Patent GB-718603-A (GB)
Title: Oxidation of hydrocarbons
IPC: C07C45/34
Filed: 1951-09-18
Abstract: Oxygen-containing organic compounds including an a -hydroxy carbonyl compound are obtained by subjecting an olefine containing four carbon atoms in admixture with a paraffin containing four carbon atoms to non-catalytic partial oxidation by reaction with oxygen under a superatmospheric pressure of 50 to 100 pounds per square inch gauge, 20 to 80 per cent by volume of the hydrocarbons being paraffinic and the oxygen and hydrocarbon-containing mixture subjected to reaction being diluted with inert gases forming 50 to 70 per cent by volume of the diluted mixture, the reaction being effected by raising the temperature of the diluted mixture to at least 550 DEG  F. while preventing subsequently any rise in temperature to above 1000 DEG  F. and quickly cooling the products after a suitable reaction time of at least 0.25 second.  It is preferred to use a hydrocarbon mixture containing between 30 and 70 per cent and particularly between 40 and 60 per cent by volume of paraffinic hydrocarbon.  In addition to the a -hydroxycarbonyl compounds there can be obtained higher yields of alcohols and aldehydes such as propionaldehyde and acrolein than are obtained by oxidizing paraffinic hydrocarbons, thus a hydrocarbon mixture containing 40 parts by volume of n-butane to each 60 parts by volume of butene-2 gives a higher yield of acrolein and propionaldehyde than is obtained from n-butane alone or from a mixture containing 15 parts by volume of n-butane to 85 parts by volume of butene-2.  Mixtures of n-butane with butene-1 or butene-2 are stated to give useful yields of 1, 2- or 2,3-butylene oxide respectively.  The oxidation products may be separated by a combination of steps, including, for instance, selective absorption, extraction and distillation.  In examples: (1) a gaseous mixture consisting of 7.5 per cent by volume of n-butane, 22.5 per cent by volume of butene-2, 3.5 per cent of oxygen and 66.5 per cent of inerts including nitrogen, carbon monoxide, and carbon dioxide is heated to 675 DEG  F. under a pressure of 100 lb./sq. inch gauge and after the temperature reaches 850-900 DEG  F. the reaction is halted within about 0.5 second by passing the mixture into a cascading stream of water; separation of the products yields methyl a -hydroxyethyl ketone and 2,3-butylene oxide; (2) a gaseous mixture consisting of 6 per cent by volume of isobutane, 24 per cent of isobutylene, 3.5 per cent of oxygen and 66.5 per cent of inerts (as in (1)) is heated to 650 DEG  F. under 100 lb./sq. inch gauge pressure and after the temperature reaches 850-900 DEG  F. further reaction is halted within 0.5 second as in (1) and the products separated to yield alpha-hydroxy isobutyraldehyde and isobutylene oxide; (3) a gaseous mixture consisting of 16 per cent by volume of butene-2, 11 per cent of n-butane, 3.6 per cent of oxygen and 69.4 per cent of inerts (as in (1)) is heated to 650 DEG  F. under a pressure of 100 lbs./sq. inch gauge and the mixture maintained at 900 DEG  F. for 0.5 second before quenching with water; the products include propionaldehyde and acrolein; when the starting mixture contains the same proportion of hydrocarbon but in which 85 per cent of the hydrocarbon is butene-2 and 15 per cent is n-butane, the combined yield of propionaldehyde and acrolein is reduced; (4) as in (3) except that the gaseous mixture contains 16 per cent by volume of n-butane and 11 per cent by volume of butene-2 and the oxidation product comprises 1,2-propylene oxide.  Specification 397,161 is referred to.