Area (outside)

= 1180 / 85 = 13.88 kW/m2

Heat coefficient = hnb is given by the equation hnb = 0.104 (Pc)0.69

(Q)0.7 (1.8(P/Pc)0.17 + 4 (P /Pc)1.2 + 10(P/Pc)10)

P = operating pressure, bar = 5.47 bar

Page
77
Pc = liquid critical pressure, bar = 81.056 bar Q

= heat flux, W/m2 = 13.88 kW/m2

hnb = 0.104 * (81.056)0.69 * (13.88 * 103)0.7 * (1.8(5.47 / 81.056)0.17 + 4 (5.47 / 81.056)1.2

+10(5.47 / 81.056)10)

= 2,219.56 W/m2 0C

Take steam condensing coefficient as 10,000 W/m2 0C

Fouling coefficient 7000 W/m2 0C and methanol fouling coefficient, essentially clean 14,000
W/m2 0C

Tube material will be in plain carbon steel = 55 W/m 0C

1/U0 = (1/2219.56) + (1/14000) + (60*10-3*ln (60/56) ) / 2*55 + (60/56)*(1/7000 + 1/10000)

U0 = 1246.17 W/m2 0C

This is close enough to original estimate of 1200 W/m2 oC for the design to stand.

Myers and Kate give some data on boiling of methanol on banks of tubes. To compare the value
estimate with their values an estimate of the boiling film temperature difference is required.

= (1246.17/2219.17) * 11.56 = 6.490C

Myers data, extrapolated gives a coefficient of around 1200 Btu/h ft2 0F at a 6.490C temperature
difference = 6200 W/m2 0C, so the estimated value of 2219.56 W/m 2 0C is certainly on the safe
side.

Check maximum allowable heat flux. Use modified Zuber equation.

Surface tension (estimated) = 20.6*10-3 N/m

L = 759.5 kg/m3 V = 0.945 kg/m3

Nt = 96

Page
78
Qcb = Kb (Pt/Do) (/ ) (g (L - v)* v2)0.25

As square arrangement Kb = 0.44

Qcb = 0.44*(90/60)*(1102*103/ ) (20.6*10-3* 9.8*(759.5 0.945)*(0.945)2)0.25

= 253,913 W/m2

= 250 kW/m2

Applying a factor of 0.7, maximum flux rate should not exceed the value

= 250*0.7 = 175 kW/m2.

Actual flux of 13.88 kW/m2 is well below maximum allowable flux rate.

Layout:

From tube sheet layout Db = 1440 m.m

Take shell diameter as twice bundle diameter Ds = 2*1440

= 2880 m.m

Take liquid level as 1600 m.m from base

From the free board layout as shown in Figure 7.19, Freeboard

= 2880 1600 = 1280 m.m, satisfactory.

Page
79
Fig.7.19. Freeboard layout

From above sketch at liquid level = 1.8 m

Surface area of the liquid = 1.8*9.6/2 = 8.64 m2

Vapor velocity at surface = (10179.468 / 34 * 3600) * (1/0.945)*(8.64)

= 0.02 m/s

Maximum allowable vapor velocity = uv = 0.2((L - v)/ v) 0.5

= 0.2*((759.068 0.945)/0.945)0.5

= 5.6 m/s

So the actual velocity is well below maximum allowable velocity. A smaller shell diameter could
be considered.

Page
80
8. SIMULATION OF METHANOL PLANT USING UnisimTM
This chapter includes the study of comparison of handmade calculations and computer
simulated results using UnisimTM design software.

Now a day, each and every industry is using advanced simulation softwares in order to observe
the process without being actually running the real plant so that they can know the faults of
designs in real process equipment and adjustment of flow rates of process streams in the plant.

The simulation software Unisim TM which is designed by Honeywell Corporation is mostly

used in many of the chemical and petro-chemical industries. Manufacture of methanol by I.C.I
low pressure technology is made to simulate using this software inorder to check the correctness
of hand calculations made and how the various process parameters like pressure and temperature
effect the operation of various equipment in the plant.

The main and side reactions used in the converter are Reactions 6.1, 6.2, 6.3 and 6.4 in which
compounds like methanol, CO2, H2O, dimethyl ether and methane are formed which are
separated at flash separator and methanol is obtained as top product of the second distillation
column and the simulated flow sheet is shown in Figure 8.1.

Fluid Package is UniSims terminology for a collection of data that includes all
the thermodynamic, component, and reaction parameters required to run the model. Select SRK
equation (Soave-Redlich-Kwong) as this method provides maximum data to the chemicals.

UniSim has put together data for a set of reactions for us called Global Rxn Set.
It only contains one reaction, Methanol Reaction, but we could add others (e.g. side reactions
that produced small quantities of methane and dimethyl ether). If our model contained an
unrelated group of reactions (e.g. if we put a water gas shift reactor on the front of the process)
we could create another Reaction Set. In this way we could model different reactors using
different reactions. The first (blue) is a material stream going from one piece of equipment to
another. The second (red) is an energy stream. These will be handled by UniSim. If all the
streams appear in the dark blue, then the whole plant is said to working fine. Having completed
the process model we will now take a look at some of the facilities in UniSim that allow us to
generate reports, do additional design tasks, and help with model development.

Page
81
. Flow sheet of simulation of manufacture of methanol

.1

Page
82
Page
83
Page
84
Page
85
Page
86
9. MATERIALS OF CONSTRUCTION

This chapter include the study of type of material used and method of the construction of
main equipment used in this process like reactors, heat exchanger, separator, distillation columns.
Methanol is non-corrosive to most metals at ambient temperatures exceptions include
lead, magnesium and platinum. Mild steel is usually selected as the construction material. Tanks
built with copper alloys, zinc (including galvanized steel), aluminium or plastics are not suitable
for methanol-water solutions. While plastics can be used for short-term storage, they are
generally not recommended for long-term storage due to deterioration effects and the subsequent
risk of contamination. Furthermore, coatings of copper (or copper alloys), zinc (including
galvanized steel) or aluminium are attacked slowly.

Many resins, nylons and rubbers, particularly nitrile (Buna-N), ethylene propylene rubber
(EPDM), Teflon and neoprene are used satisfactorily as components of equipment in methanol
service.

9.1. Methods of Construction:

Storage containers and transfer systems must be designed according to appropriate

engineering standards, and comply with all legislative requirements.

Storage tanks of welded construction are normally satisfactory. They should have secondary
containment such as dikes or bunds to reduce fire risks and prevent large spills. Large tanks and
containers must have control devices such as level gauges, conservation vents and pressure
vacuum relief valves, as well as grounding. In some locations, vapor recovery may be required.
In confined areas or buildings, ventilation systems may be necessary in order to keep airborne
concentrations of methanol below permissible exposure limits.

9.1.1. Grounding:

Carbide tipped clamps (to ensure good contact through paint) and dip tube filling are
generally used to guard against ignition from static electricity.

9.1.2. Pipes and Hoses:

Industry best practices make use of mild steel piping with welded flanges and methanol
compatible gaskets. Generally, screwed connections are not used. In most loading and unloading
Page
87
situations, the possibility of spark generation due to the accumulation of static electricity is
minimal, as the electrical conductivity of methanol is relatively high. Velocity limits should be
considered with regard to high pressure drop, hydraulic impacts, and erosion or corrosion
concerns. Non-ferrous materials should not be used for the construction of permanent pipework.
Rubber hoses should have an internal wire coil for strength and electrical continuity, and should
only be used for temporary connections. The hose material must be compatible with methanol.
All hoses should be clearly labelled for methanol service only. The ends must be capped, or
otherwise protected from contamination, when the hose is not in use. Prior to putting any new
pipework or hose into methanol service, it should be thoroughly washed with water and then with
methanol to ensure that all contaminants are removed.

9.1.3. Motors and Pumps:

Motors and associated electrical equipment used in methanol service should conform to
local or national electrical codes. Motors and pumps must be grounded. Pumps should be
dedicated to methanol service, and flushed with methanol prior to first use.

9.1.4. Vapour Controls:

Internal or external floating roofs can be used to control methanol vapor emissions from
storage tanks. Inert gas blanketing can be used to prevent the formation of explosive atmospheres
in vapor spaces inside tanks. Dry nitrogen is the preferred inert gas and should be essentially free
of carbon dioxide (CO ). The presence of CO may impact the methanol quality by increasing its
2 2

acidity. Pressure vacuum relief valves are normally used to control tank pressures.

9.1.5. Venting:

Methanol can vent to atmosphere through pressure vacuum relief valves, flame arresters or
vacuum breakers. Overflow pipes are not recommended due to condensed methanol dripping
from the pipes when the ambient temperature is below the storage temperature. This could create
a fire and environmental hazard. Reduced vapor losses will result from painting tanks white or
other reflective colours.

9.1.6. Cleaning and Maintenance:

Page
88
For all forms of transportation, methanol vessels should be inspected for cleanliness and
mechanical soundness prior to loading. Mechanical or contamination concerns should be
resolved promptly. Procedures for entry into methanol vessels and storage tanks in preparation
for cleaning and maintenance are prescribed by local regulations. The following suggestions are
made for general guidance only:

Partially fill and flush 3-4 times with water.

Open top and bottom man ways for natural ventilation. On large tanks, install air
moving devices.
Tank or vessel must test gas free. Before entry, check for safe oxygen and combustible
levels.
When unattended, man ways should be blocked to prevent entry by unauthorized
personnel.
No one should enter any confined space without a safety watch in place.
At least two escape routes should be provided from all storage and handling areas.

10. PROCESS CONTROL

This chapter includes the controlling of various streams and operating conditions of all the
equipment using a transfer function in which it contains important parameters.

Page
89
Fig.10.1. Methanol plant wide control

The key element for selection of controllers is the economic objective. In this case there is an
temperature profile as a function of time. Since the deactivation rate mainly depends on
important effect which will not be captured by steady state economic, namely the deactivation
rate of the catalyst. This subject has been studied by Lovik et al. (1998). They showed that there
is an optimal reactor temperature, we will assume that the reactor temperature is given. Therefore
a steady state analysis will be used on the remaining degrees of freedom and the process control
for whole plant is shown in Figure 10.1

The objective function:

There is a need for an objective function to control the main variables like purge flow, feed
flow, product flow and compressor energy in the synthesis loop while in distillation loop the
main variable are distillate and bottom product flow rates which vary according to temperature
and pressure in respective columns.

Let Yi be the objective function which is dependent on the variables feed flow Fo, product flow
Page
90
Bo, purge flow Po and compressor energy Uo which can be taken as linear equation as

Yi = aBo + bPo cFo dUo where a, b, c, d are some constants

This function is further simplified as

Yi = Bo Wr*Uo

The characteristics of the controlling variables can be known from the relation with this
objective function to the required operating variables like for purge flow in Figure 10.2, for
recycle compressor work in Figure 10.3, for feed flow rate in Figure 10.4. and for hydrogen
composition in recycle gas in Figure 10.4.

10.1. Variation of objective function with purge flow:

Fig.10.2.Variation of objective with purge flow

10.2. Variation of objective function with recycle compressor work:

Page
91
Fig.10.3.Variation of objective function with recycle compressor work

10.3. Variation of loss in objective function with feed flow rate:

Fig.10.4. Variation of loss in objective function with feed rate

10.4. Variation of loss in objective function with hydrogen composition in recycle gas:

Page
92
Fig.10.5.Variation of loss in objective function with hydrogen composition in recycle gas

11. SAFETY, HEALTH AND ENVIRONMENTAL ASPECTS

Page
93
This chapter includes the study of various safety, health and environmental factors along with
the material safety data sheets (MSDS) of synthesis gas (CO and H 2), methanol and dimethyl
ether.
The goal of chemical plant is not only to produce the chemicals, but to produce them
safely. In the plants chain of processes and operations, loss of control anywhere can lead to
accidents and then losses of life and property from hazards. Attempts should be made to prevent
troubles from the inspection while designing, fabricating and operating.
Safety generally involves:
1. Identification and assessments of the hazards
2. Control of hazards
3. Control of the process by provision of automatic control system, interlocks, alarm trips, etc.
4. Limitation of the loss, by press relief, plant layout, etc.

11.1. PERSONAL PROTECTION:

11.1.1. Sources of Exposure to Methanol:

Human exposure to methanol can occur via absorption, contact with eyes, inhalation and
ingestion.

1) Absorption: No serious adverse effects result from skin contact so long as repeated and
excessive exposures are avoided.

2) Eye Contact: Methanol is a mild to moderate eye irritant. High vapor concentration or liquid
contact with eyes causes irritation, tearing and burning.

3) Inhalation: Inhalation of methanol vapors is the most frequent type of exposure. The
methanol threshold limit value (TLV) for a time weighted average (TWA) is 200 ppm. This is
the maximum average concentration a worker should be exposed to over a continuous eight
hour period. The short term exposure limit (STEL) of methanol is 250 ppm. The STEL sets
limits on excursions for periods of up to 15 minutes, four times per day with at least 60
minutes between exposure periods, so long as individuals are suffering no irritation or
discomfort.

Page
94
4) Ingestion: Methanol taken by mouth may pose a serious threat to life. One to four ounces of
methanol have been known to cause fatalities. Ingestion produces similar effects to that of
inhalation of vapors, but severity and speed of appearance of symptoms are increased.

11.1.2. Symptoms and Effects of Exposure:

Methanol can cause poisoning, systemic acidosis, optic nerve damage and central nervous
system (CNS) effects. Methanol can degrease the skin, which may cause dermatitis. Symptoms
of methanol poisoning do not depend on the uptake route and develop in three stages:

1. An initial narcotic effect followed by

2. A symptom-free interval lasting 10-48 hours; and

3. Nonspecific symptoms such as abdominal pain, nausea, headache, vomiting, and lassitude,
followed by characteristic symptoms such as blurred vision, opthalmalgia, photophobia and
possibly xanthopsia. For instance

1,000 ppm will produce symptoms such as irritation of the eyes and mucous membranes.

5,000 ppm will result in a stupor or sleepiness.

50,000 ppm will result in narcosis (deep unconsciousness) in one or two hours, probably
resulting in death.

Because the compound and its harmful metabolites are eliminated slowly, methanol is regarded
as a cumulative poison.

11.1.3. First Aid Measures:

In case of methanol contact with the skin, remove contaminated clothing. Wash with soap
and water for 15 minutes. Seek medical attention if irritation occurs.
In case of methanol contact with the eyes, flush immediately with gently running water for
a minimum of 15 minutes, ensuring all surfaces and crevices are flushed by lifting lower and
upper lids. Obtain medical attention.

In case of inhalation of methanol vapors, remove the individual to fresh air, but only if it is
safe to do so. Due to the possibility of delayed onset of more serious illness, it is important to
obtain medical attention.

Page
95
Ingestion of methanol is life threatening. Onset of symptoms may be delayed for 18 to 24
hours after ingestion. Do not induce vomiting. Transport to medical attention. The individual
should remain under close medical care and observation for several days.

11.1.4. Safety Precautions:

All personnel must be aware of the hazardous properties of methanol, and exercise
caution to avoid contact with it.
At all times, avoid prolonged or repeated breathing of methanol vapors.
Proper ventilation is required to ensure safe working conditions. The type of ventilation
will depend upon such factors as dead air spaces, temperature, convection currents and
wind direction and must be considered when determining equipment location, type and
capacity.
If mechanical ventilation is used, spark-proof fans should be implemented.

11.2. FIRE SAFETY:

Methanol is defined by the National Fire Protection Association (NFPA) and the
Occupational Safety and Health Administration (OSHA) in the USA as a Class 1B flammable
liquid. Class IB flammable liquids have a flash point below 73F and a boiling point greater than
or equal to 100F. Flash point is defined as the minimum temperature at which the vapor pressure
of a liquid is sufficient to form an ignitable mixture with air near the surface of the liquid. Pure
methanol has a flash point of 12C (54F). When ambient temperature is less than the flash point,
the fire hazard is reduced. However methanol local hot spots can exceed the flash point and
methanol can be ignited. Warmer ambient conditions increase the overall fire hazard.
The lower explosive limit (LEL) of a flammable liquid is defined as the minimum
concentration of the vapor in air for which a flame can propagate. The methanol LEL is 6% by
volume.

The upper explosive limit (UEL) of a flammable liquid is defined as the maximum
concentration of the vapor in air for which a flame can propagate. The methanol UEL is 36% by
volume. The UEL corresponds to a methanol temperature of 41C (106F).

Within the approximate temperature range of 12C to 41C, methanol will produce a
concentration of vapor that is explosive upon contact with an ignition source.

Page
96
The auto ignition temperature of a substance is the minimum temperature required for
self-sustained combustion in the absence of an external ignition source. Methanol has an auto
ignition temperature of 470C (878F).

11.2.1. Safety Precautions:

The low flash point and wide explosive range require facilities to exercise caution when
handling methanol.

1. Smoking must be prohibited.

2. Vehicle access should be strictly controlled.

3. Ventilation must be sufficient to cope with the maximum expected vapor levels in buildings

4. Storage tank vents to atmosphere should be sized for fire-heated emergency vapor release.

5. Dry chemical extinguishers should be accessible for small fires. An adequate supply of hand
held and types should be available.

6. Hydrants should be strategically placed with adequate hoses.

7. Small spills should be remediated with sand, earth or other non-combustible absorbent
material, and the area then flushed with water. Larger spills should be diluted with water and
diked for later exposal.

11.2.2. Fire fighting techniques:

Methanol flames are almost invisible in daylight, producing no soot or smoke. They may be
detected by the heat generated, a heat haze, or burning of materials in the affected area.
Dry chemical powder, carbon dioxide (CO2) and alcohol-resistant foam extinguish methanol
fires by oxygen deprivation.
Water will remove heat and dilute the liquid methanol. Fog or fine sprays will absorb
methanol vapors, quench heat and provide a curtain shield for upwind advancement to a fire
source.
Small fires can be extinguished using powder, CO2, or foam in the early stages. Be aware
that the methanol may re-ignite spontaneously, due to surrounding high temperatures that
may exceed the auto ignition temperature.
In addition to methanol vapors, fire-fighters may be exposed to combustion products, such
as formaldehyde and carbon monoxide which may form under conditions of depleted
Page
97
oxygen. Therefore, fire- fighters should wear full-face, positive pressure, self-contained
breathing apparatus or an airline. Chemical protection may be provided with impervious
clothing, gloves and footwear. Suitable materials include polyvinyl plastic, neoprene or
rubber.

11.3. ENVIRONMENTAL PROTECTION:

11.3.1. Biodegradation / Aquatic Toxicity:

Methanol biodegrades easily in water and soil. Methanol in high concentrations (>1%) in
fresh or salt water can have short-term harmful effects on aquatic life within the immediate spill
area.

11.3.2. Spill Response:

If a spill occurs, stop or reduce discharge of material if this can be done without risk.
Eliminate all sources of ignition. Avoid skin contact and inhalation. Do not walk through
spilled product. Stay upwind, keep out of low-lying areas.
Prevent spilled methanol from entering sewers, confined spaces, drains, or waterways.
Maximize methanol recovery for recycling or reuse.
Leaking containers should be removed to the outdoors or to an isolated, well-ventilated area,
and the contents transferred to a suitable container.
Foam may be used for vapor suppression. Vapors can be knocked down using a water spray.
Remove spilled product with explosion proof pumps or vacuum equipment. Treat the surface
with sorbent materials, such as vermiculite or activated carbon, to remove the remaining
methanol. Remove the sorbents after use.
Soil contaminated with methanol should be removed and remediated. Spills into large
natural bodies of water, such as rivers and oceans, cannot be recovered. Sorbents such as
zeolite and activated carbon should also be considered for in situ clean up.

11.3.3. Treatment and Disposal:

Possible treatment processes for spill countermeasures include biological degradation,

reverse osmosis, carbon adsorption, steam stripping and air stripping. Large quantities of waste
methanol can either be disposed of at a licensed waste solvent company or reclaimed by filtration

Page
98
and distillation. Waste methanol or water contaminated with methanol, must never be discharged
directly into sewers or surface waters.

11.3.4. Spill Prevention:

An effective spill prevention program will include engineering controls, training and
procedures, and spill response planning.

Effective engineering controls include overfill alarms, secondary containment for tanks, such
as dikes or bunds to contain large spills, and hydrocarbon detectors within dikes. Workers must
be trained to handle methanol in a safe manner. Systems and procedures that protect the
employees, the plant and the environment should be implemented.

MATERIAL SAFETY DATA SHEET FOR DIMETYL ETHER

1. Chemical product and company identification

Product name : Dimethyl Ether

Synonym : methyl ether, wood ether, methyl oxide, Methyoxymethane

Chemical Family : ethers, aliphatic.

Manufacturer : AIR GAS INC., on behalf of its subsidiaries

2. Hazards identification

EMERGENCY OVERVIEW:

Colour : colourless

Page
99
Physical Form : liquefied gas

Odour : sweet odour

Health Hazards : respiratory tract irritation, central nervous system depression

Emergency overview : Keep away from heat, sparks and flame. Do not puncture or
incinerate container. Can cause target organ damage. Use only
with adequate ventilation. Keep container closed.

Target organs : Causes damage to the following organs: skin, eyes.

Physical Hazards : Flammable gas. May cause flash fire. Flash back hazard.
Electrostatic charges may be generated by flow, agitation, etc.
May form peroxides during prolonged storage.

Potential health effects:

Inhalation : irritation, cough, difficulty breathing, headache, drowsiness,

dizziness, loss of coordination, blurred vision, unconsciousness
Skin : Contact with rapidly expanding gas may cause burns or frostbite.

Ingestion : Ingestion is not a normal route of exposure for gases

Eyes : Contact with rapidly expanding gas may cause burns or frostbite.

3. First aid measures

No action shall be taken involving any personal risk or without suitable training. If it is suspected
that fumes are still present, the rescuer should wear an appropriate mask or self-contained
breathing apparatus. It may be dangerous to the person providing aid to give mouth-to-mouth
resuscitation.

Eye contact : Check for and remove any contact lenses. Immediately flush eyes with plenty of
water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical
attention immediately.

Skin contact : In case of contact, immediately flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes. To avoid the risk of static discharges

Page
100
and gas ignition, soak contaminated clothing thoroughly with water before removing it. Wash
clothing before reuse. Clean shoes thoroughly before reuse. Get medical attention immediately.

Inhalation : Move exposed person to fresh air. If not breathing, if breathing is irregular or if
respiratory arrest occurs, provide artificial respiration or oxygen by trained personnel. Loosen
tight clothing such as a collar, tie, belt or waistband. Get medical attention immediately.

4. Fire-fighting measures

Flammability of the product : Flammable.

Auto-ignition temperature : 349.85C (661.7F)

Flash point : Closed cup: -41.15C (-42.1F).

Flammable limits : Lower: 3.4% Upper: 27%

Products of combustion : Decomposition products may include the following materials

CO, CO2

Fire-fighting media and : In case of fire, use water spray (fog), foam or dry chemical.

In case of fire, allow gas to burn if flow cannot be shut off immediately. Apply water from a safe
distance to cool container and protect surrounding area. If involved in fire, shutoff flows
immediately if it can be done without risk.

5. Accidental release measures

Personal precautions : Immediately contact emergency personnel. Keep unnecessary

Personnel away. Use suitable protective equipment shut off gas
Supply if this can be done safely. Isolate area until gas has
dispersed.

Environmental precaution : Avoid dispersal of spilled material and runoff and contact with
Soil, waterways, drains and sewers.

Methods for cleaning up : Immediately contact emergency personnel. Stop leak if without
risk. Use spark-proof tools and explosion-proof equipment..
Page
101
6. Handling and storage

Handling: Use only with adequate ventilation. Use explosion-proof electrical (ventilating,
lighting and material handling) equipment. High pressure gas. Do not puncture or incinerate
container. Use equipment rated for cylinder pressure. Close valve after each use and when empty.
Keep container closed. Keep away from heat, sparks and flame. To avoid fire, eliminate ignition
sources. Protect cylinders from physical damage; do not drag, roll, slide, or drop. Use a suitable
hand truck for cylinder movement.

Storage: Keep container in a cool, well-ventilated area. Keep container tightly closed and sealed
until ready for use. Avoid all possible sources of ignition (spark or flame).

MATERIAL SAFETY DATA SHEET FOR METHANOL

1. Product and supplier identification

Product name : Methanol.

Recommended use : solvent, fuel, feed stock.

Restrictions on use : Do not use in a confined area without proper ventilation. Contact

lenses may cause further damage in case of splash into eye. Avoid

use near heat, flames, sparks and other sources of ignition.

Product : methanol (CH3OH).

Synonyms : methyl alcohol, methyl hydrate, wood spirit, methyl hydroxide.

Company identification : Methanex Corporation.

Importer : Methanex Methanol Company.

Page
102
2. Hazards and identification

Classification : Flammable liquid, category 1, Acute toxic category1*,

Reproductive toxicity 1B, Specific target organ toxicity.

Hazard Communication : DANGER! Extremely flammable liquid and vapor.

May cause damage to eyes and central nervous system if ingested

or inhaled.

Flammable liquid and vapor: Burns with a clean, clear flame, which is almost invisible in
daylight, or a light blue flame. Can decompose at high temperatures forming carbon monoxide
and formaldehyde. Confined space toxicity hazard. Mild central nervous system depressant
following inhalation, skin absorption or ingestion. May cause headache, nausea, dizziness,
drowsiness, and un-coordination. Severe vision effects, including increased sensitivity to light,
blurred vision, and blindness may develop following an 8-24 hour symptom-free period. Coma
and death may result.

Irritant: Causes eye irritation. Aspiration hazard. Swallowing or vomiting of the liquid may
result in aspiration (breathing) into the lungs.

3. First aid measures

Note: Emergency assistance may also be available from the local poison control center.

Eye Contact: Remove contact lenses if worn. In case of contact, immediately flush eyes with
plenty of clean running water for at least 15 minutes, lifting the upper and lower eyelids
occasionally. Obtain medical attention

Skin Contact: In case of contact, remove contaminated clothing. In a shower, wash affected
areas with soap and water for at least 15 minutes. Seek medical attention if irritation occurs or
persists. Wash clothing before reuse. Prolonged contact with methanol may defat skin tissue,
resulting in drying and cracking.

Inhalation: Remove to fresh air, restore breathing if necessary. Obtain medical attention.

Page
103
Ingestion: Swallowing methanol is potentially life threatening. Onset of symptoms may be
delayed for 18 to 24 hours after digestion. If conscious and medical aid is not immediately
available, do not induce vomiting. In actual or suspected cases of ingestion, transport to medical
facility immediately.

Ethanol significantly decreases the toxicity of methanol because it competes for the same
metabolic enzymes, and has been used to treat methanol poisoning.

4. Fire Fighting Measures

Unsuitable Extinguishing Media: General purpose synthetic foams or protein foams may work,
but much less effectively. Water may be effective for cooling, but may not be effective for
extinguishing a fire because it may not cool methanol below its flash point.

Specific Hazards: Methanol vapors may burn with an invisible flame. During a fire, carbon
monoxide, carbon dioxide and toxic gases such as formaldehyde may be generated. Vapors can
accumulate in confined spaces resulting in a toxicity and flammability hazard. Closed containers
may rupture violently and suddenly release large quantities of methanol when exposed to fire or
excessive heat for a sufficient period of time. Vapors are slightly heavier than air and may travel
long distances toward sources of ignition.

Fire Fighting Instructions: Methanol burns with a clean clear flame that is almost invisible in
daylight. Stay upwind! Isolate and restrict area access. Concentrations of greater that 25%
methanol in water can be ignited. Use fine water spray or fog to control fire spread and cool
adjacent structures or containers. Contain fire control water for later disposal. Fire fighters must
wear full face, positive pressure, self-contained breathing apparatus or airline and appropriate
protective fire fighting clothing as per NFPA. Note that methanol fires may require proximity
suits. Take care not to walk through any spilled chemical.

5. Accidental Release Measures

Small Spill: Dilute with water and mop up, or absorb with an inert dry material and place in an
appropriate waste disposal container.

Large Spill: Flammable liquid. Poisonous liquid. Keep away from heat. Keep away from
sources of ignition. Stop leak if without risk. Absorb with dry earth, sand or other
Page
104
noncombustible material. Do not get water inside container. Do not touch spilled material. Use
water spray to reduce vapors. Prevent entry into sewers, basements or confined areas; dike if
needed. Call for assistance on disposal. Be careful that the product is not present at a
concentration level above TLV. Check TLV on the MSDS and with local authorities.

Environmental Precautions: Biodegrades easily in water. Methanol in fresh or salt water may
have serious effects on aquatic life. A study on methanols toxic effects on sewage sludge
bacteria reported little effect on digestion at 0.1% while 0.5% methanol retarded digestion.
Methanol will be broken down to carbon dioxide and water.

6. Handling and Storage

Precautions for Handling: No smoking or open flame in storage, use or handling areas. Use
explosion proof electrical equipment. Ensure proper electrical grounding procedures are in place.

Storage: Store in totally enclosed equipment, designed to avoid ignition and human contact.
Tanks must be grounded, vented, and should have vapor emission controls. Tanks must be diked
as per NFPA or API Standards. A flammable mixture of methanol vapor and air is possible inside
a storage tank or transportation tank, and handlers should take appropriate precautions to reduce
the risk of ignition. Handlers must eliminate ignition sources or purge the tank with an inert gas
such as nitrogen. All equipment must be grounded - bonded when transferring product in order to
avoid static discharge from the equipment, and subsequent possible fire. Avoid storage with
incompatible materials. Anhydrous methanol is non-corrosive to most metals at ambient
temperatures except for lead, nickel, Monel, cast iron and high silicon iron. Coatings of copper
(or copper alloys), zinc (including galvanized steel), or aluminium are unsuitable for storage.
These materials may be attacked slowly by the methanol. Storage tanks of welded construction
are normally satisfactory. They should be designed and built in conformance with good
engineering practice for the material being stored. While plastics can be used for short term
storage, they are generally not recommended for long-term storage due to deterioration effects
and the subsequent risk of contamination.

Corrosion rates for several construction materials:

<0.508 mm/year : Cast iron, Monel, lead, nickel

Page
105
<0.051 mm/year : High silicon iron

Some attack : Polyethylene

MATERIAL SAFETY DATA SHEET FOR CARBON MONOXIDE

1. Chemical product and company identification

Product name : Carbon Monoxide

Synonym : Carbon oxide (CO), Exhaust Gas, Flue gas, Carbonic oxide, Carbon
oxide, Carbone, Carbonio.
Product use : Synthetic/Analytical chemistry.

Supplier : AIR GAS INC., on behalf of its subsidiaries

2. Hazards identification

Physical state : Gas(colourless gas, may be a liquid at low temperature or highpressure)

Emergency overview : Keep away from heat, sparks and flame. Do not puncture or incinerate
container. Avoid breathing gas. May cause target organ damage, based
on animal data. Use only with adequate ventilation. Keep container
closed.

Contact with rapidly expanding gases can cause frostbite.

Target organs : May cause damage to the following organs: blood, lungs, the nervous
system, heart, cardiovascular system, central nervous system (CNS).

Routes of entry : Inhalation

Potential acute health effects:

Page
106
Eyes : Contact with rapidly expanding gas may cause burns or frostbite.

Skin : Contact with rapidly expanding gas may cause burns or frostbite.

Inhalation : Toxic by inhalation.

Ingestion : Ingestion is not a normal route of exposure for gases.

3. First aid measures

No action shall be taken involving any personal risk or without suitable training. If it is suspected
that fumes are still present, the rescuer should wear an appropriate mask or self-contained
breathing apparatus. It may be dangerous to the person providing aid to give mouth-to-mouth
resuscitation.

Eye contact: Check for and remove any contact lenses. Immediately flush eyes with plenty of
water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical
attention immediately.

Skin contact: In case of contact, immediately flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes. To avoid the risk of static discharges
and gas ignition, soak contaminated clothing thoroughly with water before removing it. Wash
clothing before reuse. Clean shoes thoroughly before reuse. Get medical attention immediately.

Frostbite: Try to warm up the frozen tissues and seek medical attention.

Inhalation: Move exposed person to fresh air. If not breathing, if breathing is irregular or if
respiratory arrest occurs, provide artificial respiration or oxygen by trained personnel. Loosen
tight clothing such as a collar, tie, belt or waistband. Get medical attention immediately.

4. Fire-fighting measures

Flammability of the product : Flammable.

Auto-ignition temperature : 605C (1121F)

Flammable limits : Lower: 12.5% Upper: 74.2%

Page
107
Products of combustion : Decomposition products may include the following materials:
CO, CO2

Fire hazards in the presence : Extremely flammable in the presence of following materials
of various substances open flames, sparks and static discharge and oxidizing
materials.
Fire-fighting media : In case of fire, use water spray (fog), foam or dry chemical.

In case of fire, allow gas to burn if flow cannot be shut off immediately. Apply water from a safe
distance to cool container and protect surrounding area. If involved in fire, shut off flow
immediately if it can be done without risk.

5. Accidental release measures

Personal precautions: Immediately contact emergency personnel. Keep unnecessary personnel

away. Use suitable protective equipment. Shut off gas supply if this can be done safely. Isolate
area until gas has dispersed.

Environmental precautions: Avoid dispersal of spilled material and runoff and contact with
soil, waterways, drains and sewers.

Methods for cleaning up: Immediately contact emergency personnel. Stop leak if without risk.
Use spark-proof tools and explosion-proof equipment.

6. Handling and storage

Handling: Use only with adequate ventilation. Use explosion-proof electrical (ventilating,
lighting and material handling) equipment. High pressure gas. Do not puncture or incinerate
container. Use equipment rated for cylinder pressure. Close valve after each use and when empty.
Keep container closed. Keep away from heat, sparks and flame. To avoid fire, eliminate ignition
sources. Protect cylinders from physical damage; do not drag, roll, slide, or drop. Use a suitable
hand truck for cylinder movement.

Storage: Keep container in a cool, well-ventilated area. Keep container tightly closed and sealed
until ready for use. Avoid all possible sources of ignition (spark or flame). Segregate from
oxidizing materials. Cylinders should be stored upright, with valve protection cap in place, and

Page
108
firmly secured to prevent falling or being knocked over. Cylinder temperatures should not exceed
52 C (125 F).

MATERIAL SAFETY DATA SHEET FOR HYDROGEN

1. Chemical product and company identification

Product name : hydrogen

Synonym : Dihydrogen, o-Hydrogen; p-Hydrogen;

Product use : Synthetic/Analytical chemistry.

Supplier : AIR GAS INC., on behalf of its subsidiaries

2. Hazards identification

Physical state : Gas or Liquid.

Emergency overview : Extremely flammable; Do not puncture or incinerate container; Can

cause rapid suffocation; May cause severe frostbite;

Target organs : May cause damage to the lungs.

Routes of entry : Inhalation

Potential acute health effects:

Eyes : Contact with rapidly expanding gas may cause burns or frostbite. Contact with
cryogenic liquid can cause frostbite and cryogenic burns.

Skin : Contact with rapidly expanding gas may cause burns or frostbite. Contact with
cryogenic liquid can cause frostbite and cryogenic burns.

Inhalation : Acts as a simple asphyxiant.

Ingestion : Ingestion is not a normal route of exposure for gases Contact with cryogenic
liquid can cause frostbite and cryogenic burns.
Page
109
3. First aid measures

No action shall be taken involving any personal risk or without suitable training. If it is
suspected that fumes are still present, the rescuer should wear an appropriate mask or
selfcontained breathing apparatus. It may be dangerous to the person providing aid to give
mouth-tomouth resuscitation.

Eye contact: Check for and remove any contact lenses. Immediately flush eyes with plenty of
water for at least 15 minutes, occasionally lifting the upper and lower eyelids. Get medical
attention immediately.

Skin contact: In case of contact, immediately flush skin with plenty of water for at least 15
minutes while removing contaminated clothing and shoes. Wash clothing before reuse. Clean
shoes thoroughly before reuse. Get medical attention immediately.

Frostbite: Try to warm up the frozen tissues and seek medical attention.

Inhalation: Move exposed person to fresh air. If not breathing, if breathing is irregular or if
respiratory arrest occurs, provide artificial respiration or oxygen by trained personnel. Loosen
tight clothing such as a collar, tie, belt or waistband. Get medical attention immediately.

4. Fire-fighting measures

Flammability of the product : Flammable.

Auto-ignition temperature : 500 to 571C (932 to 1059.8F)

Flammable limits : Lower: 4% Upper: 76%

Fire hazards in the presence : Extremely flammable in the presence of following materials
of various substances oxidizing materials.

Fire-fighting media : Use an extinguishing agent suitable for the surrounding fire.

Page
110
Apply water from a safe distance to cool container and protect surrounding area. If involved in
fire, shut off flow immediately if it can be done without risk. Contains gas under pressure. In a
fire or if heated, a pressure increase will occur and the container may burst or explode.

5. Accidental release measures

Personal precautions: Immediately contact emergency personnel. Keep unnecessary personnel

away. Use suitable protective equipment. Shut off gas supply if this can be done safely. Isolate
area until gas has dispersed.

Environmental precautions: Avoid dispersal of spilled material and runoff and contact with
soil, waterways, drains and sewers.

Methods for cleaning up: Immediately contact emergency personnel. Stop leak if without risk.

6. Handling and storage

Handling: High pressure gas. Do not puncture or incinerate container. Use equipment rated for
cylinder pressure. Close valve after each use and when empty. Protect cylinders from physical
damage; do not drag, roll, slide, or drop. Uses a suitable hand truck for cylinder movement.
Never allow any unprotected part of the body to touch uninsulated pipes or vessels that contain
cryogenic liquids. Prevent entrapment of liquid in closed systems or piping without pressure
relief devices. Some materials may become brittle at low temperatures and will easily fracture.

Storage: Hydrogen Cylinders should be stored upright, with valve protection cap in place, and
firmly secured to prevent falling or being knocked over. Cylinder temperatures should not exceed
52 C (125 F).

Page
111
12. PLANT LOCATION

This chapter includes the place where the plant is decided to setup and also checking the
availabilities of all the facilities required for the plant.
The Methanol synthesis plant can be located in Dowleswaram near Rajahmundry because of its
favourable plant conditions given below:

12.1. RAW MATERIALS:

The main raw material, Natural gas is available from LNG Terminal which is set up by
Shell industries in agreement with the Kakinada Seaport limited (KSPL). It has the production
capacity of 5 million metric tonne per year so that it meets the demands of industries and house
hold gas-supply.

12.2. MARKETS:

Most of the methanol produced is mainly consumed in the present markets for the
formation of di-methyl ether and formaldehyde. Methanol produced here is sent to Aldehydes
India limited located in Haryana for the manufacture of formaldehyde. Otherwise the methanol
produced here is exported to countries like Saudi Arabia and Canada which are largest consumers
of methanol in the world.

12.3. ENERGY AVAILABILITY:

Andhra Pradesh Gas Power Corporation limited is located nearby and one more gas
power station is G.V.K. Gas power plant located at Jegurupadu was set up in the vicinity of
Rajahmundry City.

13.4. TRANSPORTATION FACILITITES:

Dowleswaram is 8 km from Rajahmundry City which is well connected by Rail and Road to
all states in India. The present Rajahmundry airport is being developed to have both domestic and
international flights. Air Cargo facilities are also catching up. The sea port facilities are excellent
as it is one of the major ports in India.

Page
112
12.5. CLIMATE:
The climate present here is slightly humid and cool. Severe conditions of temperature rise or
decline do not exist in this industrial area.

12.6. WATER SUPPLY:

The water requirement for the process plant will be 25.607 x 10 4 Kg/hr. Godavari waters are
being diverted to plant from Dowleswaram barrage. Then, there will not be any shortage for
water. Most of the water requirement for process cooling purposes sea water can be used.

12.7. WASTE DISPOSAL:

Sewage treatment plant (STP) is present in Rajahmundry near Dowleswaram. It purifies the
waste water from coolers and condensers and releases it to the nearby sea waters.

12.8. LABOR SUPPLY:

Skilled, semiskilled and unskilled labors are available in Rajahmundry. The City of Destiny is a
hub for primary, secondary and higher education.

12.9. TAXATION AND LEGAL RESTRICTIONS:

The tax rules and legalities are favourable to promote industries. The government gives good
subsidies on the raw materials provided for the manufacture of methanol.

12.10. SITE CHARECTERSTICS:

These are good for setting up an industry. The costs are moderate in and around Dowleswaram
area.

12.11. FLOOD AND FIRE PROTECTION:

No flood prone area. It is near to the industrial belt and the plant will be constructed taking
preventive measures to fire hazards and fail safe methods in any eventuality.

12.12. COMMUNITY:

All the factors are satisfied to promote community living. Rajahmundry area is a cultural
center also.

Page
113
13. PLANT LAYOUT

This chapter includes the layout of the whole plant which is shown in Figure 13.1, this
gives brief idea for understanding the overall process in the plant.

Fig.13.1. Methanol plant layout

Page
114
14. COST ESTIMATION

This chapter includes the detailed study of cost calculations done for the whole plant and find
the rate of return per annum based on methanol sales.

14.1. ESTIMATION OF PRESENT PLANT COST:

The cost estimate of the methanol plant for the production capacity of 3000 TPD according to
the rates and data available is Rs. 50*107 in the year.

Cost estimate of the plant = Rs. 50, 00, 00,000

The chemical engineering methanol plant cost index corresponding to year 1976 = 140

The chemical engineering methanol plant cost index corresponding to year 2010 = 605

The present value of the methanol plant can be estimated from both the indices as

Present value of plant = 50, 00, 00, 000 *(605/140) = Rs. 216.07*107

14.2. DETAILED COST ANALYSIS:

All the percentage ranges of calculation are obtained from the standard data book:
Plant design and economics of chemical engineering by Timmerhaus.

14.2.1. Direct costs:

Direct costs included all the below costs such as:

1. Purchased cost
2. Installation cost
3. Instrumentation and controls installation
4. Piping
5. Electrical installation
6. Building process and auxiliaries
7. Service facilities
8. Yard improvement
9. Land

Page
115
1. Purchased cost: It contains the equipment cost-15-40% of fixed capital investment

Assume 30% of the fixed capital investment = 0.3 * 216.07 * 107 = Rs. 64.82*107

2. Installation cost: It include insulation and painting costs-25-55% of purchased cost

Considering 40% of purchased cost = 0.4 * 64.82 * 107 = Rs. 25.928*107

3. Instrumentation and controls cost-6-30% of purchased cost

Considering 13% of purchased cost = 0.13 * 64.82 *107 = Rs. 8.4266*107

4. Piping installation cost-10-80% of purchased cost

Assume 45% of purchased cost = 0.45 * 64.82 * 107 = Rs. 29.169*107

5. Electrical cost-10-40% of purchased cost

Assume 15% of purchased cost = 0.15 * 64.82 * 107 = Rs. 9.723*107

6. Building process and auxiliaries-10-70% of purchased cost

Assume 40% of purchased cost = 0.4 * 64.82 * 107 = Rs. 25.928*107

7. Service facilities-30-80% of purchased cost

Assume 50% of purchased cost = 0.5 * 64.82 *107 = Rs. 32.41*107

8. Yard improvement-10-15% of purchased cost

Assume 12% of the purchased cost = 0.12 * 64.82 *107 = Rs. 7.7784*107

9. Land-4-8% of purchased cost

Assume 6% of purchased cost = 0.06 * 64.82 *107 = Rs. 3.88*107

All the costs calculated are tabulated in the Table.14.1. and the summation of all the costs give
the Total direct costs = Rs. 2.08*109

Table.14.1.Various direct costs

Type of cost Amount(Rs.107)
Page
116
Purchased cost 64.82
Installation Cost 25.928
Instrumentation and controls 8.4266
installation

Piping 29.169
Electrical installation 9.723
Building Process and 25.928
auxiliaries
Services facilities 32.41
Yard improvement 7.7784
Land 3.88
Total Direct costs 208

14.2.2. Indirect costs:

Indirect costs include the following costs such as:

1. Engineering supervision
2. Construction expenses
3. Contractor fee
4. Contingency plan

1. Engineering supervision-5-30% of direct cost

Assume 15% of direct costs = 0.15 *2.08 * 109 = Rs. 31.209*107

2. Construction expenses-6-30% of direct cost

Assume 10% of direct costs = 0.1 * 2.08 * 109 = Rs. 20.8*107

3. Contractor fee-2-7% of direct cost

Assume 4% of direct cost = 0.04 * 2.08 *109 = Rs. 8.32*107

4. Contingency costs-5-15% of present cost

Page
117
Assume 12% of present cost = 0.12 * 2.08 * 109 = Rs.24.96*107

Table.14.2. Various indirect costs

Type of cost Amount(Rs.107)
Engineering supervision 31.209
Construction expenses 20.8
Contractor fee 8.32
Contingency costs 24.96
Total indirect costs 85.289

Total indirect costs are calculated by the summation of all the costs present in Table.14.2. which
is = Rs.85.289*107

14.2.3. Fixed capital investments:

Fixed capital investments = Direct + Indirect costs = Rs. 2.93*109

14.2.4. Working capital:

Working capital = 10-20% of fixed capital investment

Assume 15% of fixed capital investment = 0.15 * 2.93 *109 = Rs. 43.993*107

14.2.5. Total capital investment:

Total capital investment = total fixed capital + working capital = Rs. 3.369*109

14.3. ESTIMATION OF MANUFACTURING COST:

14.3.1. Fixed costs:

There are mainly four types of fixed costs. They are:

1. Depreciation
2. Local taxes

3. Insurances
4. Rent

Page
118
1. Depreciation-10% of fixed capital investment for machinery and 3% of building value for

building = Rs. 30.07*107

2. Local taxes-3-4% of fixed capital investment

Assume 4% of fixed capital investment = Rs. 11.72*107

3. Insurances- 0.4-1% of fixed capital investment

Assume 0.6% of fixed capital investment = Rs. 1.758*107

4. Rent-8-12% of the rented land and buildings

Assume 10% of building value = Rs. 2.592*107

Fixed charges = 18% of product cost = Total fixed costs = Rs. 46.67*10 7 which is summation of
costs present in Table.14.3.

Total product cost = Rs. 2.56*109

Table.14.3. Various fixed costs

Type of cost Amount(Rs. 107)

Depreciation 30.07

Local taxes 11.72

Insurances 1.758

Rent 2.592

Total fixed costs 46.67

14.3.2. Direct production costs:

These direct production costs are mainly divided into following categories. They are:

1. Raw materials
Page
119
2. Operating labor
3. Direct supervisory and electrical labor
4. Utilities
5. Maintenance and repairs
6. Operating supplies
7. Laboratory charges
8. Patents and royalties

1. Raw materials-10-50% of total product cost

Assumed value, 30% of the total product cost = 0.3*2.56*109 = Rs. 76.8*107

2. Operating Labor-10-20% of the total product cost

Assume 15% of total product cost = 0.15*256*107 = Rs. 38.4*107

3. Direct supervisory and electrical labor-10-25% of operating labor

Assume 12% of operating labor = 0.12*38.4*107 = Rs. 4.608*107

4. Utilities-10-20% of total production cost

Assume 13% of total production cost = 0.13*256*107 = Rs. 33.28*107

5. Maintenance and repairs-2-10% of fixed capital investment

Assume 8% of fixed capital investment = 0.08*293*107 = Rs. 23.44*107

6. Operating supplies-10-20% of cost of maintenance and repairs

Assume 15% of maintenance and repairs = 0.15*23.44*107 = Rs. 3.516*107

7. Laboratory charges-0-20% of operating labor

Assume 15% of operating labor = 0.15*38.4*107 = Rs. 5.76*107

8. Patents and royalties-2-6% of total product cost

Assume 5% of total product cost = 0.05*256*107 = Rs. 12.8*107

Page
120
Direct production cost = Total direct production costs = Rs. 1.986*109 is given by the summation
of various costs present in Table.14.4.

Table.14.4. Various Direct production costs

Type of cost Amount(Rs. 107)
Raw materials 76.8
Operating labor 38.4
Direct supervisory and 4.608
electrical labor
Utilities 33.28
Maintenance and repairs 23.44
Operating supplies 3.516
Laboratory charges 5.76
Patents and royalties 12.8
Total direct product costs 198.6

14.3.3. Plant overhead costs:

Plant overhead costs-50-70% of operating labor+ direct supervisory + Maintenance cost

Assume 60% of total costs = Rs. 51.088*107

Total manufacturing cost = Fixed costs + Direct production costs + plant overhead costs

= 256*107 + 198.6*107 + 51.088*107

= Rs. 5.05*109

14.4. GENERAL EXPENSES:

General expenses include various costs in it. They are:

1. Administration costs
2. Distribution costs
3. Research and development costs
Page
121
1. Administration costs-40-60% of the operating labor cost

Assume 50% of the operating labor cost = Rs. 19.2*107

2. Distribution cost-2-20% of total product costs

Assume 10% of the total product cost = 0.1*256*107 = Rs. 25.6*107

3. Research and development cost-0-5% of total product cost

Assume 3% of the total product cost = 0.03*198.6*107 = Rs. 5.958*107

Total general expenses = Rs. 50.758*107 is given by the summation of various costs present in
Table.14.5.

Table.14.5. Various general expenses

Type of cost Amount(Rs. 107)
Administration costs 19.2
Distribution costs 25.6
Research and 5.958
development
Total general expenses 50.758

14.5. TOTAL PRODUCT COST:

Total product cost = Manufacturing cost + general expenses

= 5.05*109 + 50.728*107 = Rs. 5.557*109

14.5.1. Current selling price:

Cost of methanol = Rs. 27 per kg

Total selling price per annum = (3000*103) * 300 * 27

= Rs. 6.7*109 per annum

14.5.2. Gross earnings:

Page
122
Gross earnings = Total selling price Total product rate

= 6.7*109 5.557*109

= Rs. 1.143*109 per annum

14.5.3. Tax:

Assume the local tax rate as 40%

Tax on the gross earnings = 0.4*1.143*109

= Rs. 45.72*107

14.5.4. Net profits:

Net profits = Gross earnings Tax

= (114.3-45.72)*107

= Rs. 68.58*107

14.5.5. Rate of return:

Rate of return = Net profit/Fixed capital investments = 68.58*107/293*107

= 23.4%

APPENDIX

Calculation of heat capacity from standard data from the book-THE PROPERTIES OF
GASES AND LIQUIDS, 4th EDITION- ROBERT C.RYED, JOHN M.PRAUSNITZ &
BRUCE E.POLING.

The equation for the calculation of heat capacities of vapors of various compounds at different
temperatures is given by

Cp = a + b*T + c*T2 + d*T3

Page
123
Where Cp = isobaric heat capacity of a component in vapor form at temperature (T) J/mol0K

T = Temperature in kelvin 0K a, b, c, d = constants to calculate isobaric heat capacity, and

these are given in Table.Appendix-1 Tc = Critical temperature 0K

Pc = Critical pressure bar

Table.Appendix-1- Data for heat capacity calculation

0
Component Tc ( K ) Pc ( bar ) a b c d

CO 132.9 35.0 30.861 -1.285*10-2 27.89*10-6 -1.272*10-8

H2 33.2 13 27.143 92.738*10-4 -1.381*10-5 76.451*10-10

CO2 304.2 73.8 19.795 73.436*10-3 -5.602*10-5 17.153*10-9

CH3OH 512.6 81.0 21.152 70.924*10-3 25.87*10-6 -2.852*10-8

CH3OCH3 400 53.7 17.015 17.907*10-2 -5.233*10-5 -1.918*10-9

H2O 647.3 220.5 32.243 19.238*10-4 10.555*10-6 -3.596*10-9

CH4 190.6 46.0 19.251 52.726*10-3 11.974*10-6 -1.132*10-8

Prediction of overall column efficiency using OConnells Correlation

The overall column efficiency is correlated with the product of the relative volatility of the light
key component (relative to the heavy key) and the molar average viscosity of the feed, estimated
at the average column temperature. The correlation was based mainly on data obtained with
hydrocarbon systems, but includes some values for chlorinated solvents and water-alcohol
mixtures.

The method takes no account of the plate design parameters and includes only two physical
property variables. The correlation is given by the equation as below:

Page
124
Eo = 51 32.5*log (avg*avg)

The molar average liquid viscosity of the feed entering the purification column is avg = 0.101
mNs/m2

The average relative volatility is found from the equilibrium data at which the separation took
place as given in Table.Appendix-2

Table.Appendix-2-Equilibrium data at given conditions

x y
0.0084 0.103 13.55508
0.0258 0.227 11.08855
0.068 0.391 8.799672
0.137 0.568 8.282374
0.24 0.68 6.729167
0.48 0.79 4.075397
0.572 0.82 3.408702
0.741 0.906 3.368852
7.413472
avg

Substituting the calculated values in the above equation as Eo = 51 32.5*log (0.101*7.413472)

Eo = 60.2 nearly 60% of overall column efficiency.

BIBILIOGRAPHY

1. Methanol production from synthesis gas from petrochemical process technologies by

ID MALL.
2. M. Shahrokhi, G. R. B. (2005). "Modelling, simulation and control of a methanol
synthesis fixed-bed reactor." Chemical Engineering Science.
3. Froment G.F, K. M. Vanden Bussche (1996). "A Steady-State Kinetic Model for
Methanol Synthesis and the Water Gas Shift Reaction on a Commercial
Cu/ZnO/Al2O3 Catalyst."
4. Lee, S. (1990). Methanol Synthesis Technology, CRC Press.

Page
125
5. Wu-Hsun Cheng and Harold H. Kung Ed. (1994). Methanol Production and Use
Chemical Industries, CRC Press.
6. http://www.naturalgas.org
7. Control structure design for complete chemical plants. Computers and Chemical
Engineering Journal 28 (2004), 219 234.
8. Kim Aasberg-Pettersen, Charlotte Stub Nielsen, Lb Dybkjr and Jens Perregaard
(2009). "Large scale methanol synthesis from natural gas".
9. Technical information and Safe handling guide for methanol by Methanex, a
responsible care company.
10. Methanol infrastructure- D. Hart, M.A.Leach, R. Fouquet, P.J. Pearson, A.Bauen,
EnergyEnvironment Policy Research Group, TH Huxley School, Imperial College.
11. Sinnot, R. and Towler, G.: Chemical Engineering Design, 5th ed., Elsevier Ltd., UK,
2009
12. Sieve plate design from Chemical engineering Design by Coulson Richardson ,
volume-4,6th Edition.
13. G.H. Graaf, H. S., E.J. Stamhuis and A.A.C.M. Beenackers (1989). "Intra-Particle
Diffusion Limitations in Low-Pressure Methanol Synthesis." Chemical Engineering
Science.
14. Ogunnaike, B.A. (1995). A contemporary industrial perspective on process control
theory and practice. Dycord+ 95, 4th IFAC Symposium on Dynamics and Control of
Chemical Reactors, Distillation Columns, and Batch Processes.

Page
126