不同载体负载的钴基费-托合成催化剂的还原过程研究

262()Vol.26No.220076JournalofSouth-CentralUniversityforNationalities(Nat.Sci.Edition)Jun.2007a-李金林　完友军　张煜华　熊海峰(-,430074)(SiO2Al2O3TiO2)-.X-(in-situXRD)(H2-TPR),Co3O4Co3O4.:-2,2:Co3O4+H23CoO+H2O3CoO+3H23Co0+3H2O.-:Co/SiO2Co/TiO2Co/Al2O3.-;;;;X-;.O643.36A1672-4321(2007)02-0001-06StudiesontheReductionProcessoftheSupportedCobaltCatalysisforFischer-TropschSynthesisLiJinlinWanYoujunZhangYuhuaXiongHaifengAbstractThispaperfocusedonthestudyofthereductionprocessofthesupportedcobaltFischer-Tropschsynthesis(FTS)catalystswithdifferentsupport(SiO2,TiO2,Al2O3).Thecatalystswerecharacterizedwithin-situX-raydiffraction(in-situXRD),hydrogentemperature-programmedreduction(H2-TPR).ItwasfoundthatunderhydrogenatmospherethereductionofthesupportedcobaltFTScatalystsproceededintwostepsasCo3O4+H23CoO+H2O,3CoO+3H23Co0+3H2O.ThereducibilityofthesupportedcobaltFTScatalystswasfoundtobethefollowingorder:Co/SiO2Co/TiO2Co/Al2O3.KeywordsFischer-Tropschsynthesis;cobaltcatalyst;support;reduction;in-situX-raydiffraction;temperature-programmedreductionLiJinlinProf,Ph.D,KeyLaboratoryofCatalysisandMaterialsScienceoftheStateEthnicAffairsCommission&MinistryofEducation,HubeiProvince,SCUFN,Wuhan430074,China-(Fischer-TropschSynthesis,FTS)(CO+H2),.[1,2].,-[3,4].-2,,[2,5,6].-,-.,,a2007-05-25(1963-),,,,:.E-mail:[e-mail].(20590361)(20473114).,,-.-,,.1SiO2TiO2Al2O3,15%()-..3:Co/SiO2Co/TiO2Co/Al2O3.1.1:,.:¹SiO2,SiO2(SG01001,:6.8nm,:457.3m2/g,:0.78cm3/g),802005006h;ºTiO2,TiO2(DegussaP-25,:21nm,:5015m2/g),3,,24h,12012h,,8020070010h.TiO2400600,,TiO270010h,TiO2TiO2TiO2;»Al2O3,Al2O3(,:0.40.6mm,7nm,:230m2/g),802006006h.:Co(NO3)26H2O(A.R.).,,,.,,,50595,.24h,12012h,3505h.1.21.2.1　原位X-射线衍射X-(in-situX-rayDiffraction,in-situXRD)BrukerADVANCED8X-.AntonParrXRK900(25900,110bar),(H2N2CO),XRD.,.X-,40mL/min10/min150,30min,.30,(99.999%)XRD.60mL/min,50800,10/min.X-2080(2H):CuKA,40kV,20mA.XRDVANTEC-1.XRD(JointCommitteeonPowderDiffractionStandards,JCPDS).1.2.2　氢气程序升温还原(HydrogenTemperatureProgrammedReduction,H2-TPR)ZetonAltamiraAMI-200.0.1gU-,,.,30mL/min10/min150,1h,.50,(10%H2/Ar),30mL/min,50900,30min,10/min.(ThermalConductivityDetector,TCD),TCD75mA,1.22.1X-2()262.1.1　Co/SiO2在纯氢气氛下还原的原位X-射线衍射表征1Co/SiO2X-.,40,Co3O4.31.336.859.465.3Co3O4(JCPDS42-1467).219,Co3O4,,42.361.5,CoO,CoO,Co3O4CoO.275,Co3O4,CoO,Co3O4CoO.275301,CoO,CoO.,44.1,Co0,,CoOCo0.407,CoO,Co0.560,CoO,Co0,CoO,CoO.1Co/SiO2X-Fig1XRDspectraoftheCo/SiO2catalystduringreduction2.1.2　Co/TiO2在纯氢气氛下还原的原位X-射线衍射表征2Co/TiO2X-.,40,Co3O4TiO2(TiO2,Co3O4,CoOCo0).(2H)31.336.859.465.3Co3O4(JCPDS42-1467).27.536.044.154.556.768.970.1TiO2(JCPDS02-0494).282,Co3O4.,42.361.5,CoO,CoO.,Co3O4CoO.297,CoO,CoO,,44.1.Co0TiO2,CoOCo0.430,CoO,,CoO.450,Co0,.Co/TiO2Co0.2Co/TiO2X-Fig2XRDspectraoftheCo/TiO2catalystduringreduction2.1.3　Co/Al2O3在纯氢气氛下还原的原位X-射线衍射表征Co/Al2O3X-3.40,Co3O4C-Al2O3.31.336.859.465.3Co3O4.25.5535.1843.3952.5757.56C-Al2O3.32,:-306,Co3O4,Co3O4.,42.361.5,CoO,CoO,Co3O4CoO.,44.1,Co0,,.306448,CoO,CoO,,44.1,(CoOCo0).667,CoO,CoO,.3Co/Al2O3X-Fig3XRDspectraoftheCo/Al2O3catalystduringreduction,3XRD,-Co3O4,2,:Co3O4CoOCoOCo0.,2.(1)Co/SiO2,Co3O4260CoO,CoO.430,.560.(2)Co/TiO2,Co3O4297CoO,.430,.,430.(3)Co/Al2O3,Co3O4306CoO,,CoO.448,CoO.667,CoO.XRD,3-,,XRD[7],,XRD,-(CoAl2O4Co2SiO4),,-,XRD.,-,(H2-TPR)-.2.24-Co3O4H2-TPR.,:Co3O4CoOCo0.H2-TPR2,Co3O4CoOCoOCo0,21:3[8].4,Co3O42,Co3O4CoOCoOCo0,21,2.Co3O4,21:3,2.Co3O4(TiO2Al2O3SiO2),,4,32(412),,2(),TiO2[8]Al2O3[9]SiO2[10]H2-TPR.SiO2,2506002Co3O4CoO4()264-Co3O4(H2-TPR)Fig4H2-TPRprofilesofCo/SiO2,Co/TiO2,Co/Al2O3catalystsandpureCo3O4CoOCo0,691,,(),XRD[10].TiO2,343470Co3O4CoOCoOCo0.Al2O3,(353)Co3O4CoO,XRD,CoO;(507)(CoO)[9][11].X-,(SiO2TiO2Al2O3)-Co3O42,2:Co3O4CoOCoOCo0.1TPR2Tab1HydrogenconsumptionratiosoftwostepreductionsofsupportedcobaltcatalystsfromTPRTPR2(2/1)Co3O4(CoOCo/Co3O4CoO)Co/SiO22.863.0Co/TiO22.733.0Co/Al2O32.853.03H2-TPR,(),13(1),Co3O4.2:1:Co3O4+H23CoO+H2O,2:3CoO+3H23Co+3H2O.Co3O4,.1,Co/SiO2328,Co/TiO2343,Co/Al2O3353,Co3O4417.Co3O41,Co3O41,Co3O4,Co3O4Co3O4,,.2,Co/SiO2409,Co/TiO2470,Co/Al2O3507,Co3O4451.,,..2CoO.,3[11]:(1),,SiO2,CoOCo0;(2),MgO;(3),,,,TiO2Al2O3,,,.Co/Al2O32,CoOAl2O3,,Co/Al2O3SiO2TiO2Co[7,12].-Co3O4,3:Co/SiO2Co/TiO2Co/Al2O3.52,:-,,..3X-,(SiO2TiO2Al2O3)-,:(1)(SiO2TiO2Al2O3)-Co3O42,2:1:Co3O4+H23CoO+H2O,2:3CoO+3H23Co0+3H2O.(2)(SiO2TiO2Al2O3)-:Co/SiO2Co/TiO2Co/Al2O3.[1]AndersonRB.Fischer-TropschSynthesis[M].NewYork:AcademicPressInc,1984.[2]DryME.TheFischer-Tropschprocess:1950-2000[J].CatalysisToday,2002,71(3-4):227-241.[3].[J].,2003,26(2):17-24.[4],.[J].,2002,22(1):1583-1588.[5],.[M].:,2005:327-331.[6]IglesiaE,Design.Synthesisanduseofcobalt-basedFischer-Tropschsynthesiscatalysts[J].AppliedCatalysisA:General,1997,161:59-78[7]JongsomjitB,PanpranotJ.GoodwinJGJr.Co-supportcompoundformationinalumina-supportedcobaltcatalysts[J].JournalofCatalysis,2001,204(1):98-109.[8]LiJL,CovilleNJ.EffectofborononthesulfurpoisoningofCo/TiO2Fischer-Tropschcatalysts[J].AppliedCatalysisA:General,2001,208:177-184.[9]JacobsG,DasTK,ZhangYQ,etal.Fischer-Tropschsynthesis:support,loading,andpromotereffects