Patent GB-397852-A (GB)
Title: Improvements in or relating to the carrying out of chemical reactions with carbon monoxide
IPC: C01B32/40
Filed: 1932-02-29
Abstract: Acid chlorides; amines; aldehydes; acids; esters; alcohols and ethers.--Reactions in the gaseous phase involving carbon monoxide, other than the catalytic decomposition of carbon monoxide to form carbon black, are accelerated by the use of small amounts of halogens, hydrogen halides, alkyl halides, or nitrogen oxides, e.g. 0,1-5 per cent by volume.  Preferably solid catalysts or inert materials which act as catalysts in the presence of the above bodies are also employed.  The halogens and hydrogen halides are suitable for use in reactions between alcohols and carbon monoxide to form acids, esters and ethers; hydrogen halides may be used to accelerate the formation of esters from alkyl ethers and carbon monoxide, or organic acids from paraffin hydrocarbons and carbon monoxide, or organic amines from ammonia and carbon monoxide.  Alkyl halides are suitable for the preparation of acyl chlorides from alkyl chlorides and carbon monoxide.  Other reactions include the formation of acyl chlorides from hydrocarbons, chlorine and carbon monoxide, alcohols and aldehydes from carbon monoxide and steam, and aldehydes from hydrocarbons and carbon monoxide.  According to an example, a mixture of carbon monoxide, hydrogen chloride, methanol vapour; hydrogen and water vapour is passed under a pressure of 700 atmospheres through a reaction chamber containing copper chloride supported on charcoal and maintained at 350 DEG  C.  Acetic acid and methyl acetate are obtained.  Pressures from 100-1000 atmospheres may be used in the above reactions.ALSO:Reactions in the gaseous phase involving carbon monoxide, other than the catalytic decomposition of carbon monoxide to form carbon black, are accelerated by the use of small amounts of halogen, hydrogen halides, alkyl halides or nitrogen oxides, e.g. 0,1-5 per cent by volume.  Preferably solid catalysts or inert materials which act as catalysts in the presence of the above bodies are also employed.  The halogens and hydrogen halides are suitable for use in reactions between alcohols and carbon monoxide to form acids, esters and ethers; hydrogen halides may be used to accelerate the formation of esters from alkyl ethers and carbon monoxide, or organic acids from paraffin hydrocarbons and carbon monoxide, or organic amines from ammonia and carbon monoxide. Alkyl halides are suitable for the preparation of acyl chlorides from alkyl chlorides and carbon monoxide; and the oxides of nitrogen for the reaction between ammonia and carbon monoxide to give hydrocyanic acid.  Other reactions include the formation of acyl chlorides from hydrocarbons, chlorine and carbon monoxide; alcohols and aldehydes from carbon monoxide and steam, and aldehydes from hydrocarbons and carbon monoxide.  According to examples, (1) Hydrocyanic acid is obtained by passing equal volumes of carbon monoxide and ammonia together with 0,5 per cent of nitric oxide under pressure through a reaction tube lined with an inert material such as aluminium and filled with a thoria catalyst, the temperature of the catalyst being maintained at 200-750 DEG  C., preferably 400-500 DEG  C.  (2) A mixture of carbon monoxide, hydrogen chloride, methanol vapour, hydrogen and water vapour is passed under a pressure of 700 atmospheres through a reaction chamber containing copper chloride supported on charcoal and maintained at 350 DEG  C.  Acetic acid and methyl acetate being obtained.  (3) Carbon dioxide and hydrogen are obtained from a mixture of carbon monoxide and steam containing 0,1 per cent of bromine which is passed over a catalyst at a temperature of 325-400 DEG  C.  Pressures from 100-1000 atmospheres may be used in the above reactions.