The formation of ketones in the presence of carbon monoxide over CuO/ZnO/Al sub 2 O sub 3

• Published in: Journal of catalysis 1989-10, Vol.119:2
• Main Authors: Elliott, D.J., Pennella, F.
• Format: Article
• Language: English
• Subjects: 01 COAL, LIGNITE, AND PEAT; 010408 - Coal, Lignite, & Peat- C1 Processes- (1987-); 10 SYNTHETIC FUELS; 100200 - Synthetic Fuels- Production- (1990-); ALCOHOLS; ALDEHYDES; ALUMINIUM COMPOUNDS; ALUMINIUM OXIDES; CARBON COMPOUNDS; CARBON MONOXIDE; CARBON OXIDES; CATALYSTS; CATALYTIC EFFECTS; CHALCOGENIDES; CHEMICAL REACTION KINETICS; COPPER COMPOUNDS; COPPER OXIDES; CRYSTAL STRUCTURE; ELEMENTS; ESTERS; FLUIDS; GASES; HYDROXY COMPOUNDS; KETONES; KINETICS; LABELLED COMPOUNDS; METHANOL; MOLECULAR STRUCTURE; NITROGEN; NONMETALS; ORGANIC COMPOUNDS; OXIDES; OXYGEN; OXYGEN COMPOUNDS; PRESSURE DEPENDENCE; REACTION KINETICS; SURFACE PROPERTIES; SYNTHESIS; SYNTHESIS GAS; TRANSITION ELEMENT COMPOUNDS; ZINC COMPOUNDS; ZINC OXIDES
• ISSN: 0021-9517; 1090-2694
• DOI: 10.1016/0021-9517(89)90166-8

The reaction of linear primary alcohols over CuO/AnO/Al{sub 2}O{sub 3} was studied under nitrogen and under carbon monoxide at 285 C and 1 to 65 atm. The principal products for alcohols with n carbon atoms were, in addition to the corresponding aldehydes, esters with 2n carbon atoms, ketones with 2n carbon atoms, and ketones with 2n-1 carbon atoms. Under nitrogen the esters predominated, but under 65 atm of carbon monoxide the principal condensation products were ketones with 2n carbon atoms. Isotopic labeling studies showed that carbon from CO was not incorporated into the esters and ketones, that oxygen, on the other hand, was exchanged between CO and the reaction products, and that the ketones were formed by an aldol-type mechanism. The changes in selectivity observed under carbon monoxide are attributed to changes in the catalyst surface resulting from the removal of lattice oxygen by the CO and the formation of oxygen vacancies.