Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives

Alegre-Requena, Juan V.; Hafenstine, Glenn R.; Huo, Xiangchen; Guan, Yanfei; Stunkel, Jim; Baddour, Frederick G.; Unocic, Kinga A.; Klein, Bruno; Davis, Ryan E.; Paton, Robert S.; Vardon, Derek R.; Kim, Seonah

doi:10.1016/j.cej.2023.143346

Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives

Journal Article · 08 May 2023 · Biochemical Engineering Journal

DOI:https://doi.org/10.1016/j.cej.2023.143346· OSTI ID:1984221

Alegre-Requena, Juan V.; Hafenstine, Glenn R.; Huo, Xiangchen; Guan, Yanfei; Stunkel, Jim; ; Unocic, Kinga A.; Klein, Bruno; ; Paton, Robert S.; ;

Silica-supported phosphoric acid and metal phosphate catalyzed 1,3-butadiene (BDE) production from 2,3-butanediol (2,3-BDO) was studied using experimental and computational techniques. The catalyst was initially tested in a continuous flow reactor using commercially available 2,3-BDO, leading to maximum BDE yields of 63C%. Quantum chemical mechanistic studies revealed 1,2-epoxybutane is a kinetically viable and thermodynamically stable intermediate, supported by experimental demonstration that this epoxide can be converted to BDE under standard reaction conditions. Newly proposed E2 and SN2' elementary steps were studied to rationalize the formation of BDE and all detected side-products. Additionally, using quantum mechanics/molecular mechanics (QM/MM) calculations, we modeled silica-supported phosphate catalysts to study the effect of the alkali metal center. Natural population analysis showed that phosphate oxygen atoms are more negatively charged in CsH2PO4/SiO2 than in H3PO4/SiO2. In combination with temperature-programmed desorption experiments using CO2, the results of this study suggest that the improved selectivity achieved when adding the metal center is related to an increase in the basicity of the catalyst.

Research Organization:: National Renewable Energy Laboratory (NREL), Golden, CO (United States)

Sponsoring Organization:: USDOE Office of Energy Efficiency and Renewable Energy (EERE), Transportation Office. Bioenergy Technologies Office; USDOE Consortium for Computational Physics and Chemistry (CCPC); USDOE Chemical Catalysis for Bioenergy Consortium (ChemCatBio)

DOE Contract Number:: AC36-08GO28308

OSTI ID:: 1984221

Report Number(s):: NREL/JA-5100-86476; MainId:87249; UUID:77253fb8-a378-4f47-800f-8773d7efd7c2; MainAdminID:69706

Journal Information:: Biochemical Engineering Journal, Vol. 466

Country of Publication:: United States

Language:: English

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INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
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butanediol
computational chemistry
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heterogeneous catalysis
mechanistic studies
QM/MM

Experimental and Computational Studies of the Production of 1,3-Butadiene from 2,3-Butanediol Using SiO2-Supported H3PO4 Derivatives

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