硫化态NiW_Al2O3催化剂加氢脱硫活性相的研究ⅠXPS和HREM表征

0253-9837200404-0309-06309!3142003-07-29.1969..Tel[phone]E-mailniehongripp-sinopec.com.NiWAl203!.XPSHREM121MichelVrinat21MichelLacroix211100083269626WNiNiWAl203XPSHREM.NiWS2NiWS.Ni30NiWS.NiWS2W0O20%.Ni.X0643T53AStudyontheHydrodesulfurizationActivePhaseinSulfidedNiWAl203Catalyst!.XPSandHREMCharacterizationsZUODOHghua12NIEHOHg1!MichelVRINAT2SHIyahua1MichelLACROIX2LIDadOHg11ResearchInstituteofPetroleumProcessingSINOPECBeijing100083China2InstitutdeRecherchessurlaCatalyseUPRCNRS54012AoenueAlbertEinstein69626villeurbanneFranceAbstractAseriesofsulfidedNiWAl203catalystsampleswithaconstantWloadingandvariousNicontentswerepreparedbyincipientwetnessco-impregnationmethodandthesampleswereinvestigatedbymeansofX-rayphotoelectronspectrometerXPSandhighresolutionelectronmicroscopyHREMtogetabetterunder-standingofthenatureoftheactivephase.XPSandHREMcharacterizationsshowedthattheNipromoterpref-erentiallydecoratedtheedgesofWS2slabstoformthehighlyactiveNiWSmixedphase.Thesignificantsynergyeffectofabout30timespromotedbyNiinthehydrodesulfurizationHDSreactionofthiophenewasdirectlycorrelatedtotheconcentrationofNiWSphase.InadditiontheintroductionofNiinducedaslightincreaseoftheWS2lamellasstackingfrom2.8layersto3.2layersandadiminutionoftheirlengthfrom4.1to3.8nmaswellasanincreasingsulfidabilityofW0Ophasebyabout20%.ThesemorphologymodificationsmaderathersmallcontributionstothetotalHDSactivitywhichcouldnotexplainthedrasticincreaseoftheHDSactivity.KeywordsnickeltungstensulfidealuminahydrodesulfurizationX-rayphotoelectronspectrometerhighresolutionelectronmicroscopy.CoMoAl203NiMoAl203NiWAl20325420044Vol.25No.4ChineseJournalofCatalysisApril2004.NiWA12031!5.NiWA1203Ni.NiWA1203CO-MOA1203NiMOA120367.NiWA1203W03Ni0NiW04NiA1204A12W043289.W03Ni0NiW10.NiWA1203WS2NiWS2NiWS11!13.NiW214.NiCOWMOS-1.XXPSHREMWNiNiWA1203NiNiWSNi.NiWWS2.11.1NiWA120315.A1203BET270m2g.80!125m90%H2-10%H2S673K4h.0.5h.WzW03=24.8%Ni.ICPNiW.1.21.2.1XXRDBIUkeID5005XXRDCUK!=0.154184nm2#=3!80.JCPDSEVA.1.2.2XPSXPSVGESCALAB200RX..A1K!Eb=1486.6eV.A121A12174.0eV.1.2.3HREMHREMLinkISISJE0L2010200kV0.2nm..500.WS2LNL=!ni=1niLi!ni=1niN=!ni=1niNi!ni=1niSi-LiXEDX.1.3.20%.H2273K.573K15h.40minHP5890#.30m0.53mmPL0T01325naS4Al3.VsXFmFmX.22.1XRDniniWAl3XRD1.WAl3XRD14.4WS00Bragg.W.xni0.410.6000WS.nini.1NiNiWAl203XRDFig1XRDpatternsofsulfidedniWAl3catalystwithdifferentnicontentsxni100.1730.4140.60xniBulkatomicratioofnini+WinsulfidedniWAl3obtainedbychemicalanalysisthesamebelow2.2XPS673KW4fni1XPS1WniS.WniW.S1XPS2NiNiWAl203673KW4!Ni2XPSFigXPSprofilesofniWAl3catalystwithdifferentnicontentssulfidedat673KaW4fbni1xni100.1730.4140.60511NiNiWAl203Table1BindingenergyofvariousspeciesinsulfidedniWAl3catalystwithdifferentnicontentsxniEbeVS1W4f7ni13FWHM0161.43.00.17161.63.0853.7.990.41161.93.853.63.40.60161.93.853.43.77FWHMFullwidthathalfmaximumofnipeak161.6eVS-1617.169.0eVXPS.W4f3.934.0eV36.038.5eV.1418334eVW4+W4f71134niWAl3!.W452W6+.W6+W4+MarCuardt-leven-bergW4XPS2.673K69%W.NiNi=0.17Ni=0.60W4+75%84%.NiW0.2NiNiWAl203WTable2SulfidationdegreeofWspeciesinsulfidedNiWAl203catalystwithdifferentNicontentsNiWoxidecontent%Wsulfidecontent%031690.1725750.4120800.6016843NiWAl203NiFig3SurfaceatomicratiosNicontentofsulfidedNiWAl203catalyst1WAl2NiNi+WNiWAl203NiNiWS.2Ni2853.3eV.Ni=0.170.41Ni20.4eVNi2NiWS1920NiW20.Ni=0.170.41Ni2FWHM1NiNiWS.Ni=0.60Ni2.Ni=0.60NiSNiWS.Ni=0.41NiS.XPSNiWAl203NiNi=0.41NiWS.NiWAl203WAlNiNi+WNi3.WAl203WAl0.059.Ni=0.170.087.NiW.NiNi+WNi0!0.41NiNi=0.41.NiWS2NiWS21NiNi=0.41WS2Ni=0.60Ni.4!Ni=0.60NiWAl203HREMFig4HREMimageofsulfidedNiWAl203catalystwithNi=0.602.3HREMNiWAl203HREMWS221325WS2.EDX!Ni=.41NiWSNiWS.4!Ni=.6~REMSNi1.5WS25.WAl2034.4nm2.3NiNiNi!Ni=.172.8!Ni=.63.24.1nm3.8nm.5NiNiWAl203WS2Fig5LengthaandlayernumberbofslabsofWS2insulfidedNiWAl203catalystwithdifferentNicontents!Ni1=4.4nm#=2.32.17=4.1nmN=2.83.41=3.8nm#=2.94.6=3.8nm#=3.26NiNiWAl203Fig6EffectofNicontentoncatalyticactivityofsulfidedNiWAl203catalystforhydrodesulfurizationReactiontemperature573K2.46NiWAl203Ni.Ni.Ni.413.Ni.41.Ni.XPS~REMNiWAl203NiWSNiS!WS2.$$=!$WS2+$NiS!+#$NiWS!#.NiWSNiS!WS2.NiWS.NiWAl203Ni.NiWSNiNiWS2NiWS2!Ni=3134NiWAl203!.0.41.NiWAl203XPS~REMNiWS2W0O20%.Kasztelan2223WS2WNiWS.WS24.4nm3.8nmW20%26%.Ni.1Topsce~ClausenBSMassothFE.InAndersonJRBoudartMeds.~ydrotreatingCatalysisCatalysisScienceandTechnologyVol11.NewYorkSpringer-Verlag1996.222SchefferBMangnusPJMoulijnJA.Jcatal19901211183GachetCBreysseMCattenotMDecampTFretyRLacroixMdeMourguesLPortefaixJLVrinatMDuchetJC~ousniSLakhdarMTillietteMJBacheli-erJCornetDEngelhardPGueguenCToulhoat~.cataltoday19884174GrangeP.catalreO-Scieng19802111355Reinhoudt~RTroostRVanSchalkwijkSVanLangeVeldADSieSTSchulz~ChadwickDCambraJdeBeerV~JVanVeenJARFierroJLGMoulijnJA.StudSurfScicatal19971062376SchraderGLChengCP.Jcatal19838023697PayenEKasztelanSGrimblotJBonnelleJP.cataltoday198841578SchefferBMolhoekPMoulijnJA.A11lcatal1989461119CarVerJCDaVisSMGoetschDA.AcSSym1Ser198528813310LouwersSPAPrinsR.Jcatal1993139252511Topsce~ClausenBSCandiaRWiVelCMcrupS.Jcatal198168243312WiVelCCandiaRClausenBSMcrupSTopsce~.Jcatal19816824