| 摘要 |
Oxygenated compounds obtained by the action of CO, with or without H2, on organic compounds in the presence of catalysts which produce soluble metal compounds in the final product, are treated to decompose said metal compounds by introducing, at elevated temperature and a pressure of 10-80 atmos., a gas containing H2 and 0.1-50 per cent, preferably 10-50 per cent CO. Unsaturated hydrocarbons, aldehydes, ketones, alcohols, ethers, acids, halides, amides, sulphides, cyanides, sulphates, sulphonates, and esters such as vinyl esters, as well as compounds having a feeble bond which may be broken under the reaction conditions, e.g. dialkyl formals, acetals containing aromatic or cyclo-aliphatic groups, cyclic acetals such as 1,3-dioxolane, and aliphatic cyclic ethers may be formylated to yield aldehydes, ketones, and acids. Metal, e.g. iron, nickel or cobalt, carbonyls, and particularly cobalt hydrocarbonyl are suitable catalysts. The products, produced at a pressure above 100 atms., may be cooled and decompressed to the pressure required for decomposition of metal compounds, part or all of the CO liberated, if desired, being conveyed to the decomposer. The temperature therein may be up to 250 DEG C. and is preferably 150-220 DEG C. pressure is preferably 25-50 atms. The metal may be deposited on a carrier such as pumice and used as catalyst in a subsequent hydrogenation, for example of aldehydes to alcohols. In examples: aldehydes obtained by formylation of C6 or 7-C8 alkenes, using cobalt hydrocarbonyl or cobalt on kieselguhr as catalyst are treated with gas mixtures comprising H2 and 41.1 or 22 per cent CO at 25 atmos. and 180-200 DEG C.ALSO:Cobalt-hydrocarbonyl is prepared by saturating with CO a solution in air-free water of cobalt nitrate, potassium hydroxide and cyanate, acidifying with phosphoric acid, passing CO, and leading the discharged gas through a drier and a condenser. Alternatively, gas containing CO and H2 is reacted with a cobalt-containing mass at a pressure of, say, above 100 atmospheres and temperature of, say, 80-130 DEG C. A liquid such as alkene-containing hydrocarbons may be passed over to dissolve the hydrocarbonyl. |
