High-yield production of levulinic acid from cellulose and its upgrading to γ-valerolactone

Direct catalytic conversion of cellulose to levulinic acid (LA) by niobium-based solid acids and further upgrading to γ-valerolactone (GVL) on a Ru/C catalyst were realized through sequential reactions in a reactor. Firstly, using aluminium-modified mesoporous niobium phosphate as a catalyst, cellulose can be directly converted to LA with as high as 52.9% yield in aqueous solution, even in the presence of the Ru/C catalyst. To the best of our knowledge, this is the best result over a heterogeneous catalyst so far. It was found that the type of acid (Lewis and Bronsted acids) and acid strength had an influence on the yield of LA; the doping of aluminium can enhance the strong Lewis and Bronsted acids, especially the strong Lewis acid, thus resulting in the increase of LA yield from cellulose as well as from glucose and HMF. Such an enhancement by a Lewis acid on LA yield from HMF was further confirmed by adding lanthanum trifluoroacetate [(TfO)3La], a strong Lewis acid, in the catalytic system (HCl, (TfO)3H, niobium phosphate), indicating that a suitable ratio of Lewis/Bronsted acid is important for higher selectivity to LA from HMF, as well as from cellulose. Then, after replacing N2 with H2, the generated LA in the reaction mixture can be directly converted to γ-valerolactone through hydrogenation over the Ru/C catalyst without further separation of LA.

[1]  G. Centi,et al.  Direct conversion of cellulose to glucose and valuable intermediates in mild reaction conditions over solid acid catalysts , 2012 .

[2]  Xiao-hui Liu,et al.  Direct conversion of cellulose into sorbitol with high yield by a novel mesoporous niobium phosphate supported Ruthenium bifunctional catalyst , 2013 .

[3]  Xiao-hui Liu,et al.  Direct catalytic conversion of furfural to 1,5-pentanediol by hydrogenolysis of the furan ring under mild conditions over Pt/Co2AlO4 catalyst. , 2011, Chemical communications.

[4]  István T. Horváth,et al.  γ-Valerolactone—a sustainable liquid for energy and carbon-based chemicals , 2008 .

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

[6]  Shubin Wu,et al.  Advances in the Catalytic Production of Valuable Levulinic Acid Derivatives , 2012 .

[7]  Hero J. Heeres,et al.  Combined dehydration/(transfer)-hydrogenation of C6-sugars (D-glucose and D-fructose) to γ-valerolactone using ruthenium catalysts , 2009 .

[8]  Leon P.B.M. Janssen,et al.  Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid , 2007 .

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

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

[11]  Bert F. Sels,et al.  Sulfonated silica/carbon nanocomposites as novel catalysts for hydrolysis of cellulose to glucose , 2010 .

[12]  K. Han,et al.  Conversion of glucose into levulinic acid with solid metal(IV) phosphate catalysts , 2013 .

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

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

[15]  B. Lucht,et al.  Effect of NaCl on the conversion of cellulose to glucose and levulinic acid via solid supported acid catalysis , 2011 .

[16]  Michikazu Hara,et al.  Hydrolysis of cellulose by amorphous carbon bearing SO3H, COOH, and OH groups. , 2008, Journal of the American Chemical Society.

[17]  James A. Dumesic,et al.  Production of levulinic acid and gamma-valerolactone (GVL) from cellulose using GVL as a solvent in biphasic systems , 2012 .

[18]  Li Liu,et al.  Selective conversion of cellulose to levulinic acid via microwave-assisted synthesis in ionic liquids. , 2013, Bioresource technology.

[19]  K. Domen,et al.  Glucose production from saccharides using layered transition metal oxide and exfoliated nanosheets as a water-tolerant solid acid catalyst. , 2008, Chemical communications.

[20]  T. A. Nijhuis,et al.  Fructose dehydration to 5-hydroxymethylfurfural over solid acid catalysts in a biphasic system. , 2012, ChemSusChem.

[21]  Xiao-hui Liu,et al.  Mesoporous niobium phosphate: an excellent solid acid for the dehydration of fructose to 5-hydroxymethylfurfural in water , 2012 .

[22]  Leon P.B.M. Janssen,et al.  A kinetic study on the decomposition of 5-hydroxymethylfurfural into levulinic acid , 2006 .

[23]  M. Ziolek,et al.  Niobium Compounds: Preparation, Characterization, and Application in Heterogeneous Catalysis. , 1999, Chemical reviews.

[24]  T. A. Nijhuis,et al.  Glucose dehydration to 5-hydroxymethylfurfural over phosphate catalysts , 2013 .

[25]  Regina Palkovits,et al.  Depolymerization of cellulose using solid catalysts in ionic liquids. , 2008, Angewandte Chemie.

[26]  Sushil K. R. Patil,et al.  Formation and Growth of Humins via Aldol Addition and Condensation during Acid-Catalyzed Conversion of 5-Hydroxymethylfurfural , 2011 .

[27]  Angela S. Rocha,et al.  Comparative performance of niobium phosphates in liquid phase anisole benzylation with benzyl alcohol , 2008 .

[28]  A. Sarkar,et al.  Synthesis of mesoporous niobium oxophosphate using niobium tartrate precursor by soft templating method , 2009 .

[29]  Charles E. Wyman,et al.  Hydrochloric acid‐catalyzed levulinic acid formation from cellulose: data and kinetic model to maximize yields , 2012 .

[30]  David Martin Alonso,et al.  Reactive extraction of levulinate esters and conversion to γ-valerolactone for production of liquid fuels. , 2011, ChemSusChem.

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

[32]  Xiao-hui Liu,et al.  Efficient catalytic conversion of fructose into hydroxymethylfurfural by a novel carbon-based solid acid , 2011 .

[33]  Catherine Pinel,et al.  Cellulose hydrothermal conversion promoted by heterogeneous Bronsted and Lewis acids: Remarkable efficiency of solid Lewis acids to produce lactic acid , 2011 .

[34]  George W. Huber,et al.  Production of levulinic acid from cellulose by hydrothermal decomposition combined with aqueous phase dehydration with a solid acid catalyst , 2012 .

[35]  Robin D. Rogers,et al.  Dissolution of Cellose with Ionic Liquids , 2002 .

[36]  A. Frenkel,et al.  Insights into the interplay of Lewis and Brønsted acid catalysts in glucose and fructose conversion to 5-(hydroxymethyl)furfural and levulinic acid in aqueous media. , 2013, Journal of the American Chemical Society.

[37]  Xiaohong Wang,et al.  One-pot depolymerization of cellulose into glucose and levulinic acid by heteropolyacid ionic liquid catalysis , 2012 .

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

[39]  Honglei Fan,et al.  Conversion of fructose to 5-hydroxymethylfurfural using ionic liquids prepared from renewable materials , 2008 .

[40]  Zhang Yu,et al.  One-Pot Catalytic Conversion of Xylose to Furfural on Mesoporous Niobium Phosphate , 2012 .

[41]  G. Busca,et al.  Acid sites characterization of niobium phosphate catalysts and their activity in fructose dehydration to 5-hydroxymethyl-2-furaldehyde , 2000 .

[42]  K. Ebitani,et al.  Synthesis of levulinic acid from fructose using Amberlyst-15 as a solid acid catalyst , 2012, Reaction Kinetics, Mechanisms and Catalysis.

[43]  M. Hanna,et al.  Levulinic acid production based on extrusion and pressurized batch reaction , 2002 .

[44]  Xiao-hui Liu,et al.  Direct conversion of carbohydrates to 5-hydroxymethylfurfural using Sn-Mont catalyst , 2012 .

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

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