硅源对蒸氨法制备CuSiO2催化剂催化甲醇裂解制氢的影响杜泽宇

Ｒeceived2018-01-26Ｒevised2018-04-20．*[e-mail]/SiO2112!1111121．2100092．210009Cu/SiO2SiO2-aer、SiO2-gelSiO2-solCu/SiO2N2-、N2O、ICP-AES、XXＲD、H2H2-TPＲ、TEMXXPS。Cu/SiO2。Cu/SiO2-sol。280℃1MPa0．6h－1Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol10%7%CH4CO298．4%96．7%。Cu/SiO2O643．88ACatalyticperformanceofmethanoldecompositiononCu/SiO2catalystwithdifferentsilicasourcespreparedwithammoniaevaporationmethodDUZe-yu1ZHUMing12*BAOZhe-yu1SHIDa-you1CHENXiao-rong1XUYan1MEIHua121．CollegeofChemistryandChemicalEngineeringNanjingUniversityofTechnologyNanjing210009China2．CatalyticHydrogenationEngineeringTechnologyＲesearchCenterNuomengChemNanjing210009ChinaAbstractCu/SiO2catalystswerepreparedviaammoniaevaporationmethodusingfumedsilicaSiO2-aersilicagelSiO2-gelandalkalinesilicasolSiO2-solasthesilicasourcesandtheircatalyticperformanceinmethanoldecompositionwereinvestigated．ThecatalystswerecharacterizedbyN2adsorption-desorptionN2OchemisorptioninductivelycoupledplasmaatomicemissionspectroscopyICP-AESX-raydiffractionXＲDH2temperatureprogrammedreductionH2-TPＲtransmissionelectronmicroscopeTEMandX-rayphotoelectronspectroscopyXPS．TheresultsindicatethatsilicasourcecanaffectthedecompositionactivityofCu/SiO2catalysts．TheCu/SiO2-solcatalystpreparedwithalkalinesilicasolexhibitslargersurfaceareasmalleractivesitesizeandmoreuniformdispersionofCu．ThereforeitgivesCu/SiO2-solabetterdecompositionperformancethanothercatalysts．MethanolconversiononCu/SiO2-solis10%higherthanthatonCu/SiO2-aerand7%higherthanthatonCu/SiO2-gel．AdditionallybyproductsconcentrationonCu/SiO2-solisconsiderablylowerthanothercatalysts．Underthereactionconditionsof280℃1MPaand0．6h－1ofWHSVmethanolconversionof98．4%andgasyieldof96．7%canbeachieved．KeywordsmethanoldecompositionammoniaevaporationmethodCu/SiO2catalyst、。1－3。4－6。78。9、1011。Pd。12PdO－HCOsHs。Wang13Ni111。CH4CO2。Greeley1446620186JournalofFuelChemistryandTechnologyVol．46No．6Jun．2018Cu111。。Cu/SiO2。15Cu/SiO216Cu/SiO2。Ji17Cu/SiO2。、Cu/SiO2CuO181920。Cu/SiO22122Cu/SiO2Cu/SiO2。11．1。。。30%。。1．2Cu/SiO2。CuNO32·3H2OSiO230%。Cu2+0．5mol/LNH3·H2OpH11．0－12．0。0．03g/g。25℃4h90℃。pH7．0－8．0。90℃12h450℃4h。Cu/SiO236%。Cu/SiO2Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol。1．3AnkersmidBELSOＲPIIN2BET。200℃3h。N2OTPＲ。100mg200℃Ar2h60℃10%H2-Ar20mL/min5℃/min360℃S1。Ar60℃N2O30minAr30min10%H2-Ar20mL/min5℃/min360℃S22S2/S1。CuNa+OPTMA20000VICP-AES。50mg500mL。XＲDBrukerD8AdvanceXCuKα40kV40mA10°－80°20°/min。H2-TPＲTPＲ100mg200℃Ar2h10%H2-Ar20mL/min5℃/min400℃TCD。JEOLJEM-200CX。。ThermoESCALAB250XIX。1．4Cu/SiO2100cm25mm7．9g。150mL/min250℃6h。280℃6mL/h。3966Cu/SiO21MPa280℃1MPa0．6h－1。xwx=min－moutmin×100%1w=VoutVideal×100%2Videal=3minVmM3min、moutVoutVidealMVm。GC-97905Aφ3．0mm×1m100℃100℃100℃80mATCD。GC-2014XE-60135℃135℃FID。22．11。1Dong23Cu/SiO2。Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol、。。Na+ICP-AES。Cu/SiO236%Cu/SiO2-sol。Na+。1Cu/SiO2Table1TexturalpropertiesoftheCu/SiO2catalystspreparedwithdifferentsilicasourcesCatalystBETaA/m2·g－1Porevolumeav/cm3·g－1Averageporeadiameterd/nmCudispersionb/%Contentw/%cCuNaSiO2-aer359．20．8311．11－－－SiO2-gel324．90．9610．27－－－SiO2-sol192．80．24．12－－－Cu/SiO2-aer512．80．473．3520．133．2B．D．Cu/SiO2-gel555．30．422．7122．333．7B．D．Cu/SiO2-sol580．60．694．0924．834．5B．D．adeterminedbyN2adsorption-desorptionbdetectedbyN2OchemisorptioncdeterminedbyinductivelycoupledplasmaatomicemissionspectroscopyICP-AESB．D．=belowdetection2．2XＲD1Cu/SiO2XＲD。122．0°SiO2。31．2°、35．8°、57．2°63．1°24。Cu/SiO2-gelCu/SiO2-aerCu/SiO2-sol。25450℃CuOCuOH2CuO。1CuOCuO26XＲD。2Cu/SiO2250℃XＲD。243．2°、50．4°74．5°Cu0。Cu02Cu/SiO2-solCu0Cu/SiO2-aerCu/SiO2-gelCu0Cu/SiO2-aerCu/SiO2-gelCu/SiO2-solCu0。496461Cu/SiO2XＲDFigure1XＲDpatternsoftheCu/SiO2catalystspreparedwithdifferentsilicasourcesaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol2Cu/SiO2XＲDFigure2XＲDpatternsofthereducedCu/SiO2catalystspreparedwithdifferentsilicasourcesaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol2．3H2-TPＲ3Cu/SiO2H2-TPＲ。3Cu/SiO2。CuOCu0Cu+CuOLi27。Cu/SiO2-aerCu/SiO2-gel230221℃Cu/SiO2-sol216℃。Cu/SiO2-gelCu/SiO2-aerCu/SiO2-sol。3Cu/SiO2H2-TPＲFigure3H2-TPＲprofilesoftheCu/SiO2catalystspreparedwithdifferentsilicasourcesaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol2．4TEM4Cu/SiO2TEM。4Cu/SiO2-aerCu/SiO2-gelCu/SiO2-aerCuO。Cu/SiO2-solCuOCu/SiO2-solCu/SiO2-sol。4Cu/SiO2Figure4TEMimagesoftheCu/SiO2catalystspreparedwithdifferentsilicasourcesaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol5Cu/SiO2250℃TEM。5Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol2。5966Cu/SiO25Cu/SiO2Figure5TEMimagesofthereducedCu/SiO2catalystspreparedwithdifferentsilicasourcesaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol2．5XPS6Cu/SiO2XPS。6Cu/SiO2XPSFigure6XPSspectraoftheCu/SiO2catalystsaftercalcinationsaCu/SiO2-aerbCu/SiO2-gelcCu/SiO2-sol6Cu2p3/2935－936eV943eVCu+228。Yu29Cu/SiO2。Cu/SiO2Cu2p3/2Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol935．9eV。2．6Cu/SiO2280℃1MPa0．6h－12。2Cu/SiO2-aer88．7%86．1%Cu/SiO2-gel91．7%89．5%。Cu/SiO2-aerCu/SiO2-gelCu/SiO2-sol98．4%96．7%。2Cu/SiO2Table2CatalyticperformanceoftheCu/SiO2catalystswithdifferentsilicasourcesinmethanoldecompositionCatalystMethanolconversionx/%Gasyieldw/%Concentrationφ/%CH4CO2Cu/SiO2-aer88．786．11．042．12Cu/SiO2-gel91．789．50．81．93Cu