The Role of Metal Halides in Enhancing the Dehydration of Xylose to Furfural

Enslow, Kristopher R.; Bell, Alexis T.

doi:10.1002/cctc.201402842

The Role of Metal Halides in Enhancing the Dehydration of Xylose to Furfural

Journal Article · Tue Jan 13 04:00:00 EST 2015 · ChemCatChem

DOI:https://doi.org/10.1002/cctc.201402842· OSTI ID:1571033

Enslow, Kristopher R. ^[1]; Bell, Alexis T. ^[1]

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

The dehydration of xylose yields furfural, a product of considerable value as both a commodity chemical and a platform for producing a variety of fuels. When xylose is dehydrated in aqueous solution in the presence of a Brønsted acid catalyst, humins are formed via complex side processes that ultimately result in a loss in the yield of furfural. Such degradative processes can be minimized via the insitu extraction of furfural into an organic solvent. The partitioning of furfural from water into a given extracting solvent can be enhanced by the addition of salt to the aqueous phase, a process that increases the thermodynamic activity of furfural in water. Although the thermodynamics of using salts to improve liquid-liquid extraction are well studied, their impact on the kinetics of xylose dehydration catalyzed by a Brønsted acid are not. The aim of the present study was to understand how metal halide salts affect the mechanism and kinetics of xylose dehydration in aqueous solution. We found that the rate of xylose consumption is affected by both the nature of the salt cation and anion, increasing in the order no salt < K⁺ < Na⁺ < Li⁺ and no salt < Cl^- < Br^- < I^-. Furfural selectivity increases similarly with respect to metal cations, but in the order no salt < I^- < Br^- < Cl^- for halide anions. Multinuclear NMR was used to identify the interactions of cations and anions with xylose and to develop a model for explaining xylose-metal halide and water-metal halide interactions. The results of these experiments coupled with ¹⁸O-labeling experiments indicate that xylose dehydration is initiated by protonation at the C₁OH and C₂OH sites, with halide anions acting to stabilize critical intermediates. Finally, the means by which metal halides affect the formation of humins was also investigated, and the role of cations and anions in affecting the selectivity to humins is discussed.

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

Sponsoring Organization:: USDOE Office of Science (SC)

DOE Contract Number:: AC02-05CH11231

OSTI ID:: 1571033

Journal Information:: ChemCatChem, Journal Name: ChemCatChem Journal Issue: 3 Vol. 7; ISSN 1867-3880

Publisher:: ChemPubSoc Europe

Country of Publication:: United States

Language:: English

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