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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
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).
PROCESSES TO MANUFACTURE
METHANOL
There are a number of routes for production of methanol. Detailed description is
discussed one by one.
[1] FROM COAL
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.
1)heavy ends
and sulphur
removal
4)Methanol
reactor
2)Steam
reformer
3)Water shift
reactor
5)Methanol
separation and
purification
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
Methanation
4. 2 CH3OH CH3OCH3 + H2 O
Ether formation
5. CO + H2 O CO2 + H2
6. CH4 + H2 O CO + 3H2
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.
S2 =0.0318
S3=0.0956
= 3388.035 kmol/h
= 120.8113 kmol/h
Out of the total amount of methanol exiting the reactor 5% dimerizes into ether
2 CH3OH CH3OCH3 + H2 O
Methanol dimerized
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
=4840.05 kmol/h
= 14520.15 kmol/h
= 4840.05 kmol/h
= 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
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
Flowrate
4840.05kmol/h
4840.05kmol/h
Outflow
Components
Carbon monoxide
Hydrogen
Flowrate kmol/h
4840.05kmol/h
14520.15kmol/h
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
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
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
-110.35Kj/mol
2. CO + 3H2 CH4 + H2 O
-209Kj/mol
-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
997.05 GJ/h
484.74GJ/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
37KJ/mol
35.80 GJ/mol
6.27kg/m3
29003.47 m3/h
=
=
13570.58 m3/h
46.071 GJ/h
input
CO
H
CO2
CO2
CH4
CH3OH
H20
H2
HE bottom duty
28
2
44
44
16
32.04
18
2
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
8.005 x 108
Methanol kmol/h
3218.6
Dimethyl ether
0.169
water
205.4
Condenser Duty
Reboiler Duty
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
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
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
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
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
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
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.
REFRENCES
1. http://books.google.co.in/books?id=Qdnc7uKaH8C&pg=PA15&lpg=PA15&dq=ICI+low+pressure+methanol+p
rocess&source=bl&ots=tTNAgCknvt&sig=PW_lNWSq4IzfevoR2
UDMSBfoI9A&hl=en&ei=NT5OTZvvG4n2gAfyqtFC&sa=X&oi
=book_result&ct=result&redir_esc=y#v=onepage&q=quench&f=f
alse
2. http://www.topsoe.com/business_areas/gasification_based/~/media
/PDF%20files/Methanol/Topsoe_methanol_coal_gasification_pape
r.ashx
3. http://www.engineeringtoolbox.com/methanol-propertiesd_1209.html
4. http://www.sbioinformatics.com/design_thesis/Methonal/Methanol
_Material-2520Balance.pdf
5. http://www.lindeengineering.com/en/process_plants/hydrogen_and_synthesis_gas_
plants/gas_products/methanol/index.html#
6. http://www.researchandmarkets.com/reports/2168712/methanol_in
dustry_in_india