Effect of alkali metal addition on catalytic performance of Ag/ZrO2/SBA-16 catalyst for single-step conversion of ethanol to butadiene

Winkelman, Austin D.; Dagle, Vanessa Lebarbier; Lemmon, Teresa L.; Kovarik, Libor; Wang, Yong; Dagle, Robert A.

doi:10.1039/d2cy01722a

Title: Effect of alkali metal addition on catalytic performance of Ag/ZrO₂/SBA-16 catalyst for single-step conversion of ethanol to butadiene

Journal Article · Tue Dec 13 00:00:00 UTC 2022 · Catalysis Science and Technology

DOI: https://doi.org/10.1039/d2cy01722a · OSTI ID:1922810

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Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Institute for Integrated Catalysis; Washington State Univ., Pullman, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Institute for Integrated Catalysis
Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Institute for Integrated Catalysis; Pacific Northwest National Lab. (PNNL), Richland, WA (United States). Environmental Molecular Sciences Lab. (EMSL)

Here, we describe how adding Na and K to a 4Ag/4ZrO₂/SBA-16 catalyst enhances catalytic performance for single-bed conversion of ethanol to butadiene. While adding Na and K leads to a slight decrease in conversion (i.e., ~10% loss), the production of desired butadiene is significantly increased with up to 50% improvement in productivity for the 4Ag/4ZrO₂/SBA-16 catalyst promoted with 0.5% Na. The reasons for this improvement are a beneficial decrease in Lewis acid site concentration and higher Ag dispersion when Na or K are added, which results in decreased activity involving ethanol dehydration to ethylene and diethyl ether. A remarkable butadiene selectivity of 75% was achieved while maintaining high conversion (i.e., 90%) with 0.5Na/4Ag/4ZrO₂/SBA-16 catalyst. A 72-hour catalyst lifetime study shows that because of higher coke formation from polymerization of desired butadiene, catalyst deactivation occurs more rapidly with the 0.5Na/4Ag/4ZrO₂/SBA-16 (55% loss in conversion) than with 4Ag/4ZrO₂/SBA-16 (45% loss in conversion). However, this does not alter the advantageous effect of Na addition because the butadiene yield remained higher throughout the study period for 0.5Na/4Ag/4ZrO₂/SBA-16. A key finding is that during the reaction, Na limits sintering of Ag particles and promotes selective coking of the acid sites responsible for ethylene and diethyl ether formation.

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Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Biological and Environmental Research (BER)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1922810

Report Number(s):: PNNL-SA--180968

Journal Information:: Catalysis Science and Technology, Journal Name: Catalysis Science and Technology Journal Issue: 4 Vol. 13; ISSN 2044-4753

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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