Patent GB-674884-A (GB)
Title: A process for the treatment of fatty acid esters
Inventor: BLASER BRUNO
IPC: C11C3/14
Filed: 1949-04-14
Abstract: Fatty acid esters whose acid component contains non-saturated fatty acids are isomerized by heating with metal carbonyls in the presence of carbon monoxide at elevated pressures.  The carbonyls may be formed in situ.  Examples of fatty acid ester starting materials are natural fats, the fatty acid components of which contain unsaturated fatty acids, esters of monohydric alcohols with fatty acids containing one or more double bonds, e.g. the methyl, ethyl-butyl and octyl esters and corresponding esters from ethylene glycol and polyglycols.  The fatty acid components may include acids having one or more double bonds, e.g. oleic, linoleic, linolenic, erucic and fish oil fatty acids either alone or mixed with saturated fatty acids.  Catalysts include metal carbonyls such as those of iron and cobalt and those containing other atoms or groups of atoms in addition to carbon monoxide or alternatively carbonyl producing metals may be mixed with the fatty acid ester which is then heated under pressure with carbon monoxide.  The carbonyl producing metal may be deposited on a support.  The preferred temperatures are between 150 DEG  and 300 DEG  C. The metal carbonyl is removed after the reaction by filtration, adsorption on surface-active substances or washing with acids or solutions of salt.  The process may be continuous or batchwise, e.g. the reaction mixture may be heated, whilst being passed through pipes or in an autoclave with carbon monoxide under pressure.  The process results chiefly in isomerization of the fatty acid components without combination of the carbon monoxide occurring.  The melting point of the esters may be raised and the unsaturated character remains.  In examples: (1) peanut oil is heated under pressure with carbon monoxide and a catalyst containing cobalt, thorium oxide, magnesium oxide and infusorial earth, the reaction product is filtered, washed with dilute nitric acid and water and then dried; (2) peanut oil is heated under pressure with carbon monoxide in the presence of metallic cobalt which has been prereduced by heating with hydrogen; (3) and (4) wheat germ oil and a glycerine-oleine ester respectively are treated similarly to the peanut oil in (1); (5) peanut oil is heated under pressure with carbon monoxide and cobalt carbonyl obtained by heating a mixture of cobalt, thorium oxide, magnesium oxide and kieselguhr in xylol under pressure with carbon monoxide and filtering.  The melting-points of the esters in each of the examples and of the free acids obtained by saponification and acidification in examples (4) and (5) are raised.ALSO:Fatty acid esters whose acid component contains non-saturated fatty acids are isomerized by heating with metal carbonyls in the presence of carbon monoxide at elevated pressures.  The carbonyls may be formed in situ.  Examples of fatty acid ester starting materials are natural fats the fatty acid components of which contain unsaturated fatty acids, esters of monohydric alcohols with fatty acids containing one or more double bonds, e.g. the methyl, ethyl-butyl and octyl esters and corresponding esters from ethylene glycol and polyglycols.  The fatty acid components may include acids having one or more double bonds, e.g. oleic, linoeic, linolenic, erucic and fish oil fatty acids either alone or mixed with saturated fatty acids.  Catalysts include metal carbonyls such as those of iron and cobalt and those containing other atoms or groups of atoms in addition to carbon monoxide or alternatively carbonyl producing metals may be mixed with the fatty acid ester which is then heated under pressure with carbon monoxide. The carbonyl producing metal may be deposited on a support.  The preferred temperatures are between 150 DEG C. and 300 DEG C. The metal carbonyl is removed after the reaction by filtration, p adsorption on surface active substances or washing with acids or solutions of salt.  The process may be continuous or batchwise, e.g. the reaction mixture may be heated whilst being passed through pipes or in an autoclave with carbon monoxide under pressure.  The process results chiefly in isomerization of the fatty acid component without combination of the carbon monoxide occurring.  The melting point of the esters may be raised and the unsaturated character remains.  In examples: (1) Pea-nut oil is heated under pressure with carbon monoxide and a catalyst containing cobalt, thorium oxide, magnesium oxide and infusorial earth, the reaction product is filtered, washed with dilute nitric acid and water and then dried (2) pea-nut oil is heated under pressure with carbon monoxide in the presence of metallic cobalt which has been pre-reduced by heating with hydrogen (3) and (4) wheat germ oil and a glycerine-oleine ester respectively are treated similarly to the pea-nut oil in (1), (5) pea-nut oil is heated under pressure with carbon monoxide and cobalt carbonyl obtained by heating a mixture of cobalt, thorium oxide, magnesium oxide and kieselguhr in xylol under pressure with carbon monoxide and filtering.  The melting points of the esters in each of the examples and of the free acids obtained by saponification and acidification in examples (4) and (5) are raised.