Patent GB-798564-A (GB)
Title: Improvements in or relating to the preparation of olefinic carbonylic compounds
IPC: B01J23/72
Filed: 1956-06-04
Abstract: Olefinic carbonylic compounds, e.g. alpha, beta-unsaturated aldehydes and ketones, are prepared by the incomplete oxidation of an olefinic hydrocarbon with oxygen or a gas containing oxygen in the presence of a supported copper-containing catalyst which has been prepared by contacting a solid support material at 10-150 DEG  C. with a mixture of a solution of a copper salt, ammonium hydroxide, and a reducing agent comprising hydrazine or a hydrazine derivative (see Group III). Acrolein and methacrolein may be formed from propylene and isobutylene respectively. Examples describe the oxidation of propylene (a) at 250-300 DEG  C., atmospheric pressure, and a propylene to oxygen mol. ratio of 10 : 1; (b) at 400 DEG  C., 85 lbs. per sq. in. pressure, and a propylene to oxygen mol. ratio of 8 : 1. Water vapour may be added to the charge.ALSO:A supported copper-containing catalyst, for the oxidation of olefinic hydrocarbons to olefinic carbonylic compounds (see Group IV (b)), is prepared by contacting a solid support material at 10-150 DEG  C. with a mixture of a solution of a copper salt, ammonium hydroxide, and a reducing agent comprising hydrazine or a hydrazine derivative. The reducing agent may be added to a mixture of the copper salt solution, ammonium hydroxide, and the support; alternatively the support may be preheated, e.g. to 40-100 DEG  C., and contacted with a mixture of the reducing agent and the ammoniacal copper salt solution.  After formation of the deposit of copper, the support may be washed and dried in air or an atmosphere of a hydrocarbon or an inert gas at 100-250 DEG  C. Suitable copper salts are the acetate, chloride, nitrate, and sulphate.  The preferred reducing agents are hydrazine and hydrazine hydrate, but phenyl hydrazine and hydrazine sulphate may also be used.  The support is preferably granular and may be composed of pumice, diatomaceous earth silica gel, silicon, silicon carbide, boron carbide, carborundum, alumina, carbon, magnesia, thoria, bauxite, sandstone, crushed firebrick, majolica, fused zirconia, silica-alumina, gels of chromium, molybdenum, or tungsten oxides, zirconium carbide, circonium boride, or boron nitride.  The support may be pretreated by heating in steam or inert gas, treatment with hydrogen chloride, nitric acid, or hydrogen fluoride, contact with iodine, chlorine, or fluorine, or by deposition of minor amounts of silver, gold, or platinum.  The copper coating on the support may be converted to cuprous oxide by heating to 100-250 DEG  C. in an oxidizing atmosphere or by heating to 100-600 DEG  C. in an atmosphere of a hydrocarbon and oxygen.ALSO:A supported copper-containing catalyst, for the oxidation of olefinic hydrocarbons to olefinic carbonylic compounds (see Group IV(b)), is prepared by contacting a solid support material at 10 DEG -150 DEG C. with a mixture of a solution of a copper salt, ammonium hydroxide, and a reducing agent comprising hydrazine or a hydrazine derivative. The reducing agent may be added to a mixture of the copper salt solution, ammonium hydroxide, and the support; alternatively the support may be preheated, e.g. to 40 DEG -100 DEG C., and contacted with a mixture of the reducing agent and the ammoniacal copper salt solution.  After formation of the deposit of copper, the support may be washed and dried in air or an atmosphere of a hydrocarbon or an inert gas at 100 DEG -250 DEG C. Suitable copper salts are the acetate, chloride, nitrate, and sulphate.  The preferred reducing agents are hydrazine and hydrazine hydrate, but phenyl hydrazine and hydrazine sulphate may also be used.  The support is preferably granular and may be composed of pumice, diatomaceous earth, silica gel, silicon, silicon carbide, boron carbide, carborundum, alumina, carbon, magnesia, thoria, bauxite, sandstone, crushed firebrick, majolica, fused zirconia, silica-alumina, gels of chromium, molybdenum, or tungsten oxides, zirconium carbide, zirconium boride, or boron nitride.  The support may be pretreated by heating in steam or inert gas, treatment with hydrogen chloride, nitric acid, or hydrogen fluoride, contact with iodine, chlorine, or fluorine, or by deposition of minor amounts of silver, gold, or platinum.  The copper coating on the support may be converted to cuprous oxide by heating to 100 DEG -250 DEG C. in an oxidizing atmosphere or by heating to 100 DEG -600 DEG C. in an atmosphere of a hydrocarbon and oxygen.