碱催化促进Ni-W/β分子筛催化剂氢解纤维素产1,2-丙二醇的研究
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摘要
为提高纤维素催化氢解产醇类产物中1,2-丙二醇(1,2-PG)的收率,采用等体积浸渍法制备了以β分子筛为载体负载Ni和W的催化剂。结果表明,当7Ni-20W/β分子筛作为催化剂时,在240℃反应温度和6.0 MPa H_2的条件下反应30 min后,纤维素实现完全转化,1,2-PG和乙二醇(EG)产率分别达到19.3%和45.3%;不同于其他载体催化剂,β分子筛可以明显提高1,2-PG选择性。当不同碱催化剂加入到Ni-W/β分子筛催化剂反应体系后,可以进一步提高1,2-PG的选择性。尤其是当加入Ba(OH)_2后,1,2-丙二醇产率从19.3%提高了32.5%。为了探究碱催化剂在反应中的作用,以葡萄糖为底物进行了一系列的碱催化反应。结果表明,碱催化剂主要作用是有助于将葡萄糖异构化为果糖,从而促进纤维素转化为1,2-PG。催化剂在两次回收重复利用之后1,2-PG的收率只下降3.9%,乙二醇产率收率下降4.1%。
A series of Ni-W/β zeolite catalysts were prepared via incipient impregnation method in order to improve the yield of 1,2-propylene glycol(1,2-PG) in the alcohol products of cellulose hydrogenation.Under the reaction conditions of 240℃ and 6.0 MPa H_2 for 30 min,the complete conversion of cellulose was obtained and the yields of 1,2 propylene glycol and ethylene glycol(EG) were 19.3% and 45.3%,respectively.Different from other supports,the selectivity of 1,2-PG was highly improved when β zeolite was used.The selectivity of 1,2-PG was further improved after the addition of alkaline,and the yield of 1,2-PG was up to 32.5% especially for Ba(OH)_2.The function of alkaline catalysts in the reaction was also discussed based on a series of reactions using glucose as the substrate,indicating that alkaline was favorable for the isomerization of glucose to fructose and thus promoted the conversion of cellulose into 1,2-PG.After two cycles of reuse,the yield of 1,2-PG and EG slightly decreased(3.9%and 4.1%,respectively).
A series of Ni-W/β zeolite catalysts were prepared via incipient impregnation method in order to improve the yield of 1,2-propylene glycol(1,2-PG) in the alcohol products of cellulose hydrogenation.Under the reaction conditions of 240℃ and 6.0 MPa H_2 for 30 min,the complete conversion of cellulose was obtained and the yields of 1,2 propylene glycol and ethylene glycol(EG) were 19.3% and 45.3%,respectively.Different from other supports,the selectivity of 1,2-PG was highly improved when β zeolite was used.The selectivity of 1,2-PG was further improved after the addition of alkaline,and the yield of 1,2-PG was up to 32.5% especially for Ba(OH)_2.The function of alkaline catalysts in the reaction was also discussed based on a series of reactions using glucose as the substrate,indicating that alkaline was favorable for the isomerization of glucose to fructose and thus promoted the conversion of cellulose into 1,2-PG.After two cycles of reuse,the yield of 1,2-PG and EG slightly decreased(3.9%and 4.1%,respectively).
引文
[1]冯君锋,蒋剑春,徐俊明,贺小亮.生物质加压液化制备甲基糖苷与酚类物质[J].燃料化学学报,2014,42(4):434-442.(FENG Jun-feng,JIANG Jian-chun,XU Jun-ming,HE Xiao-liang.Preparation of methyl glucosides and phenols through the liquefaction of biomass with methanol under high pressure[J].J Fuel Chem Technol,2014,42(4):434-442.)
[2]张少春.纤维素催化转化制备多元醇和5-段甲基糠醛[D].大连:大连理工大学,2010.(ZHNAG Shao-chun.Catalytie conversion of cellulose into Polyols and 5-hydroxy methylfurfural[D].Dalian:Dalian University of Technology,2010.)
[3]RUPPERT A M,WEINBERG K,PALKOVITS R.Hydrogenolysis goes bio:from carbohydrates and sugar alcohols to platform chemicals[J].Angew Chem Int Ed,2012,51(11):2564-2601.
[4]LI C,WANG Q,ZHAO Z K.Acid in ionic liquid:An efficient system for hydrolysis of lignocellulose[J].Green Chem,2008,10(2):177-182.
[5]LOU C,WANG S,LIU H.Cellulose conversion into polyols catalyzed by reversibly formed acids and supported ruthenium clusters in hot water[J].Angew Chem Int Ed,2007,46(40):7636-7639.
[6]FUKOUKA A,DHEPE P L.Catalytic conversion of cellulose into sugar alcohols[J].Angew Chem Int Ed,2006,45(31):5161-5163.
[7]DENG T,LIU H.Promoting effect of SnO_x on selective conversion of cellulose to polyols over bimetallic Pt-SnO_x/Al_2O_3 catalysts[J].Green Chem,2013,15(1):116-124.
[8]JI N,ZHANG T,ZHENG M,WANG A,WANG H,WANG X,CHEN J G.Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts[J].Angew Chem Int Ed,2008,120(44):8638-8641.
[9]曹月领,王军威,李其峰,殷宁,刘振民,亢茂青,朱玉雷.Ni-WO_3/SBA-15催化剂上纤维素的水解加氢[J].燃料化学学报,2013,41(8):943-949.(CAO Yue-ling,WANG Jun-wei,LI Qi-feng,YIN Ning,LIU Zhen-min,KANG Mao-qing,ZHU Yu-lei.Hydrolytic hydrogenation of cellulose over Ni-WO_3/SBA-15 catalysts Ni-WO_3/SBA-15[J].J Fuel Chem Technol,2013,41(8):943-949.)
[10]XIAO Z,JIN S,PANG M,LIANG C.Conversion of highly concentrated cellulose to 1,2-propanediol and ethylene glycol over highly efficient CuCr catalysts[J].Green Chem,2013,15(4):891-895.
[11]ZHENG M Y,WANG A Q,JI N,PANG J F,WANG X D,ZHANG T.Transition metal-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol[J].Chem Sus Chem,2010,3(1):63-66.
[12]DONG W,SHEN Z,PENG B,GU M,ZHOU X,XIANG B,ZAHNG Y.Selective chemical conversion of sugars in aqueous solutions without alkali to lactic acid over a Zn-Sn-Beta lewis acid-base catalyst[J].Sci Rep,2016,6:26713.
[13]DIJKMANS J,GABRIELS D,DUSSELIER M,DE CLIPPEL F,VANELDEREN P,HOUTHOOFD K,MALFLIEF A,PONTIKES Y,SELS B F.Productive sugar isomerization with highly active Sn in dealuminatedβzeolites[J].Green Chem,2013,15(10):2777-2785.
[14]HIRANO Y,SAGATA K,KIT A Y.Selective transformation of glucose into propylene glycol on Ru/C catalysts combined with ZnO under low hydrogen pressures[J].Appl Catal A:Gen,2015,502:1-7.
[15]ZHANG Y,WANG A,ZHANG T.A new 3D mesoporous carbon replicated from commercial silica as a catalyst support for direct conversion of cellulose into ethylene glycol[J].Chem Commun,2010,46(6):862-864.
[16]BERMEJO-DEVAL R,ASSARY R S,NIKOLLA E,MOLINER M,ROMAN-LESHKOV Y,HWANG S-J,PALSDOTTIR A,SILVERMAN D,LOBOR F,CURTISS L A.Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites[J].Proc Natl Acad Sci,2012,109(25):9727-9732.
[17]MIZUGAKI T,YAMAKAWA T,ARUNDHATHI R,MITSUDOME T JITSUKAWA K,KANEDA K.Selective hydrogenolysis of glycerol to1,3-propanediol catalyzed by Pt nanoparticles-AlO_x/WO_3[J].Chem Lett,2012,41(12):1720-1722.
[18]KOBAYASHI H,ITO Y,KOMANOYA T,HOSAKA Y,DHEPE PL,KASAI K,HARA K,FUKOUKA A.Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts[J].Green Chem,2011,13(2):326-333.
[19]GUO X,LI Y,SHI R,LIU Q,ZHAN E,SHEN W.Co/MgO catalysts for hydrogenolysis of glycerol to 1,2-propanediol[J].Appl Catal,2009,371(1):108-113.
[20]HOLM M S,PAGAN-TORRES Y J,SARAVANAMURUGAN S,RIISAGER A,DUMESIC J A,TAARNING E.Sn-Beta catalysed conversion of hemicellulosic sugars[J].Green Chem,2012,14(3):702-706.
[2]张少春.纤维素催化转化制备多元醇和5-段甲基糠醛[D].大连:大连理工大学,2010.(ZHNAG Shao-chun.Catalytie conversion of cellulose into Polyols and 5-hydroxy methylfurfural[D].Dalian:Dalian University of Technology,2010.)
[3]RUPPERT A M,WEINBERG K,PALKOVITS R.Hydrogenolysis goes bio:from carbohydrates and sugar alcohols to platform chemicals[J].Angew Chem Int Ed,2012,51(11):2564-2601.
[4]LI C,WANG Q,ZHAO Z K.Acid in ionic liquid:An efficient system for hydrolysis of lignocellulose[J].Green Chem,2008,10(2):177-182.
[5]LOU C,WANG S,LIU H.Cellulose conversion into polyols catalyzed by reversibly formed acids and supported ruthenium clusters in hot water[J].Angew Chem Int Ed,2007,46(40):7636-7639.
[6]FUKOUKA A,DHEPE P L.Catalytic conversion of cellulose into sugar alcohols[J].Angew Chem Int Ed,2006,45(31):5161-5163.
[7]DENG T,LIU H.Promoting effect of SnO_x on selective conversion of cellulose to polyols over bimetallic Pt-SnO_x/Al_2O_3 catalysts[J].Green Chem,2013,15(1):116-124.
[8]JI N,ZHANG T,ZHENG M,WANG A,WANG H,WANG X,CHEN J G.Direct catalytic conversion of cellulose into ethylene glycol using nickel-promoted tungsten carbide catalysts[J].Angew Chem Int Ed,2008,120(44):8638-8641.
[9]曹月领,王军威,李其峰,殷宁,刘振民,亢茂青,朱玉雷.Ni-WO_3/SBA-15催化剂上纤维素的水解加氢[J].燃料化学学报,2013,41(8):943-949.(CAO Yue-ling,WANG Jun-wei,LI Qi-feng,YIN Ning,LIU Zhen-min,KANG Mao-qing,ZHU Yu-lei.Hydrolytic hydrogenation of cellulose over Ni-WO_3/SBA-15 catalysts Ni-WO_3/SBA-15[J].J Fuel Chem Technol,2013,41(8):943-949.)
[10]XIAO Z,JIN S,PANG M,LIANG C.Conversion of highly concentrated cellulose to 1,2-propanediol and ethylene glycol over highly efficient CuCr catalysts[J].Green Chem,2013,15(4):891-895.
[11]ZHENG M Y,WANG A Q,JI N,PANG J F,WANG X D,ZHANG T.Transition metal-tungsten bimetallic catalysts for the conversion of cellulose into ethylene glycol[J].Chem Sus Chem,2010,3(1):63-66.
[12]DONG W,SHEN Z,PENG B,GU M,ZHOU X,XIANG B,ZAHNG Y.Selective chemical conversion of sugars in aqueous solutions without alkali to lactic acid over a Zn-Sn-Beta lewis acid-base catalyst[J].Sci Rep,2016,6:26713.
[13]DIJKMANS J,GABRIELS D,DUSSELIER M,DE CLIPPEL F,VANELDEREN P,HOUTHOOFD K,MALFLIEF A,PONTIKES Y,SELS B F.Productive sugar isomerization with highly active Sn in dealuminatedβzeolites[J].Green Chem,2013,15(10):2777-2785.
[14]HIRANO Y,SAGATA K,KIT A Y.Selective transformation of glucose into propylene glycol on Ru/C catalysts combined with ZnO under low hydrogen pressures[J].Appl Catal A:Gen,2015,502:1-7.
[15]ZHANG Y,WANG A,ZHANG T.A new 3D mesoporous carbon replicated from commercial silica as a catalyst support for direct conversion of cellulose into ethylene glycol[J].Chem Commun,2010,46(6):862-864.
[16]BERMEJO-DEVAL R,ASSARY R S,NIKOLLA E,MOLINER M,ROMAN-LESHKOV Y,HWANG S-J,PALSDOTTIR A,SILVERMAN D,LOBOR F,CURTISS L A.Metalloenzyme-like catalyzed isomerizations of sugars by Lewis acid zeolites[J].Proc Natl Acad Sci,2012,109(25):9727-9732.
[17]MIZUGAKI T,YAMAKAWA T,ARUNDHATHI R,MITSUDOME T JITSUKAWA K,KANEDA K.Selective hydrogenolysis of glycerol to1,3-propanediol catalyzed by Pt nanoparticles-AlO_x/WO_3[J].Chem Lett,2012,41(12):1720-1722.
[18]KOBAYASHI H,ITO Y,KOMANOYA T,HOSAKA Y,DHEPE PL,KASAI K,HARA K,FUKOUKA A.Synthesis of sugar alcohols by hydrolytic hydrogenation of cellulose over supported metal catalysts[J].Green Chem,2011,13(2):326-333.
[19]GUO X,LI Y,SHI R,LIU Q,ZHAN E,SHEN W.Co/MgO catalysts for hydrogenolysis of glycerol to 1,2-propanediol[J].Appl Catal,2009,371(1):108-113.
[20]HOLM M S,PAGAN-TORRES Y J,SARAVANAMURUGAN S,RIISAGER A,DUMESIC J A,TAARNING E.Sn-Beta catalysed conversion of hemicellulosic sugars[J].Green Chem,2012,14(3):702-706.