Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO2 Catalysts

Miyake, Naomi; Brezicki, Gordon; Davis, Robert J.

doi:10.1021/acssuschemeng.1c07459

Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO₂ Catalysts

Journal Article · Tue Jan 04 00:00:00 EST 2022 · ACS Sustainable Chemistry & Engineering

DOI:https://doi.org/10.1021/acssuschemeng.1c07459· OSTI ID:1865052

Miyake, Naomi ^[1]; Brezicki, Gordon ^[2]; ^[2]

Univ. of Virginia, Charlottesville, VA (United States); University of Virginia
Univ. of Virginia, Charlottesville, VA (United States)

Although butadiene is currently a by-product of naphtha cracking, interest in producing butadiene from bio-based ethanol has increased because of the lower environmental impact of the ethanol to butadiene reaction. Furthermore, this work explores a multifunctional catalyst system composed of silica-supported Ag and ZrO₂ used for the cascade reaction of ethanol to butadiene at 573 K. The Ag and ZrO₂ components were synthesized on separate support particles enabling characterization of each component without interference from the other. High selectivity to butadiene (65%) at high ethanol conversion (75%) was achieved with an appropriate ratio of Ag and ZrO₂ in the reactor. Silver catalyzed the initial dehydrogenation of ethanol to acetaldehyde while ZrO₂ catalyzed the C-C coupling and subsequent dehydration reactions. The silica-supported ZrO₂ exhibited superior selectivity relative to bulk ZrO₂ in the Ag-promoted ethanol to butadiene reaction. Results from Zr K-edge X-ray absorption spectroscopy and UV-Vis spectroscopy showed that ZrO₂ was highly dispersed on the silica support over a range of loadings. Infrared spectroscopy of adsorbed pyridine, CO, and CO₂, and kinetics of probe reactions 1-butene double bond isomerization, 2-propanol decomposition, and ethanol hydrogenation of acetone were used to compare the acid-base nature and chemical reactivity of silica-supported ZrO₂ to bulk ZrO₂.

View Accepted Manuscript (DOE)

Research Organization:: Univ. of Virginia, Charlottesville, VA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02-95ER14549; SC0012704

OSTI ID:: 1865052

Alternate ID(s):: OSTI ID: 1903144

Journal Information:: ACS Sustainable Chemistry & Engineering, Journal Name: ACS Sustainable Chemistry & Engineering Journal Issue: 2 Vol. 10; ISSN 2168-0485

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO2 Catalysts

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Cascade Reaction of Ethanol to Butadiene over Multifunctional Silica-Supported Ag and ZrO₂ Catalysts