Patent GB-367003-A (GB)
Title: Improvements in the isolation of alcohols of high molecular weight
IPC: C07C29/14
Filed: 1930-11-05
Abstract: Alcohols of high molecular weight suitable for the preparation of ointments, creams, and polishing compositions, are made by reduction with hydrogen and a catalyst of the oxidation products of liquid or solid non-aromatic hydrocarbons such as paraffin wax or paraffin oil, and the alcohols are then extracted from the product by means of water-soluble aliphatic alcohols such as methanol, ethanol, propanol or butanol or their esters with fatty acids containing up to three carbon atoms, in the presence of water.  The quantity of water may be 1-20 per cent of the quantity of the solvent employed.  The crude oxidation product may be first treated to separate the acids and the unchanged hydrocarbon, for instance, the acids may be separated by saponification and extraction with benzine and the content of oxygen compounds in the unsaponifiable fraction may be increased by centrifuging, sweating, pressing or extracting.  The hydrogenation is effected in the liquid phase at 30-200 atmospheres pressure and at 150-300 DEG  C., and the usual catalysts such as copper, nickel, cobalt or their salts, such as copper chromites may be employed. The alcohols obtained from the oxidation product of hard paraffin contain 20 per cent of liquid alcohols with 9-14 carbon atoms and 80 per cent of solid alcohols with 15-24 carbon atoms; liquid alcohols are obtained from the oxidation products of liquid hydrocarbons. Sulphuric esters and sulphonic acids prepared from the alcohols by known methods as well as the salts of these acids are washing and emulsifying agents.  In examples (1) the oxidation product of hard paraffin is treated with caustic soda to remove the acids, and the unsaponifiable portion is separated from the greater part of the unattacked hard paraffin by centrifuging and is hydrogenated at 250 DEG  C. with a nickel catalyst at 50 atmospheres pressure; the product is stirred with methanol containing 4 per cent of water; in standing the upper layer contains about 60 per cent of the alcohols, a second extraction recovering the rest of the alcohols; (2) the unsaponifiable portion of the oxidation product of soft paraffin, obtained by treating the crude product with aqueous sodium carbonate at 160 DEG  C. and extracting the emulsion with gasoline at 70 DEG C., is hydrogenated at 190 DEG  C. and 50 atmospheres pressure with cobalt; the product is stirred with methyl formate containing 10 per cent of water; (3) soft paraffin wax is blown with 1 cubic metre of air per kilo of wax at 160 DEG  C. with boric acid as catalyst; the product is boiled with water to split the boric esters, and the product is hydrogenated at 200 DEG  C. and 100 atmospheres pressure with a nickel catalyst consisting of kieselguhr carrying 25 per cent of nickel and 0,1 per cent of copper, whereby both acids and other oxidation products are reduced to alcohols; the mixture is stirred at 45 DEG  C. with aqueous 96 per cent ethyl alcohol and filtered, a second extraction recovering the rest of the alcohols. Specifications 352,537 and 356,731 are referred to.ALSO:Alcohols of high molecular weight suitable for the preparation of ointments, creams, and polishing compositions, are made by reduction with hydrogen and a catalyst of the oxidation products of liquid or solid non-aromatic hydrocarbons such as paraffin wax or paraffin oil, and the alcohols are then extracted from the product by means of water-soluble aliphatic alcohols such as methanol, ethanol, propanol or butanol or their esters with fatty acids containing up to three carbon atoms, in the presence of water.  The quantity of water may be 1-20 per cent of the quantity of the solvent employed.  The crude oxidation product may be first treated to separate the acids and the unchanged hydrocarbon, for instance, the acids may be separated by saponification and extraction with benzine and the content of oxygen compounds in the unsaponifiable fraction may be increased by centrifuging, sweating, pressing or extracting.  The hydrogenation is effected in the liquid phase at 30-200 atmospheres pressure and at 150-300 DEG  C. and the usual catalysts such as copper, nickel, cobalt or their salts such as copper chromites may be employed.  The alcohols obtained from the oxidation product of hard paraffin contain 20 per cent of liquid alcohols with 9-14 carbon atoms and 80 per cent of solid alcohols with 15-24 carbon atoms; liquid alcohols are obtained from the oxidation products of liquid hydrocarbons. Sulphuric esters and sulphonic acids prepared from the alcohols by known methods as well as the salts of these acids are washing and emulsifying agents.  In examples (1) the oxidation product of hard paraffin is treated with caustic soda to remove the acids, and the unsaponifiable portion is separated from the greater part of the unattacked hard paraffin by centrifuging and is hydrogenated at 250 DEG  C. with a nickel catalyst at 50 atmospheres pressure; the product is stirred with methanol containing 4 per cent of water; in standing, the upper layer contains about 60 per cent of the alcohols, a second extraction recovering the rest of the alcohols; (2) the unsaponifiable portion of the oxidation product of soft paraffin, obtained by treating the crude product with aqueous sodium carbonate at 160 DEG  C. and extracting the emulsion with gasoline at 70 DEG C., is hydrogenated at 190 DEG  C. and 50 atmospheres pressure with cobalt; the product is stirred with methyl formate containing 10 per cent of water; (3) soft paraffin wax is blown with 1 cubic metre of air per kilo of wax at 160 DEG  C. with boric acid as catalyst; the product is boiled with water to split the boric esters, and the product is hydrogenated at 200 DEG  C. and 100 atmospheres pressure with a nickel catalyst consisting of kieselguhr carrying 25 per cent of nickel and 0,1 per cent of copper, whereby both acids and other oxidation products are reduced to alcohols; the mixture is stirred at 45 DEG  C. with aqueous 96 per cent ethyl alcohol and filtered, a second extraction recovering the rest of the alcohols. Specifications 352,537 and 356,731 are referred to.ALSO:Alcohols of high molecular weight suitable for the preparation of ointments, are made by reduction with hydrogen and a catalyst of the oxidation products of liquid or solid non-aromatic hydrocarbons such as paraffin wax or paraffin oil, and the alcohols are then extracted from the product by means of water-soluble aliphatic alcohols such as methanol, ethanol, propanol or butanol or their esters with fatty acids containing up to three carbon atoms, in the presence of water. The quantity of water may be 1-20 per cent of the quantity of the solvent employed.  The crude oxidation product may be first treated to separate the acids and the unchanged hydrocarbon, for instance, the acids may be separated by saponification and extraction with benzine and the content of oxygen compounds in the unsaponifiable fraction may be increased by centrifuging, sweating, pressing or extracting.  Specifications 352,537 and 356,731, [Group IV], are referred to.