| 摘要 |
Unsaturated hydrocarbons together with any oxygen-containing hydrocarbon derivatives produced in a first stage from CO and H2 at above 400 DEG C., preferably between 550 DEG and 700 DEG C., in the presence of hydrogenation catalysts which are completely free from catalytically active iron, cobalt or nickel compounds are reacted in a second stage with CO and H2 at 60 DEG -250 DEG C. in the presence of iron, nickel or preferably cobalt catalysts. Preferred CO : H2 ratios are 0.8 : 1 to 1 : 1.3. A gas mixture obtained by gasifying solid fuels at about 10-40 atmospheres with oxygen or air enriched with oxygen and steam, cf. Specification 364,407, [Group XII], may be used. Catalysts for the first stage are oxygen-containing compounds, e.g. oxides, nitrates and carbonates, of metals of the second to the seventh group of the periodic system and they may be activated by a pretreatment with, e.g. hydrogen, steam or acids. Many metals are specified whose oxygen-compounds afford catalysts and mixtures such as thoria-alumina and alumina-molybdenum oxide may be used. Compounds of metals of the first group may also be present in the catalysts as may alkalis, e.g. 3-5 per cent of K2O. The catalysts may be on carriers and disposed in one or more vessels and may be fluidized. With thoria catalysts a synthesis temperature of about 450 DEG C. may be used. The oxo synthesis is preferably at 140-180 DEG C. and advantageously at pressures of above 40 atmospheres gauge, e.g. 80, 100 and 150 atmospheres gauge. Conventional cobalt carbonylation catalysts may be used. Solvents, e.g. liquified propane or butane or reaction products may be present to aid the removal of aldehydes from the products. The aldehydes may be hydrogenated to alcohols. In an Example, CO and H2 in a volume ratio of about 1 : 1 is converted at 580 DEG C. and 100 atmospheres gauge in the presence of a catalyst consisting of alumina with some molybdenum, chromium and tungstic oxides and the products passed to an oxostage conducted at the same pressure and a temperature of about 170 DEG C. in the presence of pumice impregnated with cobalt nitrate, the aldehyde product being hydrogenated at about 160 DEG C. and in a subsequent stage at 195 DEG C. to give mainly propyl with some butyl, amyl and higher alcohols. Specifications 542,836, 692,804, 728,444, 734,577 and 750,399, [all in Group XII], also are referred to. |
