Effect of the SiO2 support on the catalytic performance of Ag/ZrO2/SiO2 catalysts for the single-bed production of butadiene from ethanol

Dagle, Vanessa Lebarbier; Flake, Matthew D.; Lemmon, Teresa L.; Lopez, Johnny Saavedra; Kovarik, Libor; Dagle, Robert A.

doi:10.1016/j.apcatb.2018.05.055

Effect of the SiO₂ support on the catalytic performance of Ag/ZrO₂/SiO₂ catalysts for the single-bed production of butadiene from ethanol

Journal Article · Sat May 19 00:00:00 EDT 2018 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2018.05.055· OSTI ID:1439097

Dagle, Vanessa Lebarbier ^[1]; Flake, Matthew D. ^[1]; Lemmon, Teresa L. ^[1]; Lopez, Johnny Saavedra ^[1]; Kovarik, Libor ^[1]; Dagle, Robert A. ^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

A ternary Ag/ZrO₂/SiO₂ catalyst system was studied for single-step conversion of ethanol to butadiene by varying the catalyst composition (Ag, Ir, or Pt metal component, Ag/ZrO₂ loading, and choice of SiO₂ support) and operating conditions (space velocity and feed gas composition). Exceptional catalytic performance was achieved over a 1%Ag/4%ZrO₂/SiO₂-SBA-16 catalyst leading to 99% conversion and 71% butadiene selectivity while operating under mild conditions (325°C, 1 atm, and 0.23 h^–1). Several classes of silica—silica gels, fumed silicas, mesoporous silicas)—were evaluated as catalyst supports, and SBA-16 was found to be the most promising choice. The SiO₂ support was found to significantly influence both conversion and selectivity. A higher SiO₂ catalyst surface area facilitates increased Ag dispersion which leads to greater conversion due to the accelerated initial ethanol dehydrogenation reaction step. By independently varying Ag and ZrO₂ loading, Ag was found to be the main component that affects ethanol conversion. ZrO₂ loading and thus Lewis acid sites concentration was found to have little impact on the ethanol conversion. Butadiene selectivity depends on the concentration of Lewis acid site, which in turn differs depending on the choice of SiO₂ support material. We observed a direct relationship between butadiene selectivity and concentration of Lewis acid sites. Butadiene selectivity decreases as the concentration of Lewis acid sites increases, which corresponds to an increase in ethanol dehydration to ethylene and diethyl ether. Additionally, adding H₂ to the feed had little effect on conversion while improving catalytic stability; however, selectivity to butadiene decreased. Lastly, catalyst regenerability was successfully demonstrated for several cycles.

View Accepted Manuscript (DOE)

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:: 1439097

Alternate ID(s):: OSTI ID: 1514854
OSTI ID: 1591653

Report Number(s):: PNNL-SA--128543; PII: S0926337318304855

Journal Information:: Applied Catalysis B: Environmental, Journal Name: Applied Catalysis B: Environmental Journal Issue: C Vol. 236; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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