2. Methanol( CH3OH)(Wood alcohol)
● Methanol(methyl alcohol) is a light, volatile,
colourless, flammable liquid with a distinctive
alcoholic odour.
● Methanol is primarily used as an industrial
solvent to help create inks, resins, adhesives,
and dyes.
● Solvent in the manufacture of important
pharmaceutical ingredients.
● Around 98 million tonnes (Mt) are produced
per annum
Methanol
3. Methanol Synthesis
● Reactions-
CO + 2 H2 <—----->CH3OH ∆H = −90.8 kJ mol−1
CO2+3H2<----->CH3OH+H2O ∆H298K = −49.5 kJ mol−1
CO2 + H2 <----->CO + H2O H298K = 41.2 kJ mol−1
● Heat of the Reaction= -49KJ/Kmol
● Equilibrium Reaction
● Also Gas Shift Reaction
4. ● Methanol synthesis is the second largest present user of hydrogen, after ammonia
synthesis.
● Useful for consuming CO2.
● A highly selective Cu/ZnO catalyst is used for this purpose. The catalyst is enriched with
ZrO2
● Methanol can be produced from natural gas, coal and renewable sources such as
municipal waste, biomass and recycled carbon dioxide
● Mainly methanol is produced on industrial scale from synthesis gas “syngas”.
● Direct CO2 to Methanol Synthesis.
5. Block flow diagram showing the different origins of syngas for the conventional process compared to
the CRI process starting from CO2 pointing out the energy intensive reforming process in the former.
10. Econimical efficiency
● The main cost of methanol production, in both cases, is hydrogen production.
● Hydrogen is produced via water electrolysis.
● Huge amount of electricity is needed for that purpose.
● In order to calculate the net present value, annual profits (Ap) for both processes
are calculated. Ap =Pm +Po - Ot -Mt,
● The calculated annual profits for the two-step and the direct methanol syntheses
are 12.02 million $ and 14.56 million $.
● Direct methanol synthesis is more profitable.
11. Energy efficiencies
● Direct methanol synthesis process is more thermodynamically
efficient.
● Operating temperatures are moderated during the direct methanol
process. in contrast to two-step synthesis using a high-temperature
RWGS reactor.
● Significant amount of hydrogen needed for the direct methanol
synthesis.
● Overall it can be concluded that direct synthesis has higher economical
and energetic efficiency.
12. Carbondioxide And Hydrogen Capture
● Chemical absorption from the flue gases of
a thermal power plant is used to capture
the CO2.
● Utilizing carbon-free electricity, hydrogen
is produced by water electrolysis.
● Captured CO2 is used for the production of
a marketable product, its capture and sale
could become a profitable business.
● Great economic and environmental
interests. Thermal Power Plant
13. Material Balance: With Chemical Reaction
Methanol is produced in the reaction of carbon dioxide and hydrogen:
CO2 + 3H2 → CH3OH + H20
● Hydrogen, carbon dioxide, and 0.400 mole % inerts.
● The reactor effluent passes to a condenser that removes essentially all of the methanol and
water formed and none of the reactants or inerts.
● The latter substances are recycled to the reactor.
● Purge stream
● The feed to the reactor contains 28.0 mole % CO2, 70.0 mole % H2, and 2.00 mole % inerts.
● The single-pass conversion of hydrogen is 60.0%.
15. Basis: 100 mol of gross feed
Assumption: Steady-state process
1. Solve for n2
n2= (0.4)(0.7) (100 mol)
n2= 28 mol
2. Elemental balance at the reactor
C: 100mol(0.28)(1)=n1(1)=n3(1)
H: 100mol(0.70) (2)=28mol(2)+n3(4)+n4(2)
O: 100mol(0.28)(2)=n1(2)+n3(1)+n4(1)
Solving through systems of equations
n1 = 14 mol n3= 14mol n4= 14mol
3. Mole balance at the condenser
nGP= n1 + n2 + n3 + n4 + 2 mol inerts=
14+28+14+14+2= 72 mol
nGP= n5 + n3 + n4
n5= nGP - n3 - n4 = 44 mol
Material Balance: With Chemical Reaction
16. 4. Compound balances at the
condenser
CH3OH: n3= n3 + 0 = 14 mol
CO2: n1= X5c(44)
H2: X5h (44)
Mole fraction in the recycle and purge
stream
X(CO2) = 0.32 X(H2) = 0.64
X(inerts) = 0.04
5. Mole balance at the splitting and
mixing point and compound balance
n5= nR + nP
44= nR + nP (splitting point)
n0 +nR= 100 (mixing point)
CO2: Xocn0+0.318nR= 100 (0.28)
Inert: 0.004n0 + 0.046nR= 2
nP=44- nR
n0= 61.9 mol nR= 38.10 mol
nP= 5.90 mol
Material Balance: With Chemical Reaction
17. 6. Solve for the composition of the fresh feed using equations from v.
x0c= [100(0.38)-0.318(38.10)]/[61.90] = 0.26
X(CO2) = 0.26
X(H2)= 0.736
X(inert) = 0.004
Material Balance: With Chemical Reaction
18. Manual Solutions
Material Balance: With Chemical Reaction
Molar Flow
Rate(mol/hr)
CO2 H2 Inerts
Feed 61.9 0.26 0.74 0.004
Recycle 38.10 0.32 0.64 0.04
Purge 5.90 0.32 0.64 0.04
25. Market Analysis
● The global methanol market size was USD 28.74
billion in 2021.
● The market is expected to grow from USD 28.74
billion to USD 39.18 billion until 2028 at a
Compound Annual Growth Rate (CAGR) of 4.5%
● Methanex Corporation, Southern Chemical
Corporation, SABIC, Zagros Petroleum are the
top players.
● The largest consumer of methanol is anticipated
to be East Asia.
26. CAPEX
A plant carrying 10,344 kmol/day of CO2 at 25
C and 1 bar.
● Land
● MS reaction system - 1,960,486 USD
● WGS reaction system- 2,843,921 USD
● Indirect costs include construction
expenses, engineering and supervision
costs are 70%.
Components Price/unit (USD)
Heat Exchanger 900
Stripper 12000
Adiabatic multi-bed
quench catalytic reactor
25000
Mixer 50000
Compressor 1000
Pressure Valves 100
27. OPEX
Labor Costs
Raw Materials and Utilities-
● CO2 price: 35 USD/Mg CO2 ; H2O price: 1 USD/Mg.
Consumption/Year Value/Year
Quantity Units Total cost (USD) USD/kgMeOH
Electricity 236,146,400 kWh 14,168,784 0.17
Low pressure steam 1,859,906 Mg 19,529,017 0.24
High pressure steam 32,824 Mg 475,942 0.24
Cooling water 103,269,680 m3 3,273,649 0.45
Total utility consumption and costs
28. Conclusion
● Methanol is a useful industrial product which can be used as a clean fuel or as
solvent to help create inks, dyes pharmaceutical ingredients etc.
● It can capture CO2 and reduce the greenhouse effect.
● BHEL has built India's first coal to methanol plant- through the gasification
route conversion of high-ash Indian coal to methanol is the first-of-its-kind
technology demonstration in India.
● Large amount of methanol is getting produced every year . The market is
expected to grow at a CAGR of 4.5%
29. Future Scope
● Methanol production from CO2 using solar-thermal energy- The system make use of
concentrated solar energy in a thermochemical reactor for the conversion of CO2
into CO. Also water gas shift to produce syngas (CO and H2) to feed a methanol
synthesis reactor
● Amine based CO2 separation system- Both the WGS and MS and the reactors
perform optimally at a specific CO2/CO molar ratio. We can adjust these ratios using
an amine-based CO2 separation system. It uses aq monoethanolamine to absorb
CO2 in different columns.
30. References
● Methanol, Wikipidea, https://en.m.wikipedia.org/wiki/Methanol
● Dana S. Marlin*, Emeric Sarron and Ómar Sigurbjörnsson, Process Advantages of
Direct CO2 to Methanol Synthesis, 2028.
https://www.frontiersin.org/articles/10.3389/fchem.2018.00446/full
● Unifolks 2022. https://www.unifolks.com/questions/methanol-ch3oh-is-produced-
in-the-reaction-of-carbon-dioxide-and-hydrogen-via-t-3276343.html
● Harshad P Pandya, Independent Consultant,Upgrading Methanol plants for Increase
in Capacity and Energy Efficiency,2022. https://ammoniaknowhow.com/upgrading-
methanol-plants-increase-capacity-energy-efficiency/
