乙醇催化重整制氢研究进展课件

乙醇催化重整制氢研究进展乙醇催化重整制氢研究进展1895乙醇催化重整制氢研究进展乙醇催化重整制氢研究进展1895一、研究背景一、研究背景热值高热值高能源危机能源危机环境友好环境友好应用广泛应用广泛来源多样来源多样氢氢 能能天然气、煤和石油等化石燃料的日益枯竭天然气、煤和石油等化石燃料的日益枯竭重整制氢、电解水制氢、光重整制氢、电解水制氢、光生物制氢、光解水制氢。生物制氢、光解水制氢。工业上，以工业上，以天然气蒸汽重整天然气蒸汽重整制氢为主。制氢为主。无污染、无碳排放无污染、无碳排放重要的传统化工原料，并且在燃重要的传统化工原料，并且在燃料电池等领域具有广阔发展空间料电池等领域具有广阔发展空间Mattos L V,et al.Chem.Rev.2012,112(7):4094-4123.Huber G W.et al.Science,2003,300(5628):2075-2077.一、研究背景热值高能源危机环境友好应用广泛来源多样氢一、研究背景热值高能源危机环境友好应用广泛来源多样氢 能能生物质能生物质能生物质能开发与利用生物质能开发与利用生物质发电生物质发电生物材料生物材料石化产品替代品石化产品替代品国家国家“十二五十二五”规划规划生物甲醇生物甲醇生物乙醇生物乙醇生物柴油生物柴油生物甘油生物甘油0.1kg甘油甘油/kg柴油柴油生物质基醇类（生物质基醇类（bio-alcohols)Zhou C H,et al.Chem.Soc.Rev.,2008,37(3):527-549.Alonso D M,et al.Chem.Soc.Rev.,2012,41(24):8075-8098.一、研究背景一、研究背景生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国生物质能生物质能开发与利用生物质发电生物材料石化产品替代品国 生物质基生物质基生物质基生物质基醇类醇类醇类醇类环境环境友好友好价廉价廉价廉价廉易储运易储运易储运易储运可再生可再生可再生可再生Why bio-alcohols?Why steam reforming?产氢效率高产氢效率高工艺成熟工艺成熟常压、中高温常压、中高温反应条件反应条件原料高效利用原料高效利用Steam reformingMattos L V,et al.Chem.Rev.2012,112(7):4094-4123.Huber G W.et al.Science,2003,300(5628):2075-2077.一、研究背景一、研究背景 生物质基醇类环境友好价廉可再生生物质基醇类环境友好价廉可再生Why bio-aBasis of Ethanol/Glycerol Steam Reforming C2H5OH+3H2O 2CO2+6H2 RenewableBiodeg-radableLow toxicityHigh vaporis-ation heatEasy handlingSulfur freeC3H8O3+3H2O 3CO2+7H2 Basis of Ethanol/Glycerol SteaReforming activity on metals C2H5OH+3H2O 2CO2+6H2 Ethanolconversionsonsupportedsingle-componentcatalystsat573K,60000h-1ofGHSV,and1:3ofS/C,dilutedin86%He.Duan&Senken.,Ind Eng Chem Res,2005,44,6381Reforming activity on metals 镍基催化剂理性设计镍基催化剂理性设计存在的挑战存在的挑战镍基催化剂具有较大镍基催化剂具有较大的开发潜力，但其存的开发潜力，但其存在易积碳，活性组分在易积碳，活性组分易烧结等问题。易烧结等问题。催化剂性质催化剂性质镍颗粒大小镍颗粒大小金属分散度金属分散度金属与载体相互作用金属与载体相互作用催化剂制备催化剂制备不同镍基前躯体影响不同镍基前躯体影响具有特殊结构的催化具有特殊结构的催化剂前躯体的制备剂前躯体的制备催化剂测试催化剂测试乙醇蒸汽重整乙醇蒸汽重整吸附强化乙醇蒸汽重整吸附强化乙醇蒸汽重整工程放大工程放大催化剂表征催化剂表征XRD、H2-TPR、TEM、XPS、TG,etc.设计和开发高活性和高稳定性的催化剂仍是生物质基醇类制氢工艺亟待解决的关键技术之一。一、研究背景一、研究背景镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但镍基催化剂理性设计存在的挑战镍基催化剂具有较大的开发潜力，但Nickel particle size:Ni/-Al2O3Ni/CeO2Ni/ZrO2ZrO2-Al2O3MgOAcid amount:MgOCeO2ZrO2-Al2O3(A)NH3-TPRS profiles of reduced nickel catalysts;(B)H2-TPR profiles of supported nickel catalysts;(C)XRD patterns of reduced nickel catalysts;(D)Oxygen storage capacity(OSC)tests of pure oxides.Surface Properties of SupportsGong et al.PCCP 2012,14,4066(Cover)Nickel particle size:OSC of suSulfurpoisoningSinteringActivityCformationNickel Challenges for Nickel Steam-Reforming catalystsParticle size of Ni metalSurface oxidation activityImprove metal dispersion and nanoconfinement effect to stabilize nickel particlesImprove surface oxygen mobilityActivitySelectivityH2 yieldProcess intensificationSorption enhanced steam reformingSulfur poisoningSinteringActivImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsImprove Ni dispersion and nanoImproved Dispersion of Ni:the Journey of Raney NiGong et al.,PCCP 2012,14,3295hydratedaluminumEnhanceddispersionandsurfaceareaofNi;additivemetalscouldtunetheselectivityImproved Dispersion of Ni:theReaction conditions:ethanol feed,3.1h-1,S/C=4Catalysts:Raney Ni reaction conditions:ethanol feed,4.6h-1,350C S/C=4Catalysts:raney Ni reaction conditions:ethanol feed,3.1h-1,S/C=4,350CLT Steam Reforming to Produce CO-Free H205101520253035404550020406080100Time/hConversion or selectivity/%Ethanol conversion H2 selectivity CO2 selectivity CO selectivity CH4 selectivityLow-Temperature Steam Reforming to Produce CO Free HydrogenGong et al.,PCCP 2012,14,3295Reaction conditions:ethanol fImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsSupported catalystsPrecursor on dispersionImprove Ni dispersion and nanoNi(CH3COO)2Ni-ACNi(NO3)2Ni-NNi(C7H7O2)2Ni-AANiCl2Ni-C-Al2O3Influence of Nickel Precursors on Nickel dispersionXRD patterns of the catalysts after 700 C reductionTEM images of the catalysts after reductionNickel particle size：Ni-ACNi-NNi-AANi-NNi-AANi-C coke deposits：Ni-ACNi-NNi-AANi-CTEM images after reactionInfluence on Glycerol Steam Reforming StabilityReaction conditions：550 C，S/CDifferentnickeldispersionandreducibilityGlycerol Glycerol Steam ReformingSteam ReformingDifferentglycerolsteamreformingactivityandstabilityDifferentnickelprecursorsNi(CHNi(CH3 3COO)COO)2 2Ni(NONi(NO3 3)2 2Ni(CNi(C5 5HH7 7OO2 2)2 2NiClNiCl2 2Effect of Nickel Precursors on Glycerol Steam ReformingGong et al.,ACS Sus Chem Eng 2013,doi:10.1021/sc400123fDifferent nickel dispersion anImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsHigh dispersioncatalysts,method to resistsinteringImprove Ni dispersion and nanoZrOCl2NH4OHN2 dryNanoarchitectural Design of NiZrO2 CatalystConventional Ni/ZrO2Nanoarchitectural Ni-ZrO2Gong et al.,Chem Commun 2013,49,4226ZrOCl2N2 dryNanoarchitectural Nanoconfinment effect in NiZrO2 catalyst NiZrO2Gong et al.,Chem Commun 2013,49,4226Nanoconfinment effect in NiZrESR activity and stability(a)Catalytic activity at 723 K.Solid symbols:NiZrO2 catalyst;hollow symbols:Ni/ZrO2 catalyst.(b)Catalytic stability at 873 K.The insets are TEM images of the used catalystsGong et al.,Chem Commun 2013,49,4226ESR activity and stabilityCataImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsHigh dispersioncatalysts,method to resistsinteringImprove Ni dispersion and nanoNanoconfinement of Ni NPs by phyllosilicates structureGong et al.,ACS Sus Chem Eng 2013,1,161Nanoconfinement of Ni NPs by p(a)Ni/SiO2P (b)Ni/SiO2INi NPs stabilized by the structureGong et al.,ACS Sus Chem Eng 2013,1,161(a)Ni/SiO2P (b)Ni/SiO2INi NReaction conditions:ethanol feed velocity,2.5 gh/mol for(c)600,(b)500,and(a)400 C,0.82 gh/mol for(d)700 C;6 vol%of ethanol in gas;S/C=4,1 atm.Stability test on(a and c)Ni/SiO2P and(b and d)Ni/SiO2I.Reaction conditions:(a and b)400 C,(c and d)600 C;1 atm,ethanol feed velocity,10 gh/mol,ethanol in feed,6 vol%for 400 C reaction;ethanol feed velocity,16.4 gh/mol,ethanol in feed,3 vol%for 600 CTEM characterization after 600 C stability test(a and b)TEM images and(c and d)HRTEM images for(a and c)Ni/SiO2P and(b and d)Ni/SiO2I.Insets are for statistics of Ni particle size.Coke deposition rate on Ni/SiO2P and Ni/SiO2IActivity and stability on Ni/PS-based catalystsGong et al.,ACS Sus Chem Eng 2013,1,161Reaction conditions:ethanol fNanoconfinement of Ni NPs by PS NanotubeNi PSCrispationReductionNi PS nanotubeNi/PSnGong et al.,Chem Commun,in press,doi:10.1039/c3cc43895cNanoconfinement of Ni NPs by PPhysical-chemical properties of Ni/PSnGong et al.,Chem Commun,in press,doi:10.1039/c3cc43895cPhysical-chemical properties oReactivity comparison of different Ni/SiO2 catalysts.Reaction conditions:1 atm,400 C,S/C=4,W/F=2.5 gh/mol,EtOH/gas=6%Ethanol steam reforming reactivity and(b)deactivation test on the reduced catalysts.Reaction conditions:(a)1 atm,400 C,S/C=4,W/F=10 gh/mol,EtOH/gas=2.5%;(b)1 atm,400 C,S/C=4,W/F=5 gh/mol,EtOH/gas=4.2%(a)Ethanol steam reforming stability test on Ni/PSn-600,reaction conditions:1 atm,500 C,S/C=4,W/F=10 gh/mol,EtOH/gas=4.2%.(b)TEM images of the catalyst after stability test.Activity and Stability on Ni/PSnGong et al.,Chem Commun,in press,doi:10.1039/c3cc43895cReactivity comparison of diffeImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsHigh dispersioncatalysts,method to resistsinteringImprove Ni dispersion and nanoNanoconfinement of Ni NPs by Perovskite structureNanoconfinement sinter resistIncrease interface,improve metal-support intertionWell disperse,reduce nickel particle sizeGong et al.,unpublished resultsNanoconfinement of Ni NPs by P图图4-7 还原后还原后的的催化剂催化剂TEM图图STEM of the catalysts after reductionStability testReaction conditions：S/C=3，LHSV=2.5 h-1，550 C，1 atmActivity and Stability on Perovskite-based catalysts Gong et al.,unpublished results图图4-7 还原后的催化剂还原后的催化剂TEM图图STEM of the caImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsHigh dispersioncatalysts,method to resistsinteringImprove Ni dispersion and nanoXRD patterns of the hydrotalcite-like precursors(a)NiMg6(b)NiMg8(c)NiMg10Transmission electron micrograph of the NiMg6 precursorFT-IR of the NiMg6 precursor(a)NiMg6(b)NiMg8(c)NiMg10Nanoconfinement by hydrotalcite-like structureGong et al.,Int J Hydrogen Energy,2010,35:6699-6708(Mg2+Ni2+)/Al3+=3XRD patterns of the hydrotalciTemperature program reduction of the oxides(a)NiMg6(b)NiMg8(c)NiMg10(d)NiOXRD patterns of the oxides(a)NiMg6(b)NiMg8(c)NiMg10 High Dispersion of Nickel Catalysts(a)(a)(c)Gong et al.,Int J Hydrogen Energy,2010,35:6699-6708Temperature program reduction XRD patterns of the reduced NiMg10 catalyst at different temperatures(a)973 K(b)1023 K(c)1123 K(d)1173 KConversion/composition(%)vs reduction temperature curves of ethanol steam reforming over the NiMg10 catalyst.Activity on hydrotalcite derived nickel catalysts 973 K 1073 K 1173 KGong et al.,Int J Hydrogen Energy,2010,35:6699-6708XRD patterns of the reduced NiImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsImprove Ni dispersion and nanoOxygen mobility of CeO2 based supportsPromote WGSREnhance adsorption of waterSuppress carbon depositionImprove dispersion of nickelOxygen storagecapacityRedoxrateH.Song,U.S.Ozkan,J.Catal.,2009,261:66-74 J.A.Farmer,C.T.Campbell,Science,2010,329:933-935Importance of Surface Oxygen MobilityOxygen mobility Promote EnhancIncrease oxygen vacancyPromote Ce4+reductionEnhance oxygen mobilityG.Balducci,M.S.Islam,J.Kasapar et al.Chem.Mater.2003,15:3781-3785X.Liu,K.Zhou,L.Wang,B.Wang,Y.Li,J.Am.Chem.Soc.2009,131:31403141Mg additionApproach for Enhancing Oxygen MobilityIncrease oxygen vacancyPromoteEnhanced Oxygen Mobility of Ni/CeOxGong et al.,AIChE J.2012,58,516Enhanced Oxygen Mobility of NiEthanol steam reforming on Ni/MgO-CeO2 catalysts.Reaction conditions:Pressure:1 atm,temperature:400C,S/C:4,Ethanol feeding W/F:33 g h/molEthanol steam reforming on Ni/7MgCe and Ni/10MgCe at different reaction conditions.(a)Pressure:1 atm,temperature:400 C,S/C:4,ethanol feeding W/F:11 g h/mol;(b)Pressure:1 atm,temperature:600 C,S/C:4,ethanol feeding W/F:33 g h/mol(a)(b)Correlation of Oxygen Mobility and ReactivityGong et al.,AIChE J.2012,58,516Ethanol steam reforming on Ni/Carbon depositions on the Ni/MgO-CeO2 catalysts after 10 h reaction(reaction conditions:1 atm,400 C,and ethanol feeding W/F 33g h/mol);inset:carbon deposition per unit Ni on the Ni/MgO-CeO2 catalystsProposed MechanismTheadditionofMggreatlyenhancestheOOSofCeO2,andsubsequentlyfacilitatetheconversionofethanolandremovalofdepositedcarbon.Gong et al.,AIChE J.2012,58,516Carbon depositions on the Ni/MImprove Ni dispersion and nanoconfinement effect of Ni NPsSkeletal NiNiZrO2Ni-CaO-Al2O3 bi-functional catalystsImprovedispersion and nanoconfinement effectImprove surface oxygen mobilityProcessintensificationNickel precursor effectNickel PS structureNickel HTLs structureNickel perovskite structureNi/MgO-CeO2 catalystsImprove Ni dispersion and nano(Ca2+Ni2+)1-xAl3+x(OH)2(An-)x/nmH2OBi-functional catalysts:adsorption and reformingBi-functional CatalystsGong et al.,Eng Environ Sci 2012,5,8942(Ca2+Ni2+)1-xAl3+x(OH)2(An-)x/Comparison of cyclic sorption capacity of NiCaOAl2O3 catalysts(carbonation in 50%CO2 for 45 min at 500 C and calcination in100%N2 for 20 min at 700 C).Comparation of NiCaOAl2O3 catalysts in the SESRE experiment.Solid line:H2 concentration,dashed line:CO2 concentration,reaction conditions:1 atm,500 C,S/C?4,120 min,desorption conditions:1 atm,700 C,30 minMultiple reactiondesorption cycles of the CA3.0 catalyst and themixture of CaO and Ni/Al2O3 catalysts(reaction conditions:1 atm,500C,S/C?4,90 min,desorption conditions:1 atm,700 C,30 min)Sorption Enhanced steam reformingGong et al.,Eng Environ Sci 2012,5,8942Comparison of cyclic sorption Bi-functional MechanismGong et al.,Eng Environ Sci 2012,5,8942Bi-functional MechanismGong et三传一反三传一反（催化剂放大）（催化剂放大）理性设计理性设计（模型催化）（模型催化）活性位本质活性位本质展望展望三传一反理性设计活性位本质展望三传一反理性设计活性位本质展望Thank you for your attention!Thank you for your attention!