One-pot conversions of lignocellulosic and algal biomass into liquid fuels.

The one-pot conversion of lignocellulosic and algal biomass into a liquid fuel, 2,5-dimethylfuran (DMF), has been achieved by using a multicomponent catalytic system comprising [DMA]⁺ [CH₃SO₃]⁻ (DMA=N,N-dimethylacetamide), Ru/C, and formic acid. The synthesis of DMF from all substrates was carried out under mild reaction conditions. The reaction progressed via 5-hydroxyemthylfurfural (HMF) in the first step followed by hydrogenation and hydrogenolysis of HMF with the Ru/C catalyst and formic acid as a hydrogen source. This report discloses the effectiveness of the Ru/C catalyst for the first time for DMF synthesis from inexpensive and readily abundant biomass sources, which gives a maximum yield of 32 % DMF in 1 h. A reaction route involving 5-(formyloxymethyl)furfural (FMF) as an intermediate has been elucidated based on the ¹H and ¹³C NMR spectroscopic data. Another promising biofuel, 5-ethoxymethylfurfural (EMF), was also synthesized with high selectivity from polymeric carbohydrate-rich biomass substrates by using a Brønsted acidic ionic liquid catalyst, that is [DMA]⁺ [CH₃SO₃]⁻, by etherification of HMF in ethanol.

[1]  Tomohisa Miyazawa,et al.  Development of a Ru/C catalyst for glycerol hydrogenolysis in combination with an ion-exchange resin , 2007 .

[2]  Julie B. Zimmerman,et al.  ALGAE AS A SOURCE OF RENEWABLE CHEMICALS: OPPORTUNITIES AND CHALLENGES , 2011 .

[3]  M. Mascal,et al.  Dramatic advancements in the saccharide to 5-(chloromethyl)furfural conversion reaction. , 2009, ChemSusChem.

[4]  Sudipta De,et al.  Microwave assisted conversion of carbohydrates and biopolymers to 5-hydroxymethylfurfural with aluminium chloride catalyst in water , 2011 .

[5]  Charles E. Wyman,et al.  Cellulose and hemicellulose hydrolysis models for application to current and novel pretreatment processes , 2000 .

[6]  Weiran Yang,et al.  Direct catalytic synthesis of 5-methylfurfural from biomass-derived carbohydrates. , 2011, ChemSusChem.

[7]  C. Zhou,et al.  Catalytic conversion of lignocellulosic biomass to fine chemicals and fuels. , 2011, Chemical Society reviews.

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

[9]  P. Jacobs,et al.  Recent Advances in the Catalytic Conversion of Cellulose , 2011 .

[10]  Bora Kim,et al.  Facile single-step conversion of macroalgal polymeric carbohydrates into biofuels. , 2010, ChemSusChem.

[11]  M. Mascal,et al.  Direct, high-yield conversion of cellulose into biofuel. , 2008, Angewandte Chemie.

[12]  J. Metzger,et al.  Production of liquid hydrocarbons from biomass. , 2006, Angewandte Chemie.

[13]  Ronald T. Raines,et al.  Simple chemical transformation of lignocellulosic biomass into furans for fuels and chemicals. , 2009, Journal of the American Chemical Society.

[14]  A. K. Patra,et al.  Microwave assisted rapid conversion of carbohydrates into 5-hydroxymethylfurfural catalyzed by mesoporous TiO2 nanoparticles , 2011 .

[15]  T. Rauchfuss,et al.  Efficient production of the liquid fuel 2,5-dimethylfuran from fructose using formic acid as a reagent. , 2010, Angewandte Chemie.

[16]  Jürgen O. Metzger Produktion von flüssigen Kohlenwasserstoffen aus Biomasse , 2006 .

[17]  Ferdi Schüth,et al.  Acid hydrolysis of cellulose as the entry point into biorefinery schemes. , 2009, ChemSusChem.

[18]  Vanete Thomaz Soccol,et al.  Biotechnological potential of agro-industrial residues. I: sugarcane bagasse , 2000 .

[19]  C. A. Knutson Use of Phenol-Sulfuric Acid Assay to Determine Composition of Starch-Oil Composites , 1997 .

[20]  P. Jacobs,et al.  Chemocatalytic conversion of cellulose: opportunities, advances and pitfalls , 2011 .

[21]  Lungang Chen,et al.  Aqueous-phase hydrodeoxygenation of carboxylic acids to alcohols or alkanes over supported Ru catalysts , 2011 .

[22]  Alexis T. Bell,et al.  A two-step approach for the catalytic conversion of glucose to 2,5-dimethylfuran in ionic liquids , 2010 .

[23]  Hongming Xu,et al.  Combustion and Emissions of 2,5-Dimethylfuran in a Direct-Injection Spark-Ignition Engine , 2010 .

[24]  Weiran Yang,et al.  One-step catalytic transformation of carbohydrates and cellulosic biomass to 2,5-dimethyltetrahydrofuran for liquid fuels. , 2010, ChemSusChem.

[25]  Johnathan E. Holladay,et al.  Metal Chlorides in Ionic Liquid Solvents Convert Sugars to 5-Hydroxymethylfurfural , 2007, Science.

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

[27]  Yuriy Román‐Leshkov,et al.  Production of dimethylfuran for liquid fuels from biomass-derived carbohydrates , 2007, Nature.

[28]  Jean-Paul Lange,et al.  Conversion of furfuryl alcohol into ethyl levulinate using solid acid catalysts. , 2009, ChemSusChem.

[29]  Chris Somerville,et al.  Feedstocks for Lignocellulosic Biofuels , 2010, Science.

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