CHEMICALS BASED ON SYNTHESIS GAS:

METHYL ALCOHOL (CH3OH)

• Methyl alcohol (methanol) is the first member of the aliphatic alcohol family
• Due to the high oxygen content of methanol (50 wt%), it is being considered as a gasoline
blending compound to reduce carbon monoxide and hydrocarbon emissions in automobile
exhaust gases.
• Methanol is produced by the catalytic reaction of carbon monoxide and hydrogen
(synthesis gas).
• Ratio required for methanol synthesis is 1:2(CO:H2)
• Ratio of CO:H2 in synthesis gas from natural gas is approximately 1:3
• So, carbon dioxide is added to reduce the surplus hydrogen.
 Uses of Methanol

• Approximately 50% of methanol production is oxidized to formaldehyde.

• it is used with many organic acids to produce the methyl esters such as methyl
acrylate, methylmethacrylate, methyl acetate, and methyl terephthalate.

• Methanol is also used to produce dimethyl carbonate and methyl-t-butyl ether, an

important gasoline additive.

• It is also used to produce synthetic gasoline using a shape selective catalyst (MTG
process).

• Olefins from methanol may be a future route for ethylene and propylene in
competition with steam cracking of hydrocarbons.
 Chemicals Based on Methanol
Hydrocarbons from Methanol
• Methanol may have a more important role as a basic building block in the
future because of the multisources of synthesis gas.
• When oil and gas are depleted, coal and other fossil energy sources could be
converted to synthesis gas, then to methanol, from which hydrocarbon fuels
and chemicals could be obtained.
• The reaction of methanol over a ZSM-5 catalyst could be considered a
dehydration, oligomerization reaction. It may be simply represented as:

• Where (CH2)n represents the hydrocarbons (paraffins + olefins + aromatics).

• Converting methanol to hydrocarbons is not as simple as it looks from the
previous equation.
• Many reaction mechanisms have been proposed, and most of them are
centered around the intermediate formation of dimethyl ether followed by
olefin formation.
• Olefins are thought to be the precursors for paraffins and aromatics:
• The main industrial route for producing formaldehyde is the catalyzed air oxidation
of methanol.

• The oxidation reaction is exothermic and occurs at approximately 400–425°C and

atmospheric pressure. Excess air is used to keep the methanol air ratio below the
explosion limits.
Uses of Formaldehyde:
1) Formaldehyde is the simplest and most reactive aldehyde.
2) Condensation polymerization of formaldehyde with phenol, urea, or melamine
produces phenol-formaldehyde, urea formaldehyde, and melamine formaldehyde
resins, respectively.
3) These are important glues used in producing particle board and plywood.
4) Formaldehyde reacts with ammonia and produces hexamethylenetetramine
(hexamine):

5) Hexamine is a cross-linking agent for phenolic resins

• Methyl Chloride (CH3CI)
• Methyl chloride is produced by the vapor phase reaction of methanol and hydrogen
chloride:

• The reaction conditions are 350°C at nearly atmospheric pressure. The yield is
approximately 95%. However, methyl chloride is primarily an intermediate for the
production of other chemicals.
• Methyl chloride from methanol may be further chlorinated to produce
dichloromethane, chloroform, and carbon tetrachloride.
• Acetic Acid (CH3COOH)
• The carbonylation of methanol is currently one of the major routes for acetic acid
production. The reaction occurs at 150°C and atmospheric pressure. A 99% selectivity is
claimed with this catalyst:

• Acetic acid is also produced by the oxidation of acetaldehyde and the oxidation of n-butane.
• However, acetic acid from the carbonylation route has an advantage over the other
commercial processes
• Because both methanol and carbon monoxide come from synthesis gas, and the process
conditions are quite mild.
Uses of Acetic Acid:

1) The main use of acetic acid is to produce vinyl acetate (44%), followed by
acetic acid esters (13%) and acetic anhydride (12%). Vinyl acetate is used
for the production of adhesives, film, paper and textiles.

2) Terephthalic acid consumes 12% of acetic acid demand. Acetic acid is also
used to produce pharmaceuticals, dyes, and insecticides.

3) Chloroacetic acid (from acetic acid) is a reactive intermediate used to

manufacture many chemicals such as glycine and carboxymethyl cellulose.
• Dimethyl Carbonate (CO(OCH3)2)

• Dimethyl carbonate (DMC) is a colorless liquid with a pleasant odor.

• It is soluble in most organic solvents but insoluble in water.

• The classical synthesis of DMC is the reaction of methanol with phosgene.

Because phosgene is toxic, a non-phosgene-route may be preferred.

• The new route reacts methanol with urea over a tin catalyst. However, the
yield is low. Dimethyl carbonate is used as a specialty solvent.