甲醇合成中CO_2作用的研究进展
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摘要
在合成气(CO/H_2)制备甲醇的过程中,向原料气中添加一定量CO_2,可以大幅提高铜基催化剂上甲醇合成的反应速率,而对于这一现象的原因尚未有统一的认识。本文对合成气(CO/H_2)制甲醇的过程中所添加的CO_2对催化剂活性中心的影响、对合成过程中所出现的中间产物的影响,以及对合成甲醇的碳源的归属的影响等方面的研究进行了总结,可以看出,CO_2的加入使得整个反应机理更加复杂。最后在此基础上对未来的研究方向进行了展望,认为相关基础研究应努力缩小和实际工业反应在条件上的差别,并把针对催化剂、反应过程的原位表征技术和理论计算相结合,以期为提高合成气制甲醇的效率提供借鉴。
Certain amount of CO_2 in syngas can significantly improve the reaction rate of methanol synthesis over Cu based catalysts, while the underline mechanism is still in controversial. This paper reviewed the research progress in the effect of CO_2 in methanol synthesis from syngas, including the active centers, the intermediates, and the carbon source. The addition of the CO_2 in the feed gas leads to a more complicated mechanism. Finally, the future research direction was briefly discussed to improve the efficiency of the methanol synthesis. We proposed that the fundamental research needs to narrow the differences with the industrial reactions especially in reaction conditions. And we should combine the in situ characterization techniques and theoretical calculations of the catalysts and reaction.
Certain amount of CO_2 in syngas can significantly improve the reaction rate of methanol synthesis over Cu based catalysts, while the underline mechanism is still in controversial. This paper reviewed the research progress in the effect of CO_2 in methanol synthesis from syngas, including the active centers, the intermediates, and the carbon source. The addition of the CO_2 in the feed gas leads to a more complicated mechanism. Finally, the future research direction was briefly discussed to improve the efficiency of the methanol synthesis. We proposed that the fundamental research needs to narrow the differences with the industrial reactions especially in reaction conditions. And we should combine the in situ characterization techniques and theoretical calculations of the catalysts and reaction.
引文
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[3]薛金召,汪希领,王先锋,等.我国甲醇新兴应用领域前景分析[J].化工进展,2016,35(s1):144-151.
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[5]PALO D R,DAGLE R A,HOLLADAY J D.Methanol steam reforming for hydrogen production[J].Chemical Reviews,2007,107(10):3992-4021.
[6]BEHRENS M.Chemical hydrogen storage by methanol:challenges for the catalytic methanol synthesis from CO2[J].Recyclable Catalysis,2015,2(1):78-86.
[7]OLAH G A,GOEPPERT A,PRAKASH G K S.Beyond oil and gas:the methanol economy[M].Germany:Wiley-VCH,2006.
[8]XU X Y,LIU Y,ZHANG F,et al.Clean coal technologies in China based on methanol platform[J].Catalysis Today,2017,298:61-68.
[9]BOZZANO G,MANEATI F.Efficient methanol synthesis:perspectives,technologies and optimization strategies[J].Progress in Energy and Combustion Science,2016,56:71-105.
[10]OTT J,GRONEMANN V,PONTZEN F,et al.Methanol.Ullmann’s encylopedia of industrial chemistry[M].Weily-VCH,2012.
[11]张明宇,王华,高文桂.真空冷冻干燥法制备CuO-ZnO-ZrO2甲醇合成催化剂[J].化工进展,2013,32(6):1290-1295.
[12]BAO Y F,HUANG C L,CHEN L M,et al.Highly efficient Cu/anatase TiO2{001}-nanosheets catalysts for methanol synthesis from CO2[J].Journal of Energy Chemistry,2018,27(2):381-388.
[13]CHU Z,CHEN H,YU Y,et al.Surfactant-assisted preparation of Cu/ZnO/Al2O3 catalyst for methanol synthesis from syngas[J].Journal of Applied Catalysis A:General,2013,366(1):48-53.
[14]KLIER K.Methanol synthesis[J].Advances in Catalysis,1982,31(10):243-313.
[15]DENISE B,SNEEDEN R P A.Oxide-supported copper catalysts prepared from copper formate:differences in behavior in methanol synthesis from CO/H2 and CO2/H2 mixtures[J].Applied Catalysis,1986,28:235-239.
[16]FAN R G,KYODO M,TAN L,et al.Preparation and application of Cu/ZnO catalyst by urea hydrolysis method for low-temperature methanol synthesis form syngas[J].Fuel Processing Technology,2017,167:69-77.
[17]WATER L G A,WILKINSON S K,SMITH R A P,et al.Understanding methanol synthesis from CO/H2 feeds over Cu/CeO2catalysts[J].Journal of Catalysis,2018,364:57-68.
[18]CHINCHEN G C,WAUGH K C,WHAN D A.The activity and state of the copper surface in methanol synthesis catalysts[J].Applied Catalysis,1986,25:101-107.
[19]JANSEN W P A,BECKERS J,HEUVEL J C,et al.Dynamic behavior of the surface structure of Cu/ZnO/SiO2 catalysts[J].Journal of Catalysis,2002,210(1):229-236.
[20]MEHTA S,SIMMONS G W,KLIER K,et al.Catalytic synthesis of methanol from CO/H2:II.Electron microscopy(TEM,STEM,microdiffraction,and energy dispersive analysis)of the Cu/ZnO and Cu/ZnO/Cr2O3 catalysts[J].Journal of Catalysis,1979,57(3):339-360.
[21]BULKO J B,HERMAN R G,KLIER K,et al.Optical properties and electronic interactions of microcrystalline Cu/ZnO catalysts[J].The Journal of Physical Chemistry,1979,83(24):3118-3122.
[22]OVESEN C V,CLAUSEN B S,SCHIOTZ J,et al.Kinetic implications of dynamical changes in catalyst morphology during methanol synthesis over Cu/ZnO catalysts[J].Journal of Catalysis,1997,168(2):133-142.
[23]LUNKENBEIN T,SCHUMANN J,BEHRENS M,et al.Formation of a ZnO overlayer in industrial Cu/ZnO/Al2O3 catalysts induced by strong metal-support interaction[J].Angewandte Chemie International Edition,2015,54(15):1-6.
[24]BEHRENS M,STUDT F,KASATKIN I,et al.The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts[J].Science,2012,336(6083):893-897.
[25]BALTES C,VUKOJEVIC S,SCHUTH F.Correlations between synthesis,precursor,and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis[J].Journal of Catalysis,2008,258(2):334-344.
[26]ZANDER S,KUNKES E L,SCHUSTER M E,et al.The role of the oxide component in the development of copper composite catalysts for methanol synthesis[J].Angewandte Chemie International Edition,2013,52(25):6536-6540.
[27]LUNKENBEIN T,GIRGSDIES F,KANDEMIR T,et al.Bridging the time gap:a copper/zinc oxide/aluminum oxide catalyst for methanol synthesis studied under industrially relevant conditions and time scales[J].Angewandte Chemie International Edition,2016,55(41):12708-12712.
[28]KLIER K,CHATIKAVANIJ V,HERMAN R G,et al.Catalytic synthesis of methanol from CO/H2:IV.The effects of carbon dioxide[J].Journal of Catalysis,1982,74(2):343-360.
[29]陈宝树,赵九生,张鎏,等.由XPS研究CO2在低压甲醇合成中的作用[J].分子催化,1989,8(4):253-259.
[30]MONNIER J R,APAI G,HANRAHAN M J.Effect of CO2 on the conversion of H2/CO to methanol over copper-chromia catalysts[J].Journal of Catalysis,1984,88(2):523-525.
[31]DAI W L,SUN Q,DENG J F,et al.XPS studies of Cu/ZnO/Al2O3ultra-fine catalysts derived by a novel gel oxalate co-precipitation for methanol synthesis by CO2+H2[J].Applied Surface Science,2001,177(3):172-179.
[32]TANG Q L,HONG Q J,LIU Z P.CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo[J].Journal of Catalysis,2009,263(1):114-122.
[33]GAO L Z,LI J T,AU C T.Mechanistic studies of CO and CO2hydrogenation to methanol over a 50Cu/45Zn/5Al catalyst by in-situ FT-IR,chemical trapping and isotope labelling methods[J].Studies in Surface Science and Catalysis,2000,130:3711-3716.
[34]LIM H W,PARK M J,KANG S H,et al.Modeling of the kinetics for methanol synthesis using Cu/ZnO/Al2O3/ZrO2 catalyst:influence of carbon dioxide during hydrogenation[J].Industrial&Engineering Chemistry Research,2009,48(23):10448-10455.
[35]SAHIBZAFA M,METCALFE I S,CHADWICK D.Methanol synthesis from CO/CO2/H2 over Cu/ZnO/Al2O3 at differential and finite conversions[J].Journal of Catalysis,1998,174(2):111-118.
[36]GRABOW L C,MAVRIKAKIS M.Mechanism of methanol synthesis on Cu through CO2 and CO hydrogenation[J].ACS Catalysis,2011,1:365-384.
[37]YANG Y,MIMS C A,MEI D H,et al.Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures:the source of C in methanol and the role of water[J].Journal of Catalysis,2013,298(1):10-17.
[38]吴贵升,赵宁,陈小平,等.CO/H2在Cu/ZrO2催化剂表面吸附行为原位红外表征[J].燃料化学学报,2001,29(6):490-493.
[39]RHODES M D,BELL A T.The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalysts Part I.Steady-state studies[J].Journal of Catalysis,2005,233(1):198-209.
[40]CHINCHEN G C,DENNY P J,PARKER D G,et al.Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts:use of 14C-labelled reactants[J].Applied Catalysis,1987,30(2):333-338.
[41]ZHANG Y L,SUN Q,DENG J F,et al.A high activity Cu/ZnO/Al2O3catalyst for methanol synthesis:preparation and catalytic properties[J].Applied Catalysis A:General,1997,158(1/2):105-120.
[42]LEE J S,LEE K H,LEE S Y,et al.A comparative study of methanol synthesis from CO2/H2 and CO/H2 over a Cu/ZnO/Al2O3 catalyst[J].Journal of Catalysis,1993,144(2):414-424.
[43]LIU G,WILLCOX D,GAELAND M,et al.The role of CO2 in methanol synthesis on Cu/Zn oxide:an isotope labeling study[J].Journal of Catalysis,1985,96(1):251-260.
[44]YANG R Q,ZHANG Y,TSUBAKI N.Dual catalysis mechanism of alcohol solvent and Cu catalyst for a new methanol synthesis method[J].Catalysis Communications,2005,6(4):275-279.
[45]ZHANG Y,YANG R Q,TSUBAKI N.A new low-temperature methanol synthesis method:mechanistic and kinetics study of catalytic process[J].Catalysis Today,2008,132(1/2/3/4):93-100.
[46]CHOI Y,FUTAGAMI K,FUJITANI T,et al.The role of ZnO in Cu/ZnO methanol synthesis catalysts-morphology effect or active site model[J].Applied Catalysis A:General,2001,208(1/2):163-167.
[2]ORTELLI E E,WAMBACH J,WOKAUN J.Methanol synthesis reactions over a CuZr based catalyst investigated using periodic variations of reactant concentrations[J].Applied Catalysis A:General,2001,216(1/2):227-241.
[3]薛金召,汪希领,王先锋,等.我国甲醇新兴应用领域前景分析[J].化工进展,2016,35(s1):144-151.
[4]LUYBEN W L.Design and control of a methanol reactor/column process[J].Industrial&Engineering Chemistry Research,2010,49(13):6150-6163.
[5]PALO D R,DAGLE R A,HOLLADAY J D.Methanol steam reforming for hydrogen production[J].Chemical Reviews,2007,107(10):3992-4021.
[6]BEHRENS M.Chemical hydrogen storage by methanol:challenges for the catalytic methanol synthesis from CO2[J].Recyclable Catalysis,2015,2(1):78-86.
[7]OLAH G A,GOEPPERT A,PRAKASH G K S.Beyond oil and gas:the methanol economy[M].Germany:Wiley-VCH,2006.
[8]XU X Y,LIU Y,ZHANG F,et al.Clean coal technologies in China based on methanol platform[J].Catalysis Today,2017,298:61-68.
[9]BOZZANO G,MANEATI F.Efficient methanol synthesis:perspectives,technologies and optimization strategies[J].Progress in Energy and Combustion Science,2016,56:71-105.
[10]OTT J,GRONEMANN V,PONTZEN F,et al.Methanol.Ullmann’s encylopedia of industrial chemistry[M].Weily-VCH,2012.
[11]张明宇,王华,高文桂.真空冷冻干燥法制备CuO-ZnO-ZrO2甲醇合成催化剂[J].化工进展,2013,32(6):1290-1295.
[12]BAO Y F,HUANG C L,CHEN L M,et al.Highly efficient Cu/anatase TiO2{001}-nanosheets catalysts for methanol synthesis from CO2[J].Journal of Energy Chemistry,2018,27(2):381-388.
[13]CHU Z,CHEN H,YU Y,et al.Surfactant-assisted preparation of Cu/ZnO/Al2O3 catalyst for methanol synthesis from syngas[J].Journal of Applied Catalysis A:General,2013,366(1):48-53.
[14]KLIER K.Methanol synthesis[J].Advances in Catalysis,1982,31(10):243-313.
[15]DENISE B,SNEEDEN R P A.Oxide-supported copper catalysts prepared from copper formate:differences in behavior in methanol synthesis from CO/H2 and CO2/H2 mixtures[J].Applied Catalysis,1986,28:235-239.
[16]FAN R G,KYODO M,TAN L,et al.Preparation and application of Cu/ZnO catalyst by urea hydrolysis method for low-temperature methanol synthesis form syngas[J].Fuel Processing Technology,2017,167:69-77.
[17]WATER L G A,WILKINSON S K,SMITH R A P,et al.Understanding methanol synthesis from CO/H2 feeds over Cu/CeO2catalysts[J].Journal of Catalysis,2018,364:57-68.
[18]CHINCHEN G C,WAUGH K C,WHAN D A.The activity and state of the copper surface in methanol synthesis catalysts[J].Applied Catalysis,1986,25:101-107.
[19]JANSEN W P A,BECKERS J,HEUVEL J C,et al.Dynamic behavior of the surface structure of Cu/ZnO/SiO2 catalysts[J].Journal of Catalysis,2002,210(1):229-236.
[20]MEHTA S,SIMMONS G W,KLIER K,et al.Catalytic synthesis of methanol from CO/H2:II.Electron microscopy(TEM,STEM,microdiffraction,and energy dispersive analysis)of the Cu/ZnO and Cu/ZnO/Cr2O3 catalysts[J].Journal of Catalysis,1979,57(3):339-360.
[21]BULKO J B,HERMAN R G,KLIER K,et al.Optical properties and electronic interactions of microcrystalline Cu/ZnO catalysts[J].The Journal of Physical Chemistry,1979,83(24):3118-3122.
[22]OVESEN C V,CLAUSEN B S,SCHIOTZ J,et al.Kinetic implications of dynamical changes in catalyst morphology during methanol synthesis over Cu/ZnO catalysts[J].Journal of Catalysis,1997,168(2):133-142.
[23]LUNKENBEIN T,SCHUMANN J,BEHRENS M,et al.Formation of a ZnO overlayer in industrial Cu/ZnO/Al2O3 catalysts induced by strong metal-support interaction[J].Angewandte Chemie International Edition,2015,54(15):1-6.
[24]BEHRENS M,STUDT F,KASATKIN I,et al.The active site of methanol synthesis over Cu/ZnO/Al2O3 industrial catalysts[J].Science,2012,336(6083):893-897.
[25]BALTES C,VUKOJEVIC S,SCHUTH F.Correlations between synthesis,precursor,and catalyst structure and activity of a large set of CuO/ZnO/Al2O3 catalysts for methanol synthesis[J].Journal of Catalysis,2008,258(2):334-344.
[26]ZANDER S,KUNKES E L,SCHUSTER M E,et al.The role of the oxide component in the development of copper composite catalysts for methanol synthesis[J].Angewandte Chemie International Edition,2013,52(25):6536-6540.
[27]LUNKENBEIN T,GIRGSDIES F,KANDEMIR T,et al.Bridging the time gap:a copper/zinc oxide/aluminum oxide catalyst for methanol synthesis studied under industrially relevant conditions and time scales[J].Angewandte Chemie International Edition,2016,55(41):12708-12712.
[28]KLIER K,CHATIKAVANIJ V,HERMAN R G,et al.Catalytic synthesis of methanol from CO/H2:IV.The effects of carbon dioxide[J].Journal of Catalysis,1982,74(2):343-360.
[29]陈宝树,赵九生,张鎏,等.由XPS研究CO2在低压甲醇合成中的作用[J].分子催化,1989,8(4):253-259.
[30]MONNIER J R,APAI G,HANRAHAN M J.Effect of CO2 on the conversion of H2/CO to methanol over copper-chromia catalysts[J].Journal of Catalysis,1984,88(2):523-525.
[31]DAI W L,SUN Q,DENG J F,et al.XPS studies of Cu/ZnO/Al2O3ultra-fine catalysts derived by a novel gel oxalate co-precipitation for methanol synthesis by CO2+H2[J].Applied Surface Science,2001,177(3):172-179.
[32]TANG Q L,HONG Q J,LIU Z P.CO2 fixation into methanol at Cu/ZrO2 interface from first principles kinetic Monte Carlo[J].Journal of Catalysis,2009,263(1):114-122.
[33]GAO L Z,LI J T,AU C T.Mechanistic studies of CO and CO2hydrogenation to methanol over a 50Cu/45Zn/5Al catalyst by in-situ FT-IR,chemical trapping and isotope labelling methods[J].Studies in Surface Science and Catalysis,2000,130:3711-3716.
[34]LIM H W,PARK M J,KANG S H,et al.Modeling of the kinetics for methanol synthesis using Cu/ZnO/Al2O3/ZrO2 catalyst:influence of carbon dioxide during hydrogenation[J].Industrial&Engineering Chemistry Research,2009,48(23):10448-10455.
[35]SAHIBZAFA M,METCALFE I S,CHADWICK D.Methanol synthesis from CO/CO2/H2 over Cu/ZnO/Al2O3 at differential and finite conversions[J].Journal of Catalysis,1998,174(2):111-118.
[36]GRABOW L C,MAVRIKAKIS M.Mechanism of methanol synthesis on Cu through CO2 and CO hydrogenation[J].ACS Catalysis,2011,1:365-384.
[37]YANG Y,MIMS C A,MEI D H,et al.Mechanistic studies of methanol synthesis over Cu from CO/CO2/H2/H2O mixtures:the source of C in methanol and the role of water[J].Journal of Catalysis,2013,298(1):10-17.
[38]吴贵升,赵宁,陈小平,等.CO/H2在Cu/ZrO2催化剂表面吸附行为原位红外表征[J].燃料化学学报,2001,29(6):490-493.
[39]RHODES M D,BELL A T.The effects of zirconia morphology on methanol synthesis from CO and H2 over Cu/ZrO2 catalysts Part I.Steady-state studies[J].Journal of Catalysis,2005,233(1):198-209.
[40]CHINCHEN G C,DENNY P J,PARKER D G,et al.Mechanism of methanol synthesis from CO2/CO/H2 mixtures over copper/zinc oxide/alumina catalysts:use of 14C-labelled reactants[J].Applied Catalysis,1987,30(2):333-338.
[41]ZHANG Y L,SUN Q,DENG J F,et al.A high activity Cu/ZnO/Al2O3catalyst for methanol synthesis:preparation and catalytic properties[J].Applied Catalysis A:General,1997,158(1/2):105-120.
[42]LEE J S,LEE K H,LEE S Y,et al.A comparative study of methanol synthesis from CO2/H2 and CO/H2 over a Cu/ZnO/Al2O3 catalyst[J].Journal of Catalysis,1993,144(2):414-424.
[43]LIU G,WILLCOX D,GAELAND M,et al.The role of CO2 in methanol synthesis on Cu/Zn oxide:an isotope labeling study[J].Journal of Catalysis,1985,96(1):251-260.
[44]YANG R Q,ZHANG Y,TSUBAKI N.Dual catalysis mechanism of alcohol solvent and Cu catalyst for a new methanol synthesis method[J].Catalysis Communications,2005,6(4):275-279.
[45]ZHANG Y,YANG R Q,TSUBAKI N.A new low-temperature methanol synthesis method:mechanistic and kinetics study of catalytic process[J].Catalysis Today,2008,132(1/2/3/4):93-100.
[46]CHOI Y,FUTAGAMI K,FUJITANI T,et al.The role of ZnO in Cu/ZnO methanol synthesis catalysts-morphology effect or active site model[J].Applied Catalysis A:General,2001,208(1/2):163-167.