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Direct Catalytic Conversion of Ethanol to C5+ Ketones: Role of PdZn Alloy on Catalytic Activity and Stability.

Ethanol can be used as a platform molecule for synthesizing valuable chemicals and fuel precursors. Direct synthesis of C 5+ ketones, building blocks for lubricants and hydrocarbon fuels, from ethanol was achieved over a stable Pd-promoted ZnO-ZrO 2 catalyst.  The sequence of reaction steps involved in the C 5+ ketone formation from ethanol was determined. The key reaction steps were found to be the in-situ generation of the acetone intermediate and the cross-aldol condensation between the reaction intermediates acetaldehyde and acetone. The formation of a Pd-Zn alloy in-situ was identified to be the critical factor in maintaining high yield to the C 5+ ketones and the stability of the catalyst. A yield of >70% to C 5+ ketones was achieved over a 0.1% Pd-ZnO-ZrO 2 mixed oxide catalyst, and the catalyst was demonstrated to be stable beyond 2000 hours on stream without any catalyst deactivation.