The electrocatalytic hydrogenation of furanic compounds in a continuous electrocatalytic membrane reactor

The electrocatalytic hydrogenation of biomass derived oxygenates in a continuous electrocatalytic membrane reactor presents a promising method of fuel and chemical production that minimizes usage of solvents and has the potential to be powered using renewable electricity. In this paper we demonstrate the use of a continuous-flow electrocatalytic membrane reactor for the reduction of aqueous solutions of furfural into furfuryl alcohol (FA), tetrahydrofurfuryl alcohol (THFA), 2-methylfuran (MF) and 2-methyltetrahydrofuran (MTHF). Protons needed for hydrogenation were obtained from the electrolysis of water at the anode of the reactor. Pd was identified as the most active monometallic catalyst of 5 different catalysts tested for the hydrogenation of aqueous furfural with hydrogen gas in a high-throughput reactor. Thus Pd/C was tested as a cathode catalyst for the electrocatalytic hydrogenation of furfural. At a power input of 0.1W, Pd/C was 4.4 times more active (per active metal site) as a cathode catalyst in the electrocatalytic hydrogenation of furfural than Pt/C. The main products for the electrocatalytic hydrogenation of furfural were FA (54–100% selectivity) and THFA (0–26% selectivity). MF and MTHF were also detected in selectivities of 8%. Varying the reactor temperature between 30 °C and 70 °C had a minimal effect on reaction rate for furfural conversion. Using hydrogen gas at the anode, in place of water electrolysis, produced slightly higher rates of product formation at a lower power input. Sparging hydrogen gas on the cathode had no effect on reaction rate or selectivity, and was used to examine the addition of recycling loops to the continuous electrocatalytic membrane reactor.

[1]  G. Tompsett,et al.  Electrocatalytic reduction of acetone in a proton-exchange-membrane reactor: a model reaction for the electrocatalytic reduction of biomass. , 2012, ChemSusChem.

[2]  Wenzheng Li,et al.  Simultaneous Generation of Mesoxalic Acid and Electricity from Glycerol on a Gold Anode Catalyst in Anion‐Exchange Membrane Fuel Cells , 2012 .

[3]  Wenzheng Li,et al.  Electrocatalytic oxidation of glycerol on Pt/C in anion-exchange membrane fuel cell: Cogeneration of electricity and valuable chemicals , 2012 .

[4]  Dennis J. Miller,et al.  Aqueous electrocatalytic hydrogenation of furfural using a sacrificial anode , 2012 .

[5]  Jingguang G. Chen,et al.  A new class of electrocatalysts for hydrogen production from water electrolysis: metal monolayers supported on low-cost transition metal carbides. , 2012, Journal of the American Chemical Society.

[6]  Carrie A. Farberow,et al.  Mixed-metal Pt monolayer electrocatalysts with improved CO tolerance. , 2011, Journal of the American Chemical Society.

[7]  J. Vohs,et al.  A direct carbon fuel cell with a molten antimony anode , 2011 .

[8]  A. Sum,et al.  Catalysis in solid oxide fuel cells. , 2011, Annual review of chemical and biomolecular engineering.

[9]  G. Huber,et al.  Production of furfural and carboxylic acids from waste aqueous hemicellulose solutions from the pulp and paper and cellulosic ethanol industries , 2011 .

[10]  C. Wyman,et al.  Renewable gasoline from aqueous phase hydrodeoxygenation of aqueous sugar solutions prepared by hydrolysis of maple wood , 2011 .

[11]  Jingguang G. Chen,et al.  Low-cost hydrogen-evolution catalysts based on monolayer platinum on tungsten monocarbide substrates. , 2010, Angewandte Chemie.

[12]  G. Tompsett,et al.  Renewable high-octane gasoline by aqueous-phase hydrodeoxygenation of C₅ and C₆ carbohydrates over Pt/Zirconium phosphate catalysts. , 2010, ChemSusChem.

[13]  D. M. Alonso,et al.  Catalytic conversion of biomass to biofuels , 2010 .

[14]  A. Dalai,et al.  Hydrodeoxygenation of oleic acid and canola oil over alumina-supported metal nitrides , 2010 .

[15]  E. Chornet,et al.  High Yield Conversion of Residual Pentoses into Furfural via Zeolite Catalysis and Catalytic Hydrogenation of Furfural to 2-Methylfuran , 2010 .

[16]  George W. Huber,et al.  Aqueous-phase hydrodeoxygenation of sorbitol with Pt/SiO2―Al2O3: Identification of reaction intermediates , 2010 .

[17]  M. Casella,et al.  Transition metal-based bimetallic catalysts for the chemoselective hydrogenation of furfuraldehyde , 2010 .

[18]  George W. Huber,et al.  Production of hydrogen, alkanes and polyols by aqueous phase processing of wood-derived pyrolysis oils , 2009 .

[19]  M. Casella,et al.  Bimetallic PtSn catalyst for the selective hydrogenation of furfural to furfuryl alcohol in liquid-phase , 2009 .

[20]  Haisheng Chen,et al.  Progress in electrical energy storage system: A critical review , 2009 .

[21]  Yuqing Wang,et al.  Nano TiO2 film electrode for electrocatalytic reduction of furfural in ionic liquids , 2009 .

[22]  S. Grigoriev,et al.  Evaluation of carbon-supported Pt and Pd nanoparticles for the hydrogen evolution reaction in PEM water electrolysers , 2008 .

[23]  Geping Yin,et al.  Understanding and Approaches for the Durability Issues of Pt-Based Catalysts for PEM Fuel Cell , 2007 .

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

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

[26]  Douglas C. Elliott,et al.  Historical Developments in Hydroprocessing Bio-oils , 2007 .

[27]  V. V. Mahajani,et al.  Kinetics of Liquid-Phase Hydrogenation of Furfuryl Alcohol to Tetrahydrofurfuryl Alcohol over a Ru/TiO2 Catalyst , 2007 .

[28]  Siti Kartom Kamarudin,et al.  Technical design and economic evaluation of a PEM fuel cell system , 2006 .

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

[30]  J. Nørskov,et al.  Hydrogen evolution over bimetallic systems: understanding the trends. , 2006, Chemphyschem : a European journal of chemical physics and physical chemistry.

[31]  Junliang Zhang,et al.  Mixed-metal pt monolayer electrocatalysts for enhanced oxygen reduction kinetics. , 2005, Journal of the American Chemical Society.

[32]  Steven T. Evans,et al.  Hydrogenation of benzene using aqueous solution of polyoxometalates reduced by CO over gold catalysts. , 2005, Journal of the American Chemical Society.

[33]  F. Barbir.  PEM electrolysis for production of hydrogen from renewable energy sources , 2005 .

[34]  Junliang Zhang,et al.  Controlling the catalytic activity of platinum-monolayer electrocatalysts for oxygen reduction with different substrates. , 2005, Angewandte Chemie.

[35]  D. Bessarabov,et al.  A simple model for solid polymer electrolyte (SPE) water electrolysis , 2004 .

[36]  E. M. Belgsir,et al.  Electrochemical investigations of the oxidation–reduction of furfural in aqueous medium: Application to electrosynthesis , 2004 .

[37]  V. V. Mahajani,et al.  Kinetics of Liquid-Phase Hydrogenation of Furfuraldehyde to Furfuryl Alcohol over a Pt/C Catalyst , 2003 .

[38]  T. Paryjczak,et al.  Platinum deposited on monolayer supports in selective hydrogenation of furfural to furfuryl alcohol , 2002 .

[39]  S. Srinivasan,et al.  Quantum jumps in the PEMFC science and technology from the 1960s to the year 2000 Part I. Fundamental scientific aspects , 2001 .

[40]  C. Lamy,et al.  Biomass conversion II: simultaneous electrosyntheses of furoic acid and furfuryl alcohol on modified graphite felt electrodes , 2001 .

[41]  W Smith,et al.  The role of fuel cells in energy storage , 2000 .

[42]  R. Baker,et al.  Furfural hydrogenation over carbon‐supported copper , 1999 .

[43]  R. Baker,et al.  Properties of Copper Chromite Catalysts in Hydrogenation Reactions , 1997 .

[44]  J. Dumesic,et al.  Catalytic routes for the conversion of biomass into liquid hydrocarbon transportation fuels , 2011 .

[45]  M. C. Leikind.  Book Reviews: Chymia: Annual Studies in the History of Chemistry , 1949 .