GB801734A - Carbonylation synthesis reaction - Google Patents

Abstract

Oxygenated compounds are prepared by reacting an olefin with carbon monoxide and hydrogen at 60-240 DEG C. and 1000-10,000 p.s.i.g. in the presence of a rhodium-containing catalyst capable of being dissolved in the reaction mixture under the reaction conditions. The rhodium catalyst may be combined with a cobalt catalyst. The olefins may be pure or as hydrocarbon mixtures containing olefins. Specified olefins are non-conjugated diolefins such as dicyclopentadiene and its alkyl derivatives, terpenes and vinylcyclohexene; mono-olefins, cyclic olefins such as cyclohexene; styrene and olefin polymers. In general, C2-20 monomeric olefins and their polymers may be used. The H2:CO ratio is generally 0.5:1 to 10:1, low ratios (0.5-1.5) being preferred for aldehyde production and higher ratios (2-4) for alcohol production. Forms in which the rhodium may be added include metallic rhodium, a rhodium oxide, a salt such as a halide, nitrate, sulfate, sulphite, oleate or stearate or a rhodium carbonyl. A preformed soluble catalyst may be used dissolved in an organic solvent. The catalyst may be deposited on a carrier, generally 1-40 per cent by weight based on rhodium of rhodium compound to the carrier. The catalyst concentration may be from about 0.002 to 20 mol. per cent based on the rhodium to the olefin. The rhodium may be recovered from the product by treatment with water at elevated temperature, e.g. 5-40 per cent by volume water at 80-200 DEG C. In examples: (1) butene-1 is carbonylated to mainly aldehyde products with some acetals and alcohol, reduced rhodium metal/alumina, rhodium sesquioxide and rhodium chloride being mentioned as catalysts; (2) a soluble catalyst is preformed in hexane solution from rhodium sesquioxide and CO/H2 mixture and used for the carbonylation of butene-1; (3) butene-1 is carbonylated using rhodium sesquioxide and the rhodium is recovered from the product by heating with water at 180 DEG C., filtering and drying, and reused; (4) butene-1 is carbonylated using rhodium sesquioxide and the product hydrogenated to amyl alcohols using a nickel catalyst; (5) dicyclopentadiene and alkyl derivatives thereof are carbonylated to the mono-unsaturated aldehyde together with some of the corresponding alcohol using rhodium sesquioxide in hexane solution; the aldehyde may be converted to the acetal and this oxonated further to the aldehyde derivative, which may be hydrolysed to the dialdehyde and subsequently reduced to a glycol; the mono-unsaturated aldehyde may also be reduced to the unsaturated alcohol with metal hydrides and this oxonated further to form, after reduction, a glycol of dicyclopentadiene.