| 摘要 |
Propionaldehyde and propanol are made by reacting ethylene with CO and H2 in the liquid phase at 140-180 DEG C. under a total pressure of 200 to less than 300 atmos. gauge in the presence of a cobalt compound dissolved in the liquid medium, the partial pressure of CO being 55-150 atmos. gauge, and the molar ratio CO:H2 not above 1:1. Temperatures of 160-170 DEG C. are preferred. The ratio of CO to H2 is preferably not above 1:3 when corrosive equipment is used. Particularly preferred ratios of CO:H2 are 1:4 to 1:1. Liquid phase conditions are achieved by the use of a high boiling inert medium or an olefine liquid under the reaction conditions such as saturated butene trimer, C8 olefines, e.g. di-isobutene and higher olefines. Specified catalysts are soluble cobalt salts such as the naphthenate, acetate, non-anoate, laurate, oleate, a -butoxybutyrate or hexahydrobenzoate. Cobalt carbonyl or hydrocarbonyl may also be obtained in situ, e.g. by the use of cobalt metal or supported cobalt, e.g. on kieselguhr. Total pressures of about 250 atmos. gauge are preferred when at 140-180 DEG C. the CO:C2H4 ratio should be above 1.5:1, preferably at least 2:1. Desirably the reaction space should be full of liquid. Products may be separated by distillation in the presence of an anti-oxidant such as 2, 4-dimethyl-6-tertiary butyl phenol. Alternatively the product may be hydrogenated to propanol, after catalyst decomposition, at, e.g. 250 atmos. gauge and 250 DEG C. over copper on chromium or copper on zinc oxide. At the higher temperature and pressure ranges diethyl ketone may also be obtained, e.g. at above 170 DEG C. and 250 atmos. gauge. In examples ethylene is treated in (1) di-isobutene with H2 and CO in the ratio of 3:1 at 250 atmos. and 160 DEG C. in the presence of cobalt naphthenate to yield C3 alcohol and aldehyde and C3 alcohol and aldehyde and in (2) saturated butene trimer is used in place of di-isobutene the products being C3 alcohol and aldehyde. Specification 679.366 is referred to. |
