| 摘要 |
Oxygen containing organic compounds such as aldehydes and alcohols are obtained by the conversion of hydrocarbons having at least one olefinic double band by the action of a gas-containing carbon monoxide and hydrogen, wherein the said gas is passed through a zone containing metallic cobalt or a cobalt compound capable of forming volatile CO- and H-containing compounds under conditions favouring the formation of these volatile compounds, and employing the latter after their formation for the conversion in a separate reaction vessel. The volatile metal compound, e.g. cobalt hydrocarbonyl, may be passed to the reaction vessel in the gaseous phase. The cobalt may be placed in the first zone on a carrier of conventional type. Cobalt compounds instanced are salts of inorganic and organic acids, carbonyl compounds and alloys and mixtures of cobalt with other metals, e.g. zinc. When metal salts, e.g. cobalt chloride are used a compound capable of binding the liberated acid radical may be present, e.g. copper, silver and zinc. All or part of the gas-containing carbon monoxide and hydrogen may be passed through the first zone and the olefines may also be present. The gas-containing carbon monoxide and hydrogen is passed through the metal containing zone at 50-140 DEG C., preferably 80-120 DEG C. with a partial pressure of the carbon monoxide and hydrogen in the gas of at least 10 atmos., preferably at least 30 atmos. Water gas may be used. In the first zone conditions are chosen to favour hydrocarbonyl formations as by using a CO : H2 ratio of 1 : 3 to 1 : 0-1. In examples: (1) preheated water gas containing 45 per cent of CO and 55 per cent of H2 is passed at 200 atmos. over a cobalt or pumice catalyst of 30 per cent cobalt content at 110 DEG C. and 2200 litres per litre of catalyst per hour, and then to the reaction vessel to convert at 140 DEG C. an octane fraction containing 88 per cent of octanes which is passed to the reaction vessel at 100 DEG C. with a throughput rate of 0.5 kgm. per litre of reaction space per hour, the pressure for the reaction is 200 atmos., the mixture leaving the vessel goes to a high pressure separator, gas and liquid are separated and the pressure in the liquid reduced to atmospheric, cobalt carbonyl compounds are released and hydrogenation effected at 180 DEG C. under 200 atmos. pressure, the product comprising 32 per cent of octanes, 62 per cent nonyl alcohols and 6 per cent of high boiling viscous oil; p (2) the above water gas is passed through the catalyst chamber as in (1) but with the addition of 2.2 litres of a C7-C8 olefin cut containing 89 per cent of olefines per litre of catalyst, the temperature being 80 DEG C. and pressure 150 atmos., the mixture is passed to the reaction vessel and reaction effected at 130 DEG C. in the presence of about 8 per cent cobalt on pumice catalyst with a throughput rate of 0.5 kgm. of catalyst per hour, pressure being 150 atmos. and the products separated and hydrogenated as in (1). |
