Research on Hydrogenolysis of Glycerol to 1, 2-Propylene Glycol by Using Supported Raney-Cu/Al_2O_3
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摘要
New supported Raney-Cu catalyst was prepared from pseudo-boehmite powder and copper aluminum alloy powder.It could be used in a continuous-flow fixed-bed reactor and it was also a good catalyst for hydrogenolysis of glycerol to propylene glycol after the two raw materials were processed by the following procedures:molding,drying,calcination,and leaching.XRD,H_2-TPR,as well as SEM technique were employed to study the physicochemical properties of the catalysts,and the hydrogenolysis of glycerol to 1,2-propylene glycol(1,2-PDO)was used as a probe to evaluate the performance of supported skeletal copper catalysts.The test result indicated that CuAl_2 was the main crystal phase of precursor after the dried strips were calcined at 850 ℃ in air.A part of CuAl_2 was oxidized to α-Al_2 O_3,which was the main contributor to the strength of Raney-Cu/Al_2 O_3, while the remaining CuAl_2 was converted to active skeletal copper after the leaching process.The effects of reaction temperature,hydrogen pressure,LHSV,hydrogen-oil ratio,glycerol concentration,and alkaline additives on the catalytic performance were studied in water or ethanol,respectively.Conversion of glycerol and selectivity of 1,2-PDO were 30.9% and 91.4% in water,or 99.0% and 73.6% in the ethanol system,respectively,when the reaction was performed at a temperature of 215 ℃,a H_2 pressure of 3 MPa,a LHSV of 1.0 h~(-1),a hydrogen-oil ratio of 500,and a glycerol concentration of 20%(ethyl alcohol solution).
New supported Raney-Cu catalyst was prepared from pseudo-boehmite powder and copper aluminum alloy powder.It could be used in a continuous-flow fixed-bed reactor and it was also a good catalyst for hydrogenolysis of glycerol to propylene glycol after the two raw materials were processed by the following procedures:molding,drying,calcination,and leaching.XRD,H_2-TPR,as well as SEM technique were employed to study the physicochemical properties of the catalysts,and the hydrogenolysis of glycerol to 1,2-propylene glycol(1,2-PDO)was used as a probe to evaluate the performance of supported skeletal copper catalysts.The test result indicated that CuAl_2 was the main crystal phase of precursor after the dried strips were calcined at 850 ℃ in air.A part of CuAl_2 was oxidized to α-Al_2 O_3,which was the main contributor to the strength of Raney-Cu/Al_2 O_3, while the remaining CuAl_2 was converted to active skeletal copper after the leaching process.The effects of reaction temperature,hydrogen pressure,LHSV,hydrogen-oil ratio,glycerol concentration,and alkaline additives on the catalytic performance were studied in water or ethanol,respectively.Conversion of glycerol and selectivity of 1,2-PDO were 30.9% and 91.4% in water,or 99.0% and 73.6% in the ethanol system,respectively,when the reaction was performed at a temperature of 215 ℃,a H_2 pressure of 3 MPa,a LHSV of 1.0 h~(-1),a hydrogen-oil ratio of 500,and a glycerol concentration of 20%(ethyl alcohol solution).
New supported Raney-Cu catalyst was prepared from pseudo-boehmite powder and copper aluminum alloy powder.It could be used in a continuous-flow fixed-bed reactor and it was also a good catalyst for hydrogenolysis of glycerol to propylene glycol after the two raw materials were processed by the following procedures:molding,drying,calcination,and leaching.XRD,H_2-TPR,as well as SEM technique were employed to study the physicochemical properties of the catalysts,and the hydrogenolysis of glycerol to 1,2-propylene glycol(1,2-PDO)was used as a probe to evaluate the performance of supported skeletal copper catalysts.The test result indicated that CuAl_2 was the main crystal phase of precursor after the dried strips were calcined at 850 ℃ in air.A part of CuAl_2 was oxidized to α-Al_2 O_3,which was the main contributor to the strength of Raney-Cu/Al_2 O_3, while the remaining CuAl_2 was converted to active skeletal copper after the leaching process.The effects of reaction temperature,hydrogen pressure,LHSV,hydrogen-oil ratio,glycerol concentration,and alkaline additives on the catalytic performance were studied in water or ethanol,respectively.Conversion of glycerol and selectivity of 1,2-PDO were 30.9% and 91.4% in water,or 99.0% and 73.6% in the ethanol system,respectively,when the reaction was performed at a temperature of 215 ℃,a H_2 pressure of 3 MPa,a LHSV of 1.0 h~(-1),a hydrogen-oil ratio of 500,and a glycerol concentration of 20%(ethyl alcohol solution).
引文
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[13]Guo L,Zhou J,Mao J,et al.Supported Cu catalysts for the selective hydrogenolysis of glycerol to propanediols[J]Applied Catalysis A:General,2009,367(1/2):93-98
[14]Wang Y,Luo G,Xu X,et al.Preparation of supported skeletal Ni catalyst and its catalytic performance on dicyclopentadiene hydrogenation[J].Catalysis Communications,2014,53(30):15-20
[15]Ma Y Q.Effect of High pressure heat treatment on microstructure and thermal expansion coefficients of CuAl alloy[J].Materials Transactions,2013,54(4):40-543
[16]Lee S Y,Jung J S,Yang E H,et al.Hydrogenolysis of glycerol to 1,2-propanediol over clay based catalysts[J].JNanosci Nanotechnol,2015,15(11):8783-8789
[17]Wang C C,Jiang H,Chen C L.Solvent effect on hydrogenolysis of glycerol to 1,2-propanediol over CuZnO catalyst[J].Chemical Engineering Journal,2015344-350
[18]Vasiliadou E S,Heracleous E,Vasalos I A,et al.Rubased catalysts for glycerol hydrogenolysis-Effect of support and metal precursor[J].Applied Catalysis B:Environmental,2009,92(1):90-99
[19]Zhao J,Yu W,Li D,et al.Catalytic dehydrationhydrogenation of glycerol to 1,2-propylene glycol at ambient hydrogen pressure[J].Chinese Journal of Catalysis,2010,31(2):200-204
[20]Balaraju M,Jagadeeswaraiah K,Prasad P S S,et al Catalytic hydrogenolysis of biodiesel derived glycerol to 1,2-propanediol over Cu-MgO catalysts[J].Catalysis Science&Technology,2012,2(9):1967-1976
[21]Pandhare N N,Pudi S M,Biswas P,et al.Vapor phase hydrogenolysis of glycerol to 1,2-propanediol overγ-Al2O3supported copper or nickel monometallic and coppernickel bimetallic catalysts[J].Journal of the Taiwan Institute of Chemical Engineers,2016,61:90-96
[22]Zhou W,Zhao Y,Ma X B.Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO2catalyst[J].CIESC Journal,2015,66(8):2999-3006
[23]Maris E P,Davis R J.Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts[J].Journal of Catalysis,2007,249(2):328-337
[24]Lu X K,Feng J,Fu H Y,et al.The effect of Pt/TiO2catalyzed hydrogenation of glycerol[C]//National Conference on Environmental Catalysis and Environmental Materials.Chengdu:2009:336-337
[2]Hu Jiye,Liu X,Wang B,et al.Reforming and hydrogenolysis of glycerol over Ni/ZnO catalysts prepared by different methods[J].Chinese Journal of Catalysis2012,33(7/8):1266-1275
[3]Jiménez I.Hydrogenolysis of glycerol to obtain1,2-propanediol on Ce-promoted Ni/SBA-15 catalysts[J]Applied Catalysis B:Environmental,2012,117/118:253-259
[4]Feng Y S,Liu C,Kang Y M,et al.Selective hydrogenolysis of glycerol to 1,2-propanediol catalyzed by supported bimetallic PdCu-KF/γ-Al2O3[J].Chemical Engineering Journal,2015,281:96-101
[5]Gandarias I,Arias P L,Requies J,et al.Hydrogenolysis of glycerol to propanediols over a Pt/ASA catalyst:The role of acid and metal sites on product selectivity and the reaction mechanism[J].Applied Catalysis B:Environmental,2010,97(1):248-256
[6]Guo X,Li Y,Shi R,et al.Co/MgO catalysts for hydrogenolysis of glycerol to 1,2-propanediol[J].Applied Catalysis A:General,2009,371(1/2):108-113
[7]Checa M,Marinas A,Marinas J M,et al.Deactivation study of supported Pt catalyst on glycerol hydrogenolysis[J].Applied Catalysis A:General,2015,507:34-43
[8]Checa M,Auneau F,Hidalgo J.Catalytic transformation of glycerol on several metal systems supported on ZnO[J]Catalysis Today,2012,196(1):91-100
[9]Miyazawa T,Kusunoki Y,Kunimori K,et al.Glycerol conversion in aqueous solution under hydrogen over Ru/C+anion-exchange resin and its reaction mechanism[J]Journal of Catalysis,2006,240(2):213-221
[10]Raju G,Devaiah D,Reddy P S,et al.Hydrogenolysis of bioglycerol to 1,2-propanediol over Ru/CeO2 catalysts:influence of CeO2 characteristics on catalytic performance[J].Applied Petrochemical Research,2014,4(3):297-304
[11]Feng J,Xiong W,Jia Y,et al.Hydrogenolysis of glycerol to 1,2-propanediol over Ru/TiO2 catalyst[J].Chinese Journal of Catalysis,2011,32(9):1545-1549
[12]Wang S,Li Y,Liu H.Selective hydrogenolysis of glycerol to propylene glycol on MgO-Al2O3 dispersed Cu catalysts[J].Acta Chimica Sinica,2012,70(18):1897-1903
[13]Guo L,Zhou J,Mao J,et al.Supported Cu catalysts for the selective hydrogenolysis of glycerol to propanediols[J]Applied Catalysis A:General,2009,367(1/2):93-98
[14]Wang Y,Luo G,Xu X,et al.Preparation of supported skeletal Ni catalyst and its catalytic performance on dicyclopentadiene hydrogenation[J].Catalysis Communications,2014,53(30):15-20
[15]Ma Y Q.Effect of High pressure heat treatment on microstructure and thermal expansion coefficients of CuAl alloy[J].Materials Transactions,2013,54(4):40-543
[16]Lee S Y,Jung J S,Yang E H,et al.Hydrogenolysis of glycerol to 1,2-propanediol over clay based catalysts[J].JNanosci Nanotechnol,2015,15(11):8783-8789
[17]Wang C C,Jiang H,Chen C L.Solvent effect on hydrogenolysis of glycerol to 1,2-propanediol over CuZnO catalyst[J].Chemical Engineering Journal,2015344-350
[18]Vasiliadou E S,Heracleous E,Vasalos I A,et al.Rubased catalysts for glycerol hydrogenolysis-Effect of support and metal precursor[J].Applied Catalysis B:Environmental,2009,92(1):90-99
[19]Zhao J,Yu W,Li D,et al.Catalytic dehydrationhydrogenation of glycerol to 1,2-propylene glycol at ambient hydrogen pressure[J].Chinese Journal of Catalysis,2010,31(2):200-204
[20]Balaraju M,Jagadeeswaraiah K,Prasad P S S,et al Catalytic hydrogenolysis of biodiesel derived glycerol to 1,2-propanediol over Cu-MgO catalysts[J].Catalysis Science&Technology,2012,2(9):1967-1976
[21]Pandhare N N,Pudi S M,Biswas P,et al.Vapor phase hydrogenolysis of glycerol to 1,2-propanediol overγ-Al2O3supported copper or nickel monometallic and coppernickel bimetallic catalysts[J].Journal of the Taiwan Institute of Chemical Engineers,2016,61:90-96
[22]Zhou W,Zhao Y,Ma X B.Continuous hydrogenolysis of glycerol to 1,2-propanediol on highly active Cu/SiO2catalyst[J].CIESC Journal,2015,66(8):2999-3006
[23]Maris E P,Davis R J.Hydrogenolysis of glycerol over carbon-supported Ru and Pt catalysts[J].Journal of Catalysis,2007,249(2):328-337
[24]Lu X K,Feng J,Fu H Y,et al.The effect of Pt/TiO2catalyzed hydrogenation of glycerol[C]//National Conference on Environmental Catalysis and Environmental Materials.Chengdu:2009:336-337