An Efficient Catalyst for the Conversion of Fructose into Methyl Levulinate

The catalytic alcoholysis of fructose in methanol to methyl levulinate was performed by using phosphotungstic acid iron catalysts. The catalysts were characterized by powder X-ray diffraction, infrared spectroscopy, and X-ray fluorescence spectroscopy. The results showed that the exchanging of H+ with Fe3+ ions could modify the acidity of H3PW12O40 and introduce some Lewis acidity into the molecules. The highest yield of methyl levulinate was obtained over the Fe-HPW-1 catalyst. This catalyst showed 100 % fructose conversion with 73.7 % yield of methyl levulinate at 130 °C, 2 MPa for 2 h, and it could be reused at least five times without obvious loss of activity. The results suggest that the combination of Brønsted acidity with some Lewis acidity could effectively promote the conversion of fructose in methanol to methyl levulinate.Graphical Abstract

[1]  T. Okuhara.  Water-tolerant solid acid catalysts. , 2002, Chemical reviews.

[2]  Nobusuke Kobayashi,et al.  Effects of Brønsted and Lewis acidities on activity and selectivity of heteropolyacid-based catalysts for hydrolysis of cellobiose and cellulose , 2009 .

[3]  K. Shimizu,et al.  Polyvalent-metal salts of heteropolyacid as efficient heterogeneous catalysts for Friedel–Crafts acylation of arenes with carboxylic acids , 2008 .

[4]  Prasant Kumar Rout,et al.  Production of first and second generation biofuels: A comprehensive review , 2010 .

[5]  Jie Fu,et al.  One-pot preparation of methyl levulinate from catalytic alcoholysis of cellulose in near-critical methanol. , 2012, Carbohydrate research.

[6]  D. Hayes.  An examination of biorefining processes, catalysts and challenges , 2009 .

[7]  A. J. Hunt,et al.  Green chemistry and the biorefinery: a partnership for a sustainable future , 2006 .

[8]  M. Misono,et al.  Heteropolyacids. Versatile green catalysts usable in a variety of reaction media , 2000 .

[9]  A. Corma,et al.  Chemical routes for the transformation of biomass into chemicals. , 2007, Chemical reviews.

[10]  Jiping Ma,et al.  Direct conversion of fructose-based carbohydrates to 5-ethoxymethylfurfural catalyzed by AlCl3·6H2O/BF3·(Et)2O in ethanol , 2013 .

[11]  Lu Lin,et al.  Catalytic Conversion of Cellulose to Levulinic Acid by Metal Chlorides , 2010, Molecules.

[12]  Lu Lin,et al.  Extremely low sulfuric acid catalyst system for synthesis of methyl levulinate from glucose , 2012 .

[13]  Lu Lin,et al.  Conversion of carbohydrates biomass into levulinate esters using heterogeneous catalysts , 2011 .

[14]  Dong-Shik Kim,et al.  Recent progress in gasification/pyrolysis technologies for biomass conversion to energy , 2009 .

[15]  Wen‐Sheng Dong,et al.  Highly efficient production of lactic acid from cellulose using lanthanide triflate catalysts , 2013 .

[16]  Shigeru Shimada,et al.  Mixed-acid systems for the catalytic synthesis of methyl levulinate from cellulose , 2011 .

[17]  Anders Riisager,et al.  Conversion of mono- and disaccharides to ethyl levulinate and ethyl pyranoside with sulfonic acid-functionalized ionic liquids. , 2011, ChemSusChem.

[18]  N. Amin,et al.  Optimization of levulinic acid from lignocellulosic biomass using a new hybrid catalyst. , 2012, Bioresource technology.

[19]  A. Corma,et al.  Synthesis of transportation fuels from biomass: chemistry, catalysts, and engineering. , 2006, Chemical reviews.

[20]  Mark Mascal,et al.  Comment on processes for the direct conversion of cellulose or cellulosic biomass into levulinate esters. , 2010, ChemSusChem.

[21]  Ivan V. Kozhevnikov,et al.  Catalysis by Heteropoly Acids and Multicomponent Polyoxometalates in Liquid-Phase Reactions. , 1998, Chemical reviews.

[22]  Xun Hu,et al.  Levulinic esters from the acid-catalysed reactions of sugars and alcohols as part of a bio-refinery , 2011 .

[23]  L. Vane,et al.  Multi-stage continuous culture fermentation of glucose-xylose mixtures to fuel ethanol using genetically engineered Saccharomyces cerevisiae 424A. , 2010, Bioresource technology.

[24]  Anders Riisager,et al.  Solid acid catalysed formation of ethyl levulinate and ethyl glucopyranoside from mono- and disaccharides , 2012 .

[25]  Havva Balat,et al.  Progress in biodiesel processing , 2010 .

[26]  Xiaohong Wang,et al.  Conversion of fructose and glucose into 5-hydroxymethylfurfural catalyzed by a solid heteropolyacid salt , 2011 .

[27]  K. Shimizu,et al.  Polyvalent-metal salts of heteropolyacid as catalyst for Friedel-Crafts alkylation reactions , 2008 .

[28]  D. Petraccone,et al.  New Process for the Acid-Catalyzed Conversion of Cellulosic Biomass (AC3B) into Alkyl Levulinates and Other Esters Using a Unique One-Pot System of Reaction and Product Extraction , 2011 .

[29]  Yulei Zhu,et al.  Design of a highly active silver-exchanged phosphotungstic acid catalyst for glycerol esterification with acetic acid , 2013 .

[30]  Lu Lin,et al.  Solid acid catalyzed glucose conversion to ethyl levulinate , 2011 .

[31]  Jean-Paul Lange,et al.  Valeric biofuels: a platform of cellulosic transportation fuels. , 2010, Angewandte Chemie.

[32]  Leon P.B.M. Janssen,et al.  Green Chemicals: A Kinetic Study on the Conversion of Glucose to Levulinic Acid , 2006 .

[33]  B. Lucht,et al.  Conversion of cellulose to glucose and levulinic acid via solid-supported acid catalysis , 2010 .

[34]  Mark Mascal,et al.  High-yield conversion of plant biomass into the key value-added feedstocks 5-(hydroxymethyl)furfural, levulinic acid, and levulinic esters via 5-(chloromethyl)furfural , 2010 .

[35]  R. Sharma,et al.  Levulinate Esters from Biomass Wastes , 2001 .

[36]  N. Essayem,et al.  Cellulose Reactivity in Supercritical Methanol in the Presence of Solid Acid Catalysts: Direct Synthesis of Methyl-levulinate , 2011 .