Catalytic Conversion of Carbohydrates to Levulinate Ester over Heteropolyanion-Based Ionic Liquids.

An efficient one-pot approach for the production of levulinate ester from renewable carbohydrates is demonstrated over heteropolyanion-based ionic liquid (IL-POM) catalysts with alcohols as the promoters and solvents. The relationships between the structure, acidic strength, and solubility of the IL-POM in methanol and the catalytic performance were studied intensively. A cellulose conversion of 100 % could be achieved with a 71.4 % yield of methyl levulinate over the catalyst [PyPS]3 PW12 O40 [PyPS=1-(3-sulfopropyl)pyridinium] at 150 °C for 5 h. This high efficiency is ascribed to the reasonably high activity of the ionic liquid (IL) catalyst and reaction coupling with rapid in situ esterification of the generated levulinic acid with the alcohol promoter, which allows the insolubility of cellulose encountered in biomass conversion to be overcome. Furthermore, the present process exhibits high feedstock adaptability for typical carbohydrates and handy catalyst recovery by a simple self-separation procedure through temperature control.

[1]  P. Jessop,et al.  Direct Conversion of Mono- and Polysaccharides into 5-Hydroxymethylfurfural Using Ionic-Liquid Mixtures. , 2016, ChemSusChem.

[2]  Hiroyuki Asakura,et al.  Stabilizing a Platinum1 Single-Atom Catalyst on Supported Phosphomolybdic Acid without Compromising Hydrogenation Activity. , 2016, Angewandte Chemie.

[3]  N. Yan,et al.  Rational control of nano-scale metal-catalysts for biomass conversion. , 2016, Chemical communications.

[4]  Maria-Magdalena Titirici,et al.  Levulinic Acid Biorefineries: New Challenges for Efficient Utilization of Biomass. , 2016, ChemSusChem.

[5]  Xiaohong Wang,et al.  Single step conversion of cellulose to levulinic acid using temperature-responsive dodeca-aluminotungstic acid catalysts , 2016 .

[6]  J. Albert,et al.  Expanding the scope of biogenic substrates for the selective production of formic acid from water-insoluble and wet waste biomass , 2015 .

[7]  Amruta Morone,et al.  Levulinic acid production from renewable waste resources: Bottlenecks, potential remedies, advancements and applications , 2015 .

[8]  Yue Shen,et al.  One-pot synthesis of levulinic acid from cellulose in ionic liquids. , 2015, Bioresource technology.

[9]  Xianhai Zeng,et al.  In Situ Catalytic Hydrogenation of Biomass-Derived Methyl Levulinate to γ-Valerolactone in Methanol. , 2015, ChemSusChem.

[10]  R. Bogel-Łukasik,et al.  Acidic ionic liquids as sustainable approach of cellulose and lignocellulosic biomass conversion without additional catalysts. , 2015, ChemSusChem.

[11]  Shiqiang Zhao,et al.  Direct production of ethyl levulinate from carbohydrates catalyzed by H-ZSM-5 supported phosphotungstic acid. , 2015 .

[12]  Yanhui Yang,et al.  One-pot transformation of cellobiose to formic acid and levulinic acid over ionic-liquid-based polyoxometalate hybrids. , 2014, ChemSusChem.

[13]  N. Yan,et al.  Enhanced conversion of carbohydrates to the platform chemical 5-hydroxymethylfurfural using designer ionic liquids. , 2014, ChemSusChem.

[14]  N. Essayem,et al.  Synthesis and Applications of Alkyl Levulinates , 2014 .

[15]  A. Amarasekara,et al.  Acidic Ionic Liquid Catalyzed One-Pot Conversion of Cellulose to Ethyl Levulinate and Levulinic Acid in Ethanol-Water Solvent System , 2014, BioEnergy Research.

[16]  T. Fujitani,et al.  Esterification of levulinic acid with ethanol over sulfated Si-doped ZrO2 solid acid catalyst: Study of the structure–activity relationships , 2014 .

[17]  B. Weckhuysen,et al.  Formation, molecular structure, and morphology of humins in biomass conversion: influence of feedstock and processing conditions. , 2013, ChemSusChem.

[18]  James A. Dumesic,et al.  Gamma-valerolactone, a sustainable platform molecule derived from lignocellulosic biomass , 2013 .

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

[20]  Pei-sheng Ma,et al.  SO₃H-functionalized acidic ionic liquids as catalysts for the hydrolysis of cellulose. , 2013, Carbohydrate polymers.

[21]  G. Dibó,et al.  Microwave-assisted conversion of carbohydrates to levulinic acid: an essential step in biomass conversion , 2013 .

[22]  P. Gallezot,et al.  Conversion of biomass to selected chemical products. , 2012, Chemical Society reviews.

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

[24]  Xue-hui Li,et al.  SO3H-functionalized ionic liquid: efficient catalyst for bagasse liquefaction. , 2011, Bioresource technology.

[25]  S. Tsang,et al.  One step catalytic conversion of cellulose to sustainable chemicals utilizing cooperative ionic liquid pairs , 2011 .

[26]  A. Bell,et al.  A study of the acid-catalyzed hydrolysis of cellulose dissolved in ionic liquids and the factors influencing the dehydration of glucose and the formation of humins. , 2011, ChemSusChem.

[27]  William F. Smith,et al.  Ethyl levulinate: a potential bio-based diluent for biodiesel which improves cold flow properties. , 2011 .

[28]  M. Himmel,et al.  Multi-scale visualization and characterization of lignocellulosic plant cell wall deconstruction during thermochemical pretreatment , 2011 .

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

[30]  Joseph J. Bozell,et al.  Technology development for the production of biobased products from biorefinery carbohydrates—the US Department of Energy’s “Top 10” revisited , 2010 .

[31]  A. Amarasekara,et al.  Hydrolysis and Decomposition of Cellulose in Brönsted Acidic Ionic Liquids Under Mild Conditions , 2009 .

[32]  G. R. Rao,et al.  Characterization of hybrid molecular material prepared by 1-butyl 3-methyl imidazolium bromide and phosphotungstic acid , 2008 .

[33]  Juben Nemchand Chheda,et al.  Katalytische Flüssigphasenumwandlung oxygenierter Kohlenwasserstoffe aus Biomasse zu Treibstoffen und Rohstoffen für die Chemiewirtschaft , 2007 .

[34]  G. Huber,et al.  Liquid-phase catalytic processing of biomass-derived oxygenated hydrocarbons to fuels and chemicals. , 2007, Angewandte Chemie.

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

[36]  L. Janssen,et al.  Kinetic study on the acid-catalyzed hydrolysis of cellulose to levulinic acid , 2007 .

[37]  David K. Johnson,et al.  Biomass Recalcitrance: Engineering Plants and Enzymes for Biofuels Production , 2007, Science.

[38]  A. Fukuoka,et al.  Catalytic conversion of cellulose into sugar alcohols. , 2006, Angewandte Chemie.

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

[40]  Robert J. Davis,et al.  Location, acid strength, and mobility of the acidic protons in Keggin 12-H3PW12O40: a combined solid-state NMR spectroscopy and DFT quantum chemical calculation study. , 2005, Journal of the American Chemical Society.

[41]  H. Olivier-Bourbigou,et al.  Determination of an acidic scale in room temperature ionic liquids. , 2003, Journal of the American Chemical Society.

[42]  Tom Welton,et al.  Room-temperature ionic liquids: solvents for synthesis and catalysis. 2. , 1999, Chemical reviews.

[43]  Abraham Nudelman,et al.  NMR Chemical Shifts of Common Laboratory Solvents as Trace Impurities. , 1997, The Journal of organic chemistry.

[44]  F. Peral,et al.  Self-association of imidazole and its methyl derivatives in aqueous solution. A study by ultraviolet spectroscopy , 1997 .

[45]  Y. Izumi,et al.  Alkali metal salts and ammonium salts of Keggin-type heteropolyacids as solid acid catalysts for liquid-phase Friedel-Crafts reactions , 1995 .

[46]  Sai An,et al.  Efficient conversion of levulinic acid or furfuryl alcohol into alkyl levulinates catalyzed by heteropoly acid and ZrO2 bifunctionalized organosilica nanotubes , 2016 .

[47]  Wang Furong,et al.  Conversion of Cellulose to Butyl Levulinate in Bio-Butanol Medium Catalyzed by Acidic Ionic Liquids , 2015 .

[48]  Jun Wang,et al.  Heteropolyanion-based ionic liquids: reaction-induced self-separation catalysts for esterification. , 2009, Angewandte Chemie.