hasuploaded_CeO2BaMnAl11O19-催化

2004624,373376ACTACHIMICASINICAVol.62,2004No.4,373376CeO2/BaMnAl11O19-aX,aaaaa,bX(ab116023)BaMAl11O19-(M=Mn,Co,Ce),M.Mn,Mn,.Ce,,Mn.CeMnCeO2/BaMnAl11O19-,.100h,CeO2/BaMnAl11O19-,.,,,CeO2PreparationofCeO2/BaMnAl11O19-CatalystsandApplicationinMethaneCombustionXU,Jin2GuangaTIAN,Zhi2JianX,aWANG,Jun2WeiaXU,Yun2PengaXU,Zhu2ShengaLIN,Li2Wua,b(aLaboratoryofNaturalGasUtilizationandAppliedCatalysis,bStateKeyLaboratoryofCatalysis,DalianInstituteofChemicalPhysics,ChineseAcademyofSciences,Dalian116023)AbstractCeO2hadaloweractivityforhydrocarbonoxidationaccordingtothecorrelationbetweentherateofhydrocarbonoxidationandmetal2oxygenbondstrength(volcanoplot).However,theCH4combustionactivityofthenanosizedCeO2supportedonbariumhexaaluminateswassohighthatthetemperaturefor10%conversionwascomparablewiththatofnoblemetaloxidecatalysts.SucharesulthasattractedconsiderableattentionduetoeffectofpreparationonthestructureandcombustionactivityofCeO22containingcatalysts.Inpresentwork,BaMAl11O19-(M=Mn,Co,Ce)catalystswerepreparedbyreversemicroemulsion.EffectofMonphasecomposition,specificsurfaceareaandCH4combustionactivitywasinvestigated.2Al2O3andCeO2arethemajorphaseintheBaMnAl11O19-andBaCeAl11O19-catalysts,respectively,whileBaCoAl11O19-catalystconsistsof2Al2O3and2Al2O3phase.TheBaCeAl11O192hasthehighestsurfaceareaamongthethreecatalysts,butitscombustionactivityislowerthanthatoftheBaMnAl11O192catalyst.OnthebasisoftheresultsfromBaMAl11O19-(M=Mn,Co,Ce)catalysts,CeO2/BaMnAl11O19-catalystswereprepared.Itnotonlyhasahigherspecificareabutalsohasahigheractivityformethanecombustion.Theresultsfromthe100hactivitytestshowedthatCeO2/BaMnAl11O19-mightbeacandidateforcatalyticgasturbinecombustor.Keywordsmethane,catalyticcombustion,reversemicroemulsion,CeO2,15002000,N2NOx(NOx)[1].NOx,CO[2].XE2mail:[e-mail]19,2003;revisedJuly14,2003;acceptedOctober26,2003.(No.G1999022401).©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.[3].Pd,Pt,,,.,Cu,Co,Mn,Ce[4].Zarur[5],CeO2Pd,Pt.,.,,,,.Ce,,Ce.11.1[5].,(A.R.,),Span60(),(A.R.,),(A.R.,)(A.R.,)(A.R.,)W/O,(A.R.,)(A.R.,).(A.R.,)W/O,,,,,12002h,[6,7].1.2X(XRD)RagakuD/max2rBX,Cu,40kV,50mA.BETMicromeriticsASAP2010,N2.BET.,1203502h.(TEM)JEOL200CX.,.,.1.3(15mm),1%99%,,48000h-1..T10(10%).T10,.22.1BaMAl11O19-(M=Mn,Co,Ce)M1BaMAl11O19-(M=Mn,Co,Ce)XRD.1BaMAl11O19-(M=Mn,Co,Ce,CeMn)XRDFigure1XRDspectraofBaMAl11O19-(M=Mn,Co,Ce,CeMn)catalysts:2Al2O3;:2Al2O3;:2Al2O3;Ce:CeO2M=Mn,2Al2O3.M=Co,2Al2O32Al2O3;M=Ce,CeO2.,Mn.Eguchi[8](ABAl11O19-;A=Sr,Ba,La,Pr,Nd,Sm;B=Cr,Mn,Fe,Co,Ni,Cu),.,,.M=Co,,2Al2O3Co.Ce,+4Al3+,CeO2,[8].2.2BaMAl11O19-(M=Mn,Co,Ce)M.[9]:,.,.,,;,,,.M=Mn,32.1m2/g;M=Co5411m2/g;M=Ce7912m2/g.Al2O3Ba2+2Al2O3,.XRD,BaCoAl11O19-BaCeAl11O19-BaMnAl11O19-,.:Co,Ce;Al2O3Al2O3,Al2O3[10],2Al2O32Al2O3[11].473Vol.62,2004©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.2.3BaMAl11O19-(M=Mn,Co,Ce)MBaMAl11O19-(M=Mn,Co,Ce)2.2BaMAl11O19-(M=Mn,Co,Ce,CeMn)Figure2CatalyticcombustionofmethaneonBaMAl11O19-(M=Mn,Co,Ce,CeMn)catalystsBaMAl11O19-(M=Mn,Co,Ce),M=Mn,;M=Ce;M=Co..Zarur[5],CeO2.Connell[12],CeO2,,.[4]:Mn,Co,Ce,Al2O3,NiO.,Ce,,Co,Mn.,.2.4CeO2/BaMnAl11O19-100h:Mn,CeCo.CeCo,Ce.,CeO2/BaMnAl11O19-.XRD(1),2Al2O3,CeO2(2Al2O3).BaCeAl11O19-7911m2g-113613m2g-1.CeO2/BaMnAl11O19-BaMnAl11O19-(2),(T10)455,BaMnAl11O19-,BaCeAl11O19-BaCeAl11O19-55,115180.Palmqvist[13]CeO22%Mn,,.Ce4+.,:,,Ce4+[1416].,,MnCe.Ce,,Mn(XRDMn).Mn,.,CeMn.CeO2/BaMnAl11O19-100h,3.3CeO2/BaMnAl11O19-Figure3100hactivitytestofCeO2/BaMnAl11O19-catalyst,(780)(48000h-1)100h,.4CeO2/BaMnAl11O19-TEM.4,CeO2/BaMnAl11O19-20nm(4a),120050nm(4b),(780)100h,(4).3BaMAl11O19-(M=Mn,Co,Ce),M=Mn,Mn,.M=Co,Ce,,,M=Mn.CeO2/BaMnAl11O19-,,.573No.4:CeO2/BaMnAl11O19-©1995-2004TsinghuaTongfangOpticalDiscCo.,Ltd.Allrightsreserved.4CeO2/BaMnAl11O19-TEM(a);(b)1200;(c)100hFigure4TEMmicrographsofCeO2/BaMnAl11O19-catalyststreatedunderdifferentconditions(a)theprecursoraftersupercriticaldrying;(b)aftercalcinatingat1200for2h;(c)after100hactivitytestReferences1McCarty,J.G.Nature2000,403(6765),35.2AhlstrÊm2Silver,A.F.;Odenbrand,C.U.I.Appl.Catal.,A1997,153(12),157.3Johansson,E.M.;Danielsson,K.M.;Pocoroba,J.E.;Haralson,E.D.;Jaras,S.G.Appl.Catal.,A1999,182(1),199.4Trimm,D.L.Appl.Catal.1983,7,249.5Zarur,A.J.;Ying,J.Y.Nature2000,403,65.6Xu,J.2G.;Tian,Z.2J.;Wang,J.2W.;Xu,Y.2P.;Xu,Z.2S.;Lin,L.2W.Chin.J.Catal.2002,23(5),477(inChinese).(,,,,,,,2002,23(5),477.)7Xu,J.2G.;Tian,Z.2J.;Wang,J.2W.;Xu,Y.2P.;Xu,Z.2S.;Lin,L.2W.Chem.Eng.OilGas2002,31(5),229(inChinese).(,,,,,,,2002,31(5),229.)8Eguchi,K.;Inoue,H.;Sekizawa,K.;Arai,H.Stud.Surf.Sci.Catal.1996,103,417.9Zwinkels,M.F.M.;Aaras,S.G.J.;Menon,P.G.;Griffin,T.A.Catal.Rev.2Sci.Eng.1993,35(3),319.10Schaper,H.;Doesburg,E.B.M.;VanReijen,L.L.Appl.Catal.1983,7,211.11Kato,A.;Yamashita,H.;Kawagoshi,H.;Matsuda,S.J.Am.Ceram.Soc.1987,70(7),C157.12Connell,M.O.Catal.Today1999,47,123.13Palmqvist,A.E.C.;Johansson,E.M.;Jaras,S.G.;Danielsson,K.M.;Pocoroba,J.E.;Haralson,E.D.Catal.Lett.1998,56,69.14Kudo,T.;Obayashi,H.J.Electrochem.Soc.1975,122,142.15Yashiro,H.;Ohuchi,T.;Eguchi,K.;Arai,H.J.