Patent GB-386725-A (GB)
Title: Improvements in the oxidation of organic compounds
Filed: 1931-09-28
Abstract: Aliphatic or cycloaliphatic compounds containing at least six carbon atoms are treated in the liquid phase with a gaseous oxidant in the presence of a catalyst comprising (1) a salt of an alkali metal with a higher carboxylic acid, i.e. a carboxylic acid containing at least six carbon atoms, and (2) an aluminium salt of a higher carboxylic acid.  The materials which may be treated include montan wax, paraffin wax, ceresine, paraffin oil, heavy or middle oils, gas oil, naphthene hydrocarbons, hydrocarbons obtained from coal, brown coal, tar or mineral oils by destructive hydrogenation or low-temperature carbonization, animal or vegetable oils or fats such as wool fat, coconut, sesame, rapeseed, cottonseed, linseed or castor oils or residues from the purification of these materials, fractions of turpentine oil boiling above 300 DEG  C., and non-aromatic alcohols and ketones obtainable from hydrocarbons by oxidation.  The oxidant may be oxygen, air, or a mixture of oxygen or nitrogen oxides with air. The reaction temperature may be 100-200 DEG  C., preferably 130-170 DEG  C.  The proportion of catalyst does not exceed about 3 per cent of the material treated.  The reaction products generally include acids, esters, alcohols, aldehydes, and ketones.  The carboxylates forming the catalyst may be oleates, naphthenates, palmitates, cinnamates, abietates, or other resinates, or salts of crude or isolated acid oxidation products of hydrocarbons.  The catalyst may be added in one batch or in portions during the process. In the examples, (1) a petroleum fraction boiling between 180 and 350 DEG  C. is treated with air at 160 DEG  C. in the presence of sodium palmitate and aluminium palmitate; (2) hydrocarbons boiling between 180 and 300 DEG  C., obtained by the destructive hydrogenation of brown coal tar, are treated with finely subdivided air at 160 DEG  C. in the presence of lithium oleate and aluminium stearate; (3) paraffin wax is treated with air at 150 DEG  C. in the presence of aluminium abietate and a potassium salt obtained by saponifying the crude oxidation products of paraffin wax with caustic potash; the product is separated from unchanged initial material by extraction with liquid sulphur dioxide; (4) a mixture of paraffin wax and neutral oxidation products of paraffin wax is treated with air at 150 DEG  C. in the presence of potassium palmitate and aluminium rosinate.  Specifications 252,327, 255,020, 256,922, 257,886, 303,268, and 310,069, [all in Class 2 (iii), Dyes &c.], are referred to.  The Provisional Specification describes the use of catalysts comprising alkali-metal and aluminium compounds which are converted in the process into salts of the fatty acids formed, and refers in this connection to the use of oxides, hydroxides, carbonates and carbides of the metals specified.ALSO:Aliphatic or cycloaliphatic compounds containing at least 6 carbon atoms are treated in the liquid phase with a gaseous oxidant in the presence of a catalyst comprising (1) a salt of an alkali metal with a higher carboxylic acid, i.e. a carboxylic acid containing at least 6 carbon atoms, and (2) an aluminium salt of a higher carboxylic acid.  The carboxylates forming the catalyst may be oleates, naphthenates, palmitates, cinnamates, abietates or other resinates, or salts of crude or isolated acid oxidation products of hydrocarbons.  In the examples the catalysts used are (1) sodium palmitate and aluminium palmitate; (2) lithium oleate and aluminium stearate; (3) aluminium abietate and a potassium salt obtained by saponifying the crude oxidation products of paraffin wax with caustic potash; (4) potassium palmitate and aluminium rosinate.  Specifications 252,327, 255,020, 256,922, 257,886, 303,268, and 310,069, [all in Class 2 (iii), Dyes &c.], are referred to.  The Provisional Specification describes the use of catalysts comprising alkali-metal and aluminium compounds which are converted in the process into salts of the fatty acids formed, and refers in this connection to the use of oxides, hydroxides, carbonates, and carbides of the metals specified.