657. FIELD, E., AND HILL, B. L. (Standard Oil Co. of Indiana). Higher Alcohols From Aldehydes. United States Patent 2,587,576, Mar. 6, 1952; appl. filed Dec. 2, 1050, Serial No. 198,918; 10 claims (Cl. 260-638).

Patent Abstracts

657. FIELD, E., AND HILL, B. L. (Standard Oil Co. of Indiana). Higher Alcohols From Aldehydes. United States Patent 2,587,576, Mar. 6, 1952; appl. filed Dec. 2, 1050, Serial No. 198,918; 10 claims (Cl. 260-638).

Normal aldehydes having 2-4 C atoms per mol. Are subjected to 120º-200º and 1,000-10,000 p. s. i. g. in the presence of CO and H₂, in a mol ratio of about 2:1 to 1:4 and about 0.01-0.2 gm.-atoms of Co per mol of reactant aldehyde as a Co carbonyl or Co hydrocarbonyl. By maintaining the reactants under these conditions long enough to establish a mol velocity of not more than 10 mols of aldehyde per hr. per gm.-atom of Co, a condensation hydrogenation of the aldehyde is effected and a polymeric primary alcohol derivative is obtained having at least 2 times as many C atoms per mol. As the aldehyde employed. Thus, acetaldehyde will produce some n-butraldehyde will produce octyl alcohol. Addition of H₂O to the reaction enhances the tendency of these aldehydes to form the condensation products. The solvent for the reaction can be any hydrocarbon solvent. The catalyst can be added as preformed Co carbonyl or hydrocarbonyl or as an aqueous Co salt in a H₂O solution or suspended in oil, or as a H₂O-insoluble compound, such as a slurry or dust of powdered metallic Co. If the catalyst is not preformed 0.1-5% of an inorganic S compound, such as NH₄HS or H₂S, that will convert Co to CoS is introduced into the reactant zone to ensure initial reaction and conversion. In 1 example using acetaldehyde the product contained 11% ethanol, 20% n-butanol, 30% 2-methyl-1-pentanol, and a balance of bottom distillation products, with paraldehyde the product contained 2% ethanol, 11% butanol, 38% mixed hexanols, about 34% mixed octanols, and 15% higher boiling products.