Kinetics of hydrogenation and hydrogenolysis of 2,5-dimethylfuran over noble metals catalysts under mild conditions

Louie, Ying Lin; Tang, Joseph; Hell, Alexander M. L.; Bell, Alexis T.

doi:10.1016/j.apcatb.2016.09.046

Title: Kinetics of hydrogenation and hydrogenolysis of 2,5-dimethylfuran over noble metals catalysts under mild conditions

Journal Article · Wed Mar 01 00:00:00 EST 2017 · Applied Catalysis B: Environmental

DOI:https://doi.org/10.1016/j.apcatb.2016.09.046· OSTI ID:1571080

Louie, Ying Lin ^[1];

^[1];

^[1]; Bell, Alexis T. ^[1]

Univ. of California, Berkeley, CA (United States). Energy Biosciences Inst., and Dept. of Chemical and Biomolecular Engineering

Ketones, derived via the selective ring-opening hydrogenation of biomass-derived furanic compounds, are useful synthons for the production of fuels and lubricant. In this study, 2,5-dimethylfuran (DMF) was used as a model to investigate the liquid-phase hydrogenation of substituted furans over noble metals. The activity and selectivity of carbon-supported Pt, Pd, Rh, and Ru were compared under identical conditions. Pt/C exhibited the highest activity and selectivity for C—O bond hydrogenolysis, whereas all other catalysts exhibited a high selectivity for ring hydrogenation to form 2,5-dimethyltetrahydrofuran. The reaction kinetics were measured in detail for liquid-phase hydrogenation of DMF over Pt/C, under conditions that excluded the effects of internal or external mass transfer (333 K–363 K, p_H2 = 0.41–0.69 MPa). A reaction mechanism is proposed to explain the parallel formation of 2,5-dimethyltetrahydrofuran, 2-hexanone, and 2-hexanol. This mechanism is consistent with what is known about the adsorption of DMF on Pt, and explains why ring opening occurs directly from adsorbed DMF and not via secondary reaction of 2,5-dimethyltetrahydrofuran. The kinetics of DMF hydrogenation are well represented by the mechanism and the assumption of non-competitive adsorption of organic species and hydrogen atoms. The step involving C—O bond cleavage of the aromatic ring had the highest activation energy, 45.4 kJ/mol, and is favored over the steps involving C═C bond hydrogenation of the furan ring at elevated temperatures and low p_H2. Finally, the reaction kinetics reveal that DMF hydrogenation can be tuned to produce 2-hexanone with 92% selectivity at 100% conversion under relatively mild liquid phase conditions (0.41 MPa, 393 K).

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Research Organization:: Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)

Sponsoring Organization:: USDOE Office of Science (SC)

Grant/Contract Number:: AC02-05CH11231

OSTI ID:: 1571080

Journal Information:: Applied Catalysis B: Environmental, Vol. 202, Issue C; ISSN 0926-3373

Publisher:: ElsevierCopyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 36 works

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Spectroscopic characterization of a highly selective NiCu ₃ /C hydrodeoxygenation catalyst Goulas, Konstantinos A.; Lee, Jennifer D.; Zheng, Weiqing Catalysis Science & Technology, Vol. 8, Issue 23 https://doi.org/10.1039/c8cy01280f	journal	January 2018

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
dimethylfuran
hydrogenation
platinum
ring-opening
kinetic models

Title: Kinetics of hydrogenation and hydrogenolysis of 2,5-dimethylfuran over noble metals catalysts under mild conditions

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