Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-
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Selective Aerobic Oxidation of 5-Hydroxymethylfurfural in Water Over Solid Ruthenium Hydroxide Catalysts with Magnesium-Based Supports Yury Y. Gorbanev • Søren Kegnæs Anders Riisager
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Received: 22 June 2011 / Accepted: 16 September 2011 / Published online: 1 October 2011 Ó Springer Science+Business Media, LLC 2011
Abstract Solid catalyst systems comprised of ruthenium hydroxide supported on magnesium-based carrier materials (spinel, magnesium oxide and hydrotalcite) were investigated for the selective, aqueous aerobic oxidation of the biomass-derived chemical 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid (FDA), a possible plastics precursor. The novel catalyst systems were characterized by nitrogen physisorption, XRPD, TEM and EDS analysis, and applied for the oxidation with no added base at moderate to high pressures of dioxygen and elevated temperatures. The effects of support, temperature and oxidant pressure were studied and optimized to allow a quantitative yield of FDA to be obtained. Keywords 5-Hydroxymethylfurfural 2,5-Furandicarboxylic acid Aerobic oxidation Ruthenium hydroxide catalysts
1 Introduction Biomass is a viable feedstock for production of both chemicals and novel fuels, which eventually can replace crude oil and gas (fossil feedstocks) as major raw materials [1]. 5-Hydroxymethylfurfural (HMF) is a product of the
Electronic supplementary material The online version of this article (doi:10.1007/s10562-011-0707-y) contains supplementary material, which is available to authorized users. Y. Y. Gorbanev S. Kegnæs A. Riisager (&) Centre for Catalysis and Sustainable Chemistry, Department of Chemistry, Technical University of Denmark, DK-2800 Kgs. Lyngby, Denmark e-mail: [email protected]
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dehydration of hexose carbohydrates obtained from lignocellulosic biomass by, e.g. enzymatic hydrolysis [2, 3]. HMF can be readily oxidized to different potentially important products, such as maleic anhydride [4], 2,5-diformylfuran (DFF) [5, 6], 2,5-furandicarboxylic acid (FDA) (Scheme 1) or its dimethyl ester [7–11]. FDA has been established by the US Department of Energy (DOE) biomass program as one of the 12 chemicals that in the future can be used as chemical building block from biomass in biorefineries [12, 13]. In particular, the two carboxylic groups present in FDA make it a valuable polymer building block and hence a possible renewable alternative to terephthalic, isophthalic, adipic and other currently used acids, produced from fossil-based resources [14]. Ruthenium-based catalysts are generally known for their aptitude in aerobic oxidation reactions [15–17] including applications for oxidation of alcohols to produce aldehydes or ketones. Hence, homogeneous Ru-complex catalysts have been found to generate aldehydes or ketones in almost quantitative yields when employed in organic solvents [18, 19] or ionic liquids [20]. A more preferred way to oxidize HMF involves heterogeneous catalysis, due to ease of catalyst separation in possible industrial processes [1]. Accordingly, supported
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