Selective Hydrogenolysis of Glycerol to 1,2-Propanediol over Highly Active and Stable Cu/MgO Catalyst in the Vapor Phase

Highly active, selective, and stable Cu/MgO catalyst was developed for hydrogenolysis of glycerol to 1,2-propanediol (1,2-PDO) in vapor phase. The effect of metal loading, temperature, pressure and weight hourly space velocity (WHSV) on glycerol conversion and 1,2-PDO yield was investigated in a down flow fixed bed tubular reactor. Catalytic results demonstrated that Cu/MgO catalyst promoted the selective hydrogenolysis of C–O bond and limited the cleavage of C–C bond which significantly reduced the selectivity of undesirable products. Very high yield (95.5%) of 1,2-PDO was obtained with 100% conversion of glycerol over 10 wt % Cu/MgO catalyst at very low WHSV of 1.2 h–1, 220 °C, and 0.75 MPa pressure. The superior performance of 10 wt % Cu/MgO catalyst was attributed to the presence of bifunctional acidic-basic sites, small particle size, and synergetic interaction between copper nanoparticles and MgO support. Time-on-stream study and the characterization results of fresh and used catalyst confirmed the ...

[1]  Shashi Kumar,et al.  Selective hydrogenolysis of glycerol to 1,2‐propanediol over highly active copper–magnesia catalysts: reaction parameter, catalyst stability and mechanism study , 2016 .

[2]  P. Biswas,et al.  Vapor phase hydrogenolysis of glycerol to 1,2-propanediol over γ-Al2O3 supported copper or nickel monometallic and copper–nickel bimetallic catalysts , 2016 .

[3]  P. S. Prasad,et al.  Cesium exchanged tungstophosphoric acid supported on tin oxide: An efficient solid acid catalyst for etherification of glycerol with tert-butanol to synthesize biofuel additives , 2016 .

[4]  Xiaohong Wang,et al.  Fabrication of sulfonated carbon catalyst from biomass waste and its use for glycerol esterification , 2015 .

[5]  B. Sarkar,et al.  Selective Hydrogenolysis of Glycerol to 1,2-Propanediol Over Bimetallic Cu-Ni Catalysts Supported on γ-Al2O3 , 2015 .

[6]  Ashish Kumar,et al.  Vapor-phase hydrogenolysis of glycerol over nanostructured Ru/MCM-41 catalysts , 2015 .

[7]  Chih H. Wang,et al.  Hydrogenolysis of glycerol to 1,2-propanediol on copper core-porous silica shell-nanoparticles , 2015 .

[8]  S. Douglas,et al.  Understanding the role of Co in Co–ZnO mixed oxide catalysts for the selective hydrogenolysis of glycerol , 2015 .

[9]  Fereshteh Meshkani,et al.  Carbon dioxide reforming of methane for syngas production over Co–MgO mixed oxide nanocatalysts , 2015 .

[10]  S. Bagheri,et al.  Catalytic conversion of biodiesel derived raw glycerol to value added products , 2015 .

[11]  R. Augustine,et al.  An Efficient, Selective Process for the Conversion of Glycerol to Propylene Glycol Using Fixed Bed Raney Copper Catalysts , 2014 .

[12]  J. Yi,et al.  Effect of nickel on catalytic behaviour of bimetallic Cu–Ni catalyst supported on mesoporous alumina for the hydrogenolysis of glycerol to 1,2-propanediol , 2014 .

[13]  J. Sueiras,et al.  Conversion of glycerol over 10%Ni/γ-Al2O3 catalyst , 2014 .

[14]  Satoshi Sato,et al.  Effect of Ag loading on Cu/Al2O3 catalyst in the production of 1,2-propanediol from glycerol , 2014 .

[15]  C. Pinel,et al.  Synthesis of different ZnO-supported metal systems through microemulsion technique and application to catalytic transformation of glycerol to acetol and 1,2-propanediol , 2014 .

[16]  R. Luque,et al.  Continuous flow transformations of glycerol to valuable products: an overview , 2014 .

[17]  L. Gu,et al.  Selective hydrogenolysis of glycerol to 1,2-propanediol over MgO-nested Raney Cu , 2014, Reaction Kinetics, Mechanisms and Catalysis.

[18]  Catherine Especel,et al.  Polyol hydrogenolysis on supported Pt catalysts: Comparison between glycerol and 1,2-propanediol , 2014 .

[19]  W. Ning,et al.  Multiwall carbon nanotube-pillared layered Cu0.4/Mg5.6Al2O8.6: an efficient catalyst for hydrogenolysis of glycerol , 2013 .

[20]  Xiufang Chen,et al.  Role of ReOx in Re-modified Rh/ZrO2 and Ir/ZrO2 catalysts in glycerol hydrogenolysis: Insights from first-principles study , 2013 .

[21]  Yulei Zhu,et al.  Promoting effect of boron oxide on Cu/SiO2 catalyst for glycerol hydrogenolysis to 1,2-propanediol , 2013 .

[22]  S. Sterchele,et al.  Resin-Based Catalysts for the Hydrogenolysis of Glycerol to Propylene Glycol , 2013, Topics in Catalysis.

[23]  Kangnian Fan,et al.  Physically mixed ZnO and skeletal NiMo for one-pot reforming-hydrogenolysis of glycerol to 1,2-propanediol , 2013 .

[24]  M. Misra,et al.  Simultaneous production of glyceric acid and hydrogen from the photooxidation of crude glycerol using TiSi2 , 2012 .

[25]  P. S. Prasad,et al.  Catalytic hydrogenolysis of biodiesel derived glycerol to 1,2-propanediol over Cu–MgO catalysts , 2012 .

[26]  C. Rode,et al.  Continuous Dehydration and Hydrogenolysis of Glycerol over Non-Chromium Copper Catalyst: Laboratory-Scale Process Studies , 2012 .

[27]  G. Yadav,et al.  Hydrogenolysis of Glycerol to 1,2-Propanediol over Nano-Fibrous Ag-OMS-2 Catalysts , 2012 .

[28]  Xinwen Guo,et al.  Ag/Al2O3 for glycerol hydrogenolysis to 1,2-propanediol: activity, selectivity and deactivation , 2012 .

[29]  Andreas Martin,et al.  Recent developments in dehydration of glycerol toward acrolein over heteropolyacids , 2012 .

[30]  Z. Hou,et al.  Hydrogenolysis of glycerol on bimetallic Pd-Cu/solid-base catalysts prepared via layered double hydroxides precursors , 2011 .

[31]  P. Arias,et al.  Liquid-phase glycerol hydrogenolysis to 1,2-propanediol under nitrogen pressure using 2-propanol as hydrogen source , 2011 .

[32]  R. Gläser,et al.  Catalytic activity of bifunctional transition metal oxide containing phosphated alumina catalysts in the dehydration of glycerol , 2011 .

[33]  H. Friedrich,et al.  Direct Hydrogenolysis of Highly Concentrated Glycerol Solutions Over Supported Ru, Pd and Pt Catalyst Systems , 2011 .

[34]  Yonghai Feng,et al.  Gas phase hydrogenolysis of glycerol catalyzed by Cu/ZnO/MOx (MOx = Al2O3, TiO2, and ZrO2) catalysts , 2011 .

[35]  B. Nagaraja,et al.  Production of hydrogen through the coupling of dehydrogenation and hydrogenation for the synthesis o , 2011 .

[36]  P. Claus,et al.  Selective hydrogenolysis of glycerol over copper catalysts both in liquid and vapour phase: Correlation between the copper surface area and the catalyst's activity , 2011 .

[37]  Rasika B. Mane,et al.  Selective Hydrogenolysis of Glycerol to 1,2-Propanediol: Comparison of Batch and Continuous Process Operations† , 2010 .

[38]  Junhua Wang,et al.  Biodiesel derived glycerol hydrogenolysis to 1,2-propanediol on Cu/MgO catalysts. , 2010, Bioresource technology.

[39]  W. Yuan,et al.  Kinetics of Hydrogenolysis of Glycerol to Propylene Glycol over Cu-ZnO-Al2O3 Catalysts , 2010 .

[40]  Wenjie Shen,et al.  MgO-supported Cu nanoparticles for efficient transfer dehydrogenation of primary aliphatic alcohols , 2009 .

[41]  Masahiro Yokota,et al.  Dehydration–hydrogenation of glycerol into 1,2-propanediol at ambient hydrogen pressure , 2009 .

[42]  I. Fonseca,et al.  Glycerol acetylation over dodecatungstophosphoric acid immobilized into a silica matrix as catalyst , 2009 .

[43]  Satoshi Sato,et al.  Selective Conversion of Glycerol into 1,2-Propanediol at Ambient Hydrogen Pressure , 2009 .

[44]  Yulei Zhu,et al.  Direct Conversion of Glycerol into 1,3-Propanediol over Cu-H4SiW12O40/SiO2 in Vapor Phase , 2009 .

[45]  Long Huang,et al.  Continuous production of 1,2‐propanediol by the selective hydrogenolysis of solvent‐free glycerol under mild conditions , 2008 .

[46]  Yuguo Zheng,et al.  Commodity chemicals derived from glycerol, an important biorefinery feedstock. , 2008, Chemical reviews.

[47]  Satoshi Sato,et al.  Vapor-phase reaction of polyols over copper catalysts , 2008 .

[48]  G. Suppes,et al.  Low-pressure packed-bed gas phase conversion of glycerol to acetol , 2008 .

[49]  Hua Chen,et al.  Hydrogenolysis of glycerol to glycols over ruthenium catalysts: Effect of support and catalyst reduction temperature , 2008 .

[50]  K. R. Rao,et al.  Vapor phase selective hydrogenation of furfural to furfuryl alcohol over Cu–MgO coprecipitated catalysts , 2007 .

[51]  Julien Chaminand,et al.  Glycerol hydrogenolysis on heterogeneous catalysts , 2004 .

[52]  J. Hanson,et al.  Reduction of CuO and Cu2O with H2: H embedding and kinetic effects in the formation of suboxides. , 2003, Journal of the American Chemical Society.

[53]  David G. Barton,et al.  Bifunctional pathways in catalysis by solid acids and bases , 1997 .

[54]  A. Corma,et al.  Organic reactions catalyzed over solid acids , 1997 .

[55]  M. Barteau,et al.  Kinetics and Selectivity of 2-Propanol Conversion on Oxidized Anatase TiO2 , 1997 .