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Methanol from synthesis gas

Applications of methanol
Product (in w.%) 1988 1996 2005
Formaldehyde 39 35 38
Acetic acid 6 7 11
Methyl halides 7 7 7
MTBE 12 27 20
Dimethyl terephthalate 3 2 2
Methyl amines 4 4 4
Methyl methacrylate 3 3 4
Solvents 9 4 4
Others 17 11 13
Sum (in mio t/a) 17,3 24,3 32,1
Methanol from syngas
CO + 2H2 ⇌ CH3OH (ΔH = -92 kJ/mol)

CO2 + 3H2 ⇌ CH3OH + H2O (ΔH = -50 kJ/mol)


CO + H2O ⇌ CO2 + H2
(ΔH = -41 kJ/mol)

• Several side-products that are


thermodynamically more stable than
methanol.

• As the reactions are exothermic


➜ Good temperature control in the
reactor important.
• The catalyst needs to be active and
selective towards methanol

Mechanism of methanol formation


Methanol synthesis mechanism

Rate determining step

Cu/ZnO/Al2O3 catalysts
CuO (wt %) > 55
ZnO (wt %) 21-25
Al2O3 (wt %) 8-10

H2 H2 : H2O = 1 : 3 H2 : CO = 95 : 5
Equilibrium CO conversion to methanol

Zn/Cr2O3

Cu/ZnO/Al2O3

Synthesis gas for methanol production

• Optimum H2/CO ratio : 2


– Lower ratio: increased production of by-products
– Higher ratio: excess hydrogen needs to be purged
• A small amount of CO2 increases the catalyst activity

ATR
H2 – CO2
Module M = 2 =
CO + CO2
Purification of syngas

Low concentrations of impurities, such as sulfur (especially newer


catalysts are very sensitive against poisoning)

The feed (syngas) purification section may consist of the following


steps:
• Hydrogenation
• Chlorine Absorption
• Sulphur Absorption
• Trace removal of Sulphur (final purification)

Industrial processes
Natural
Compression Distillation
gas Reforming

Desulfurization Cooling Methanol


synthesis
Methanol
product

• ICI/LINDE – low pressure process


• Lurgi – low pressure process
• BASF – high pressure process
• UK – Wesseling high pressure process
Types of reactors used for efficient cooling

(a)
• Cooling with water bath; (b)cooling with water coils; (c) cooling with cold feed;
(d) feed gas quench; (e) feed–effluent heat exchange by periodic flow reversal;
(f) lateral flow; (g) fluidised bed.

Linde/ICI low pressure synthesis


Steam
Circulating
water Boiler
feed water
Gas

Circulating water Gas exit


Linde/ICI – low pressure synthesis
• Temperature 240 – 260 °C
• Pressure 50 – 100 bar
• Catalyst Cu-Zn-Al-Oxides
→ catalyst is very sensitive against poisoning and
requires very low concentrations of impurities.

99.9% MeOH

The Lurgi – low pressure process


• Temperature: 250 – 260 °C
• Pressure: 50 – 80 bar
• Catalyst: modified CuO-ZnO catalyst
• Reactor type: multi-tubular reactors Mega methanol plants
(5000 tons/d)

Syngas is partially converted in the 1st


reactor and is sequentially fed to the 2nd
where the cooling medium is cold syngas
BASF – high pressure process

• Temperature: 320 – 380 °C


• Pressure: 340 bar
• Catalyst: ZnO-Cr2O3 (Zn:Cr ratio: 70:30)
Catalyst is very resistant against poisons in low concentrations
→ long life time (several years)
• Very short residence time to avoid side reactions (1-2 sec)
• Low conversions per one single pass (12-15%)
• At several inlets along the reactor cold feed is added to control
the temperature.

UK – Wesseling high pressure process

• Temperature: 350°C
• Pressure: 300 bar
• Catalyst: ZnO-Cr2O3
→ similar conditions like in the BASF process

Difference:
Lower partial pressure for CO (13 bar) used:
• Reactor can be built from steal as Fe(CO)5 is not produced
• Purity of methanol very good
New industrial developments

Company Catalsty Temperature (°C) Pressure (bar)


Haldor-Topsøe CuO-ZnO-Cr2O3 230-260 100-150
Vulcan ZnO-Cr2O3 270-330 150-250
Pritchard CuO Unknown 100-250
Catalyst & CuO-ZnO-Al2O3 240-250 100-250
Chemical Inc.

BASF CuO-ZnO-Al2O3 200-350 50-250


Mistubishi Gas CuO + promoters 200-280 50-150
Chemical

Methanol production with medium pressure processes

Methanol synthesis slurry process


Methanol future

Reducing the cost of production by installing “Mega”production facilities using as


raw material low-cost natural gas is opening up new promising areas for methanol
uses as a motor fuel, gasoline additive, feedstock for chemical synthesis, source
of carbon for protein production

New applications of MeOH for the production of


• Ethylene and/or propylene, MTP
• Dimethyl ether as a substitute for diesel fuel
• Liquid fuels (substitute of gasoline or raw material for gasoline production
MTG process
• Hydrogen or feed material for power generating systems or
• Use in integrated schemes combined with an ammonia/urea complex
• Methanol consumption for fuel cells to be used in automobiles, for power
generation and portable equipment is bound to increase in the near future.