4.6 Article

Single-step conversion of cellulose to 5-hydroxymethylfurfural (HMF), a versatile platform chemical

Journal

APPLIED CATALYSIS A-GENERAL
Volume 361, Issue 1-2, Pages 117-122

Publisher

ELSEVIER SCIENCE BV
DOI: 10.1016/j.apcata.2009.04.002

Keywords

5-Hydroxymethylfurfural; HMF; Ionic liquid; 1-Alkyl-3-methylimidazolium chloride; 1-Ethyl-3-methyl-imidazolium chloride; Glucose; Cellobiose; Maltose; Cellulose conversion; Paired metal chlorides; CuCl2; CrCl2

Funding

  1. Pacific Northwest National Lab (PNNL) [DE-AC06-76RL01830]

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The ability to use cellulosic biomass as feedstock for the large-scale production of liquid fuels and chemicals depends critically on the development of effective low temperature processes. One promising biomass-derived platform chemical is 5-hydroxymethylfurfural (HMF), which is suitable for alternative polymers or for liquid biofuels. While HMF can currently be made from fructose and glucose, the ability to synthesize HMF directly from raw natural cellulose would remove a major barrier to the development of a sustainable HMF platform. Here we report a single-step catalytic process where cellulose as the feed is rapidly depolymerized and the resulting glucose is converted to HMF under mild conditions. A pair of metal chlorides (CuCl2 and CrCl2) dissolved in 1-ethyl-3-methylimidazolium chloride ([EMIM]Cl) at temperatures of 80-120 degrees C collectively catalyze the single-step process of converting cellulose to HMF with an unrefined 96% purity among recoverable products (at 55.4 +/- 4.0% HMF yield). After extractive separation of HMF from the solvent, the catalytic performance of recovered [EMIM]Cl and the catalysts was maintained in repeated uses. Cellulose depolymerization occurs at a rate that is about one order of magnitude faster than conventional acid-catalyzed hydrolysis. In contrast, single metal chlorides at the same total loading showed considerably less activity under similar conditions. (C) 2009 Published by Elsevier B.V.

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