Hydrogenation of aldehydes

In a continuous process for the production of an aliphatic alcohol containing 2 to 10 carbon atoms by catalytic hydrogenation of an aliphatic aldehyde containing from 2 to 10 carbon atoms, which comprises:

• (i) vaporizing said aldehyde in a hydrogen-containing stream to form a hydrogenation mixture containing vaporous aldehyde and hydrogen, in which mixture the hydrogen:aldehyde molar ratio lies in the range of from about 2:1 to about 100:1;
• (ii) continuously feeding said hydrogenation mixture to a catalytic aldehyde hydrogenation zone containing a charge of a hydrogenation catalyst comprising a reduced mixture of copper oxide and zinc oxide and maintained at a temperature in the range of from about 75.degree. C. to about 300.degree. C. and at a pressure in the range of from about 5 kg/cm.sup.2 absolute to about 50 kg/cm.sup.2 absolute;
• (iii) recovering a product mixture comprising a major amount of product alcohol, a minor amount of by-product ester containing twice as many carbon atoms as the aldehyde and derived from an alkyl carboxylic acid containing the same number of carbon atoms as the product alcohol and from the product alcohol, and excess hydrogen;
• (iv) recycling excess hydrogen to step (i)
• (v) separating by-product ester from product alcohol;
• (vi) supplying make-up hydrogen containing gas;
• (vii) vaporizing by-product ester from step (v) in make-up hydrogen containing gas of step (vi) to form a vaporous mixture containing by-product ester and hydrogen in excess of the stoichiometric amount required to effect hydrogeneolysis of said ester to form, per mole of ester, 2 moles of product alcohol, the vapor pressure of said by-product ester in said vaporous mixture being at least about 0.2 kg/cm.sup.2 ;
• (viii) contacting said vaporous mixture from step (vii) in a secondary catalytic hydrogenation zone with a catalyst consisting essentially of a reduced mixture of copper oxide and zinc oxide, said secondary catalytic hydrogenation zone being maintained at a temperature of from about 160.degree. C. to about 220.degree. C. and at a pressure of from bout 5 kg/cm.sup.2 absolute to about 50 kg/cm.sup.2 absolute;
• and
• (ix) admixing a resulting mixture consisting of excess hydrogen and product alcohol from the secondary catalytic hydrogenation zone with the product mixture of step (iii), whereby express hydrogen from the secondary catalytic hydrogenation zone provides make-up hydrogen for the catalytic aldehyde hydrogenation zone.

In a continuous process for the production of an aliphatic alcohol containing 2 to 10 carbon atoms by catalytic hydrogenation of an aliphatic aldehyde containing 2 to 10 carbon atoms by reaction of a hydrogenation mixture containing the aldehyde and hydrogen in a catalytic aldehyde catalyst effective for the hydrogenation of aldehydes and maintained under aldehyde hydrogenation conditions, followed by recovery of a reaction mixture containing, in addition to product alcohol, a minor amount of a by-product ester containing twice as many carbon atoms as the product alcohol, said ester being derived from an alkyl carboxylic acid containing the same number of carbon atoms at the product alcohol and from the product alcohol, the improvement comprising separating by-product ester from the reaction mixture, and passing an essentially aldehyde-free vaporous mixture comprising by-product ester and hydrogen, in which mixture the vapour pressure of said by-product ester is at least about 0.05 kg/cm.sup.2 over a catalyst consisting of a reduced mixture of copper oxide and zinc oxide and from 0 to 20 percent by weight of at least one carrier material, in a secondary catalytic hydrogenation zone, at a temperature in the range of from about 150.degree. C. to about 240.degree. C. and at a pressure in the range of from about 5 kg/cm.sup.2 absolute up to bout 50 ,kg/cm.sup.2 absolute, and recovering from said secondary catalytic hydrogenation zone a reaction mixture that is substantially free from by-product ester and contains a substantially quantitative yield of further product alcohol corresponding to 2 moles of further product alcohol per mole of by-product ester treated in the secondary catalytic hydrogenation zone.