Project Plant Design for

manufacturing of methanol
BITS PILANI K.K. BIRLA GOA CAMPUS
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A REPORT ON

MANUFACTURING OF METHANOL

UNDERTAKEN BY
NEH VIVEK KOVALE

2010A1PS418G

ANIT AGARWAL

2010A1PS408G

On partial fulfillment of the course

SPECIAL PROJECTS CHE C491
INSTRUCTOR INCHARGE : Dr. SRINIVAS KRISHNASWAMY
Under the guidance of
Ms. Parul Sahu

Department of Chemical Engineering

BITS PILANI K.K BIRLA GOA CAMPUS
Jan-May 2014

TABLE OF CONTENTS
Title

Page No.

ABSTRACT.3
INTRODUCTION4-7
AVAILABLE PROCESSES TO MANUFACTURE METHANOL8-13
PROCESS DESCRIPTION FOR NATURAL GAS ROUTE14
MATERIAL BALANCE.15-21
ENERGY BALANCE..22-28
REFRENCES..29

ABSTRACT
This project report begins with a brief discussion about the history of
methanol manufacture, its characteristics & applications with an
overview of the economic aspects. The next part of report introduces
the study of the different process routes for the manufacture of
methanol and the selection of a process depending upon the
advantages and flexibilities it provides. The selected manufacturing
process of methanol used natural gas as feed-stock. The report
progresses with detailed material and energy balance for all the
equipments involved in the process. The result obtained from the
balances can be further used for designing the equipments of interest
and evaluation of material, energy and cost involved.

INTRODUCTION
Methanol also called wood alcohol is the simplest known alcohol. It was earlier
manufactured by destructive distillation of wood thus it is also called wood
alcohol. It finds direct applications as denaturant, antifreeze, solvent and used in
fuel blending. Apart from that, it is a primary raw material for intermediate
chemicals like formaldehyde, dimethyl ether, low prices ethylene and biodiesels
through transesterification.

Historical Development
Methanol was first isolated in 1661 by Robert Boyle, when he produced it via the
distillation of buxus (boxwood). Its elemental composition was first determined in
1834 by Jean-Baptiste Dumas and Eugene Peligot. In 1923, the German
chemists Alwin Mittasch and Mathias Pier, working for BASF, developed a means
to convert synthesis gas into methanol and today it one of the most heavily
traded chemicals today with a total demand of roughly 27 to 29 million metric
tons.
Maximum amount of methanol today is manufactured by synthesis gas reforming
using a catalyst (mixed Al Zn Cu oxide) The synthesis gas here is manufactured
using several carbon sources like biomass , coal , natural gas.
In this report we have provided the brief description of the three main routes of
methanol manufacturing that is through coal, bio-mass, natural gas used as
source of natural gas. Considering the advantages and disadvantages of all the
three processes we conclude that natural gas route is the most suitable for
manufacturing of methanol.
A basis of 2500 tons of methanol-production (99% by mass) per day has been
chosen. The material and energy balance were done for the entire plant and the
each and individual components separately.

Properties
Methanol (CH3OH) is a simple one-carbon alcohol that is a colorless and tasteless
liquid with a faint odor. Other names are Methyl-alcohol and Wood-alcohol. It is
most commonly produced from natural gas but can also be derived from
renewable bio-feed stocks and from coal through gasification.
It is a light, flammable, colorless liquid which is volatile and has a distinct odor
whose Boiling point: 67.4 C, Melting point: -97.6 C. It is a polar liquid at room
temperature.

Applications
Methanol is a basic building block and a raw material for many derivatives in the
chemical industry. It is used to produce formaldehyde, acetic acid and a variety of
other chemical intermediates. These derivatives are ultimately used in the
manufacture of countless products that we find in our everyday lives, including:
resins, adhesives, paints, inks, foams, silicones, plastic bottles, polyester, solvents
and windshield washer fluid. A significant amount of methanol is also used to
make MTBE (methyl tertiary butyl ether), an additive used in cleaner burning
gasoline. In the latter years DME (di methyl ether) has emerged as an alternative
clean burning fuel. Methanol is also widely considered to be a potential
hydrogen carrier for many future fuel cell applications.
The methanol
economy
is
a
suggested
future economy in
which methanol replaces fossil fuels as a means of energy storage, ground
transportation fuel, and raw material for synthetic hydrocarbons and their
products. It offers an alternative to the proposed hydrogen economy or ethanol
economy.
Methanol is a fuel for heat engines and fuel cells. Due to its high octane rating it
can be used directly as a fuel in flex-fuel cars (including hybrid and plug-in
hybrid vehicles) using existing internal combustion engines (ICE). Methanol can
also be used as a fuel in fuel cells, either directly in Direct Methanol Fuel
Cells (DMFC) or indirectly (after conversion into hydrogen by reforming).

Methanol is a liquid under normal conditions, allowing it to be stored,

transported and dispensed easily, much like gasoline and diesel fuel is currently. It
can also be readily transformed by dehydration into dimethyl ether, a diesel fuel
substitute with a cetane number of 55.
Methanol can be efficiently produced from a wide variety of sources including
still-abundant fossil fuels (natural gas, coal, oil shale, tar sands, etc.), but also
agricultural products and municipal waste, wood and varied biomass.
Methanol may be viewed as a compact way of storing hydrogen. One m3 of
methanol at ambient pressure and temperature contains 1660 Nm3 (normal cubic
meters) of hydrogen gas (H2). This may be compared to liquid hydrogen where
one m3 of liquid hydrogen (LH2) at -253C contains only 788 Nm3 of hydrogen gas.
The commercial AA grade methanol contained 1% water by mass rest of it is
considered to be methanol.

PROCESSES TO MANUFACTURE
METHANOL
There are a number of routes for production of methanol. Detailed description is
discussed one by one.
[1] FROM COAL

Figure No. 1: Block diagram representation for the process

First, coal is pre-processed by methods such as crushing, sizing and drying
to prepare it for the coal gasification process. During the coal conversion process,
the coal is decomposed in a high pressure and temperature using steam and an
oxygen supply, represented by the following equation.
The coal is decomposed using gasifier the example of a common gasifier used in
industry is a lurgi gasifier shown below:

where the stoichiometry of the reaction is depended on coal composition. The

result is synthesis gas which then proceeds through an acid gas removal step.
During acid gas removal, the hydrogen sulfide and carbon dioxide are recovered
in a solvent absorption process. Then, the H2S enters a Claus unit where is it
converted into elemental sulfur according to the following equation

Next, the synthesis gas must be prepared by going through a water-gas

shift reactor to achieve the desired syngas ratio (H:CO) of 2:1. The water-gas shift
reaction is a commonly used method for further enhancing the yield of hydrogen.
The governing equation for water-gas shift reactor is as follows

The subsequent reactions for manufacturing of methanol remain identical for the
two processes in which a methanol reactor is used to convert the synthesis gas
coming out of the water-gas shift reactors into the desired methanol product. The
reactor has a (Cu-Zn-Al oxide based) in zones the reactor is quench cooled in
which the relatively cooler feed enter the outer shell and helps keep reactor
temperature low along with heat exchangers that give out heat to maintain the
reactor at 550K.
The methane, hydrogen and carbon dioxide generated are removed and the
hydrogen obtained is recycled where as the ether impurities are removed via the
ether column operating at about 5bar pressure.

[2] FROM NATURAL GAS

1)heavy ends
and sulphur
removal

4)Methanol
reactor

2)Steam
reformer

3)Water shift
reactor

5)Methanol
separation and
purification

Figure No. 2: Block flow diagram for natural gas route

The process is consists of following steps:
Natural gas pretreatment
The natural gas contains about 94% methane that is our desired raw material
because higher hydrocarbons have a tendency to block the reformer tubes and
moreover it is important to treat natural gas to remove sulphur content present
in it.
Methane reforming
Steam methane reforming uses an external source of hot gas to heat tubes in
which a catalytic reaction takes place that converts steam and lighter
hydrocarbons such as methane into hydrogen and carbon monoxide, using
heavier hydrocarbon feed chokes up the reformer tubes and fouls the catalyst the
temperature of the reformer is about 1100K the steam of gas exiting the reformer
are used to heat up the feed to the reformer rest of the heat is rejected via a heat
exchanger.

Water shift reactor

This reactor brings the CO:H2 ratio to about 1:4 , because the higher CO partial
pressure causes the fouling of the catalysts in the methanol reactor the CO
content is reduced in this reactor and simultaneously the hydrogen content is
increased via the water gas shift reaction .

Methanol reactor
The methanol reactor used is a quench type reaction where the catalyst used is
(Cu-Zn-Al oxide based) it is placed in zones the cold feed enters longitudinally
along the reactor length the heat exchangers and the cold feed are used to keep
the reactor temperature in control.
The feed CO to hydrogen ratio is carefully controlled because increase in CO
concentration might cause catalyst poisoning via formation of higher organic
compounds thus it is advisable to maintain the CO:H2 ratio between 1:3 -4.Apart
from preventing catalyst poisoning the extra Hydrogen also helps in carrying
away the hot catalyst bed heat.
The reactor has an inner and outer shell the cold feed first enters the outer shell
and then carries away a part of the heat generated before finally coming in
contact with the zoned catalysts.

Purification
The purification process for this process is the same as that of the previous
described coal based process
The process that was selected was the natural gas process
Advantages of natural gas process
The ease of handling of natural gas
In other raw materials we have to deal with higher hydrocarbons and other
poisons that poison the catalysts
The problem of residue is not present in case of solid carbon sources like
biomass and coal

PROCESS DESCRIPTION
The feed to the process is natural gas that contains on an average 94% by volume
of methane the feed enters at ambient temperature at 25bar pressure. The
heavier components and sulphur content of the feed gas is removed to avoid
fouling of catalyst. The steam for the same enters at 540K into the steam
reformer at 25 bar.
The reformer feed is preheated using heat rejected by reformer exiting gases the
temperature of the feed is raised to 780K .The reformer has a nickel catalyst
present in form of tubes the temperature of the reactor is around 1100K .External
heat has to be supplied here since the steam reforming reaction here is
endothermic.
The exit gas from the reformer has a CO:H2 ratio of approx 1:2 to raise the
hydrogen concentration to a CO:H2 ratio of 1:3 we add steam as limiting reagent
in water shift reactor to obtain the desired ratio. The water shift reaction is an
exothermic reaction and thus the heat is removed via a heat exchanger the exit
stream of the reactor is around 400K.
The exit gasses from the shift reactor are compressed to about 50bar using a
compressor and fed into the methanol reactor at around 530K .The gas exiting the
reformer is cooled down and sent to an ether tower to remove ether and excess
water from methanol product .

MASS BALANCE
For mass balance we assume plant capacity to be 2500 Tons per day of 99% by
weight methanol product
The reactions involved in the entire process are
1. CO + 2H2 CH3OH

Methanol formation

2. CO + 3H2 CH4 + H2 O

Methanation

3. 2CO + 2H2 CH4 + CO2

Methanation

4. 2 CH3OH CH3OCH3 + H2 O

Ether formation

5. CO + H2 O CO2 + H2

Water gas shift reaction

6. CH4 + H2 O CO + 3H2

Steam methane reforming

In this process we back calculate the amount of natural gas required from the
amount of methanol produced in the plant per day.
In the following material and energy balances we have taken the entire feed
entering the reformer to be pure methane. We also neglect the side reactions in
the reformer because of their lower K value as compared to steam reforming
reaction.
In the stream exiting the methanol reactor we assume that 5% of the methanol
dimerizes into ether we take into account the amount of methanol lost to ether
while making our feed amount calculations.
We have assumed that the only reactions happening in the methanol reactor are
methanol formation reactions and methanation reactions.
Apart from that 94% of the feed by volume is taken to be methane rest of it is
either higher hydrocarbons or sulphur containing organic compounds.

Amount of methanol product to be produced = 2500 tons per day

Accounting for 99% purity by mass amount of pure methanol produced
= 0.99 x 2500 = 2475 TPD
Thus kmols of methanol produced per hour = 3218.633 kmol/h
5% of feed exiting the reactor is converted into ether so the amount of methanol
that exits the reactor = 3218.633/0.95 = 3388.035 kmol/h
For the following reactions the selectivities are taken under consideration:
CO + 2H2 CH3OH
S1 = 0.875
CO + 3H2 CH4 + H2 O

S2 =0.0318

2CO + 2H2 CH4 + CO2

S3=0.0956

Moles of methanol formed = 3388.035 kmol/h

So amount of CO consumed in all reactions can be calculated out by = Moles of
methanol formed/Selectivity of the methanol formation reaction
=3388.035/0.875
=3872.04 kmol/h
Total hydrogen consumed in the process = 7501.697 kmol/h
But since we require CO is to hydrogen ratio as 1:4 unused hydrogen
= (amount of CO used) x 4 - 7501.697 kmol/h = 7986.462 kmol/h
This unused hydrogen may be extracted via membrane of PSA process and be
recycled or might sold, since hydrogen has a commercial value.

CO consume by first reaction

= 3388.035 kmol/h

The remaining CO is used up by methanation reactions = 484.005 kmol/h

The amount consumed by reaction 2

= 120.8113 kmol/h

The amount consumed by reaction 3

=363. 1937 kmol/h

Out of the total amount of methanol exiting the reactor 5% dimerizes into ether
2 CH3OH CH3OCH3 + H2 O
Methanol dimerized

0.05 * 3388.035 kmol/h = 169.4017 kmol/h

Water formed in the process

84.7 kmol/h

In the water gas shift reactor the feed syngas has a molar CO:H2 ratio of about 1:3
But the gas exiting has a ratio of 1:4
In the water gas shift reaction 1 mole of steam converts one mole of CO and
produces 1 mole of hydrogen gas this number of moles of steam added are
calculated by

3872.04 X 1

15488.16 X 3
The number of moles of hydrogen added comes out to be

=968.01 kmol/h

Thus moles of CO entering

=4840.05 kmol/h

Moles of hydrogen entering reactor

= 14520.15 kmol/h

In steam reforming the principle reaction is

CH4 + H2 O CO + 3H2
So moles of CO produced = moles of methane consumed = moles of water
consumed
Thus
Methane entering reformer

= 4840.05 kmol/h

Steam entering reformer

= 4840.05 kmol/h

Natural gas is 94% by volume of methane , amount of natural gas feed required
=4840.05/0.94
=5148.989 kmol/hr
The average molecular weight of natural gas

= 19 g/Mol

Weight of natural gas required

=2347.9 Tons Per Day

Mass of steam required

=2090.9 Tons perDay

Overall component balance is shown below:

For component 1(heavy ends removal)

Inflow
Component
Natural gas

Flowrate in kmol/h
5148.9kmol/h

Outflow : Stream A
Component
Methane
Heavy ends and sulphur content

Flowrate in kmol/h
4840.05kmol/h
344.85kmol/h

For Component 2 (steam reformer)

Inflow
Component
Methane
Steam

Flowrate
4840.05kmol/h
4840.05kmol/h

Outflow
Components
Carbon monoxide
Hydrogen

Flowrate kmol/h
4840.05kmol/h
14520.15kmol/h

For component 3 (water gas shift reaction)

Inflow
Components
Carbon monoxide
Hydrogen
Steam(water)

Flowrate kmol/h
4840.05kmol/h
14520.15kmol/h
968.01kmol/h

Outflow stream
Component
Carbon monoxide
Hydrogen
Carbon Dioxide

Flowrate kmol/h
3872.04 kmol/hr
15488.16 kmol/hr
968.01 kmol/hr

For component 4(methanol reactor)

Inflow
Component
Carbon monoxide
Hydrogen

Flowrate kmol/h
3872.04 kmol/hr
15488.16 kmol/hr

Outflow
Components
Methanol
Carbon dioxide
Methane
Hydrogen
Water

Flowrate kmol/h
3388.035kmol/h
181.5968 kmol/h
302.4081 kmol/h
7986.462 kmol/h
120.8113kmol/h

For component 5 (purification section)

Inflow stream
Components
Methanol
Carbon dioxide
Methane
Hydrogen
Water

Flowrate
3388.035kmol/h
181.5968 kmol/h
302.4081 kmol/h
7986.462 kmol/h
120.8113kmol/h

Outflow stream
Components
Methanol
DME
Hydrogen
Carbon dioxide
Water
Methane

Flowrate
3218.633kmol/h
84.7kmol/h
7986.462 kmol/h
181.5968 kmol/h
205.41 kmol/h
302.4081 kmol/h

ENERGY BALANCE

STREAM No
1
2
3
5
6
8
11
12

TEMP K
298.15
780
1173
623
404.6
550
292
385.53

The reference temperature for the calculations is taken to be 298.15 K. The

energy balance is done directly from the reformed methane feed, that is the
natural gas reforming section hasnt been included in energy balance
considerations.
Same as in case of energy balance the heat of reactions of reactions with lower K
values has been neglected and the energy considerations have been taken only
for a given set of reactions.

The reactions and their heats are mentioned below

1. CO + 2H2 CH3OH

-110.35Kj/mol

2. CO + 3H2 CH4 + H2 O

-209Kj/mol

3. 2CO + 2H2 CH4 + CO2

-252kj/mol

4. 2 CH3OH CH3OCH3 + H2 O

-184kj/mol

5. CO + H2 O CO2 + H2

-37 Kj/mol

6. CH4 + H2 O CO + 3H2

+206kj/mol

As you can see from the above reactions the only reaction that requires the
supply of heat is the steam methane reforming reaction, all the other reactions
produce heat being exothermic and Heat exchanges have to be deployed for
removal of this heat.
The feed enters at 25bar pressure and at 298.15K so the by the reference
temperature taken
mCpdT = 0
the steam enters at 540K so energy entering along with steam at 25bar pressure
is
= 60.91GJ/h
The methane and steam feed is preheated to about 780K heat consumed in that
is
=83.3 GJ/h
Heat consumed per mole of methane reformed is

206KJ/mol

Heat consumed by methane reforming is

997.05 GJ/h

Total energy carried away by CO and H2 leaving reformer =

484.74GJ/h

So amount of heat input required is

= Ho/p - Hi/p - Hsteam + Hreaction
=1337.56 GJ/h

The total heat lost when the exit gases from the reformer are cooled to 623K
=

304.75 GJ/h

The feed is preheated using this heat so the amount of heat lost via the heat
exchanger
=
304.75 83.3GJ/h
=

221.45GJ/h

179.9GJ/h

The heat entering the shift reactor with CO and H2 feed

Heat generated by reaction per mole CO

37KJ/mol

Heat generated by the moles of CO reacted

35.80 GJ/mol

Temperature of reactant effluent stream is determined by

=(Hinput stream + Hreaction)/mCp +298.15 K
=404.6 K
For the stream the average density at 23.5 bar

6.27kg/m3

Volume of inflow into the compressor is

29003.47 m3/h

Volume of outflow at 50bar

So work done by adiabatic compressor

=
=

13570.58 m3/h

46.071 GJ/h

For methanol reactor

input
CO
H
CO2

Flow rate Kmol/h

Mwt
3872.4
15448.16
967.65

CO2
CH4
CH3OH
H20
H2

Flow rate Kmol/h

Mwt
181.5968
302.4081
3388.035
120.8113
7986.462
11979.3132

reactor heat produced

r1
r2
r3

HE bottom duty

28
2
44

44
16
32.04
18
2

Mass flow kg/h

temp
Cp KJ/kgK
mcpdt
108427.2
404.66
1.02
11779552.69
30896.32
404.66
14.32
47123784.06
42576.6
404.66
0.844
3827399.614
62730736.37
Mass flow kg/h
Cp
mCp
TK
mCpT KJ/h
7990.2592
0.844 6743.778765
533
1583776.443
4838.5296
2.226 10770.56689
533
2529467.634
108552.6414
1.93 209506.5979
533
49202624.52
2174.6034
2.18 4740.635412
533
1113338.227
15972.924
14.32 228732.2717
533
53717774
460493.8506
108146980.8

Reaction heat KJ/kmol Kmol

KJ/h
110352
3388.035
373876438.3
209000
120.8113
25249561.7
252054
90.7984
22886099.91
422012099.9
376595855.5

The heat lost to heat exchangers present inbuilt the reactor to maintain reactor
temperature at about 550K is
=
376.59 GJ/h
The ether, water and methanol is separated in a distillation column the energy
balance for which has been carried out using CHEMCAD.
Energy balance for 1) distillate 2) bottom product 3) for the ether tower

Temp K

292.4

Pressure bar

enthalpy KJ/h

1.72 x 107

Methanol kmol/h

0.0321866

Dimethyl Ether

84.5306

water

4.860441 x 10-8

Temp K

385.53

Pressure bar

Enthalpy exiting Kj/h

8.005 x 108

Methanol kmol/h

3218.6

Dimethyl ether

0.169

water

205.4

Condenser Duty

9.5 x 106 KJ/h

Reboiler Duty

1.256 x 108 KJ/h

For stream 1
Components
CH4
H2O

Flow
kmol/h
4840.05
4840.05

Mol wt

Cp KJ/Kg K

dT ,K

mCpdT

16
18

2.226
2.18

0
0

0
0
0

Inlet Steam Methane Reformer

Components

Flow kmol/h

Mol wt

Cp KJ/Kg K

dT ,K

CH4
H2O

4840.05
4840.05

16
18

2.226
2.18

780
780

mCpdT
GJ/h
83.3
91.51

Outlet Steam Methane Reformer

Components
H2
CO

Flow
kmol/h
14520.15
4840.05

Mol wt

Cp KJ/Kg K

dT ,K

2
28

14.32
1.06

874.85
874.85

mCpdT
GJ/h
363.81
123.67
489.48

Inlet Water Gas shift reactor

Components
H2
CO

Flow
kmol/h
14520.15
4840.05

Mol wt

Cp KJ/Kg K

dT ,K

2
28

14.32
1.06

324.85
324.85

mCpdT
GJ/h
135.09
46.67
181.75

Outlet Water Gas Shift Reactor

Components
CO
H2
CO2

Flow
Kmol/h
3872.04
15488.16
968.01

Mol Wt
28
2
44

Cp
KJ/Kgk
1.06
14.32
.833

dt,K

mCpdT,
GJ/h
43.6
168.2
13.46
225.26

379.35
379.35
379.35

Inlet methanol reactor

Components
CO
H2
CO2

Flow
Kmol/h
3872.4
15448.16
968.01

Mol Wt
28
2
44

Cp
KJ/KgK
1.02
14.32
0.833

dT , K
225
225
225

mCpdT ,
GJ/h
24.88
99.55
8.99
132.38

Outlet methanol reactor

Components
CH4
H2
CO2
CH3OH
H2O

Flow
Kmol/h
302.408
7986.4
181.59
3388.03
120.811

Mol Wt

Cp KJ/KgK

dT , K

16
2
44
32
18

2.226
14.32
0.833
1.93
2.18

371.85
371.85
371.85
371.85
371.85

mCpdT ,
GJ/h
171.1

The parameters for the remaining 2 streams have been evaluated using
CHEMCAD.

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alse
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