Direct Catalytic Conversion of Ethanol to C 5+ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Subramaniam, Senthil; Guo, Mond F.; Bathena, Tanmayi; Gray, Michel; Zhang, Xiao; Martinez, Abraham; Kovarik, Libor; Goulas, Konstantinos A.; Ramasamy, Karthikeyan K.

doi:10.1002/ange.202005256

Direct Catalytic Conversion of Ethanol to C ₅₊ Ketones: Role of Pd–Zn Alloy on Catalytic Activity and Stability

Journal Article · Fri Jul 03 00:00:00 EDT 2020 · Angewandte Chemie

DOI:https://doi.org/10.1002/ange.202005256· OSTI ID:1637130

Subramaniam, Senthil ^[1]; ^[1]; Bathena, Tanmayi ^[2]; Gray, Michel ^[3]; Zhang, Xiao ^[1]; Martinez, Abraham ^[3]; Kovarik, Libor ^[3]; Goulas, Konstantinos A. ^[2]; ^[3]

Chemical and Biological Processing Group Pacific Northwest National Laboratory Richland WA 99354 USA, The Gene and Linda Voiland School of Chemical Engineering and Bioengineering Washington State University Pullman WA 99164 USA
Chemical, Biological, and Environmental Engineering Oregon State University Corvallis OR 97331 USA
Chemical and Biological Processing Group Pacific Northwest National Laboratory Richland WA 99354 USA

Abstract

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.

View Accepted Manuscript (Publisher)

Sponsoring Organization:: USDOE

OSTI ID:: 1637130

Journal Information:: Angewandte Chemie, Journal Name: Angewandte Chemie Journal Issue: 34 Vol. 132; ISSN 0044-8249

Publisher:: Wiley Blackwell (John Wiley & Sons)Copyright Statement

Country of Publication:: Germany

Language:: English

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