ZSM-5-分子筛-入门化-讲座

ThesynthesisofZSM-5bytemplatefreecrystallizationmethodSichaoHuangDepartmentofRareEarthEngineeringInnerMongoliaUniversityofScience&TechnologyBaotouPresentationatComprehensiveelectrochemicallaboratory,Octo,12,20111.when?ZSM-5wassuccessfulsynthesisedin1972byMobil[1].Acatalyzerthatinitiallyusedinpetrochemicalindustry.Introduction2.what?1)Akindofzeolites:ThefullnameisZeoliteSoconyMobile-Five.Ref:[1]R.J.Argauer,G.R.Landolt,USPat.3,702,886,1972.2)Structure:Zeolitesarecrystallinemicroporousaluminosilicateswithperiodicarrangementsofcagesandchannels[2].3)TheframeworkofZSM-5:Ref:[2]ChengY,WangL,LiJ,etal.PreparationandcharacterizationofnanosizedZSM-5zeolitesintheabsenceoforganictemplate[J].MaterialsLetters,2005,59(27):3427-3430.Ref:[3]DatabaseofZeoliteStructures:[010]Ref:[3]DatabaseofZeoliteStructures:[100]ThechannelsofZSM-5Ref:[3]DatabaseofZeoliteStructures:[100]Ref:[3]DatabaseofZeoliteStructures::orthorhombicPnma(#62)a=20.07Åb=19.92Åc=13.42Åα=90.0°β=90.0°γ=90.0°ChemicalFormula:|Na+n(H2O)16|[AlnSi96-nO192]-MFI,n27Frameworkdensity:17.9T/1000Å3Ref:[3]DatabaseofZeoliteStructures::{[100]105.1x5.5-[010]105.3x5.6}***(3-dimensional)Ref:[3]DatabaseofZeoliteStructures:)function:shapeselectivitye.g.Thedisproportionatedreactionofmethylbenzeneandthealkylationreactionofcarbinol.REL.DisRelativediffusioncoefficientRef:[4]徐如人,庞文琴.分子筛与多孔材料化学[M].科学出版社,2004.5)Generaltemplateagent:Organicamines.ThemostrepresentativeisTPAOH.ThemolecularformulaofTPAOH6)Whynon-template?ThedisadvantageofTPA+cation[5]:highproductioncost,contaminationbywastewater,airpollutionarisingfromthermaldecompositionoforganicspeciescontainedinchannelsystem,cokedepositduetoincompletedecomposition.Ref:[5]KimSD,NohSH,SeongKH,etal.CompositionalandkineticstudyontherapidcrystallizationofZSM-5intheabsenceoforganictemplateunderstirring[J].MicroporousandMesoporousMaterials,2004,72(1-3):185-192.7)Thecruxoftheprogram:Itisdifficulttosynthsisedsilicarichzeolite.Narrowmaterialconfect.Lowrelativecrystallization.Mixedcrystal.Ref:[6]顾文应.无模板剂水热法合成ZSM-5沸石的研究[D].大连理工大学能源化工,2010.Experimental1)SolutionADissolving1.6gNaOH（NaOH≥96.0wt.%）and0.656gNaAlO2in62gdeionizedwaterinabreaker.Themixturewerethoroughlymixedbystirring.1.Preparationofnanosizedtemplate-freeZSM-5zeolite2)SolutionBTaking33.84mLsilicasolinabreaker.3)abovesynthesisgelThesolutionBwasslowlyaddedtothesolutionAunderstirringathighspeed.Themolarcompositionoftheabovesynthesisgelwas12Na2O:100SiO2:2Al2O3:2500H2O.Stirringthegel2hafterthesolutionAandBmixed.ThentheabovesynthesissolutionpriortobeingtransferredtoaTeflon-linedstainlesssteelautoclaveandwasagedfor12hatroomtempreture.4)crystallizationTheabovesynthesissolutionhydrothermallytreatedfor24hinanovenatatemperatureof180℃.Afterthehydrothermaltreatment,theproductswererecovered,thoroughlywashedwithdeionizedwater,andthendriedatroomtemperature.Flowchartofexperiment2.GeneralcharacterizationXRDSEMTEMFT-IRResultsanddiscussion1.X-raydiffractionstudiesThestandardXRDpatternofZSM-5MyXRDpattern,amorphous.2.SEMstudiesIftheparticlesizebetween5μmto100μmMordeniteZSM-5Ref:[7]NaYoungKang，BuSupSong，ChulWeeLee，WonChoonChoi，KyungByungYoon，Yong-KPark.TheeffeetofNaSO4saltonthesynthesisofZSM-5bythetemplatefreecrystallizationmethod[J].MicroporousandMesoporousMaterials(2008)GoodfigurebytemplateagentBytemplateRef:[8]I.Jirka,P.Sazama,A.Zikánová,etal.Low-temperaturethermalremovaloftemplatefromhighsilicaZSM-5.Catalyticeffectofzeoliticframework[J].MicroporousandMesoporousMaterials,2011,137(1-3):8-17.3.TEMstudiesIftheexperimentissuccessfulRef:[9]ChengY,LiaoRH,LiJS,etal.SynthesisresearchofnanosizedZSM-5zeolitesintheabsenceoforganictemplate[J].JournalofMaterialsProcessingTechnology,2008,206(1-3):445-452.4.FT-IRstudiesThestandardIRspectraofZSM-5Thepresenceoftheinfraredbandat550cm-1,whichhasbeenassignedtothefive-memberedringofthepentasilzeolitestructure[10,11].PentasilchainRef:[10]C.E.A.Kirschhock,R.Ravishankar,F.Verspeurt,P.J.Grobet,P.A.Jacobs,J.A.Martens,J.Phys.Chem.,B103(1999)4965.[11]J.C.Jansen,F.J.VanderGaag,H.VanBekkum,Zeolites4(1984)369AsymmetricstretchvibrationoftheT–Obond(at1225cm-1),whichhasbeenassignedtoexternallinkages(betweenTO4tetrahedral)andisastructure-sensitiveIRbandofZSM-5zeolite[12].Ref:[12]E.M.Flanigen,H.Khatami,H.A.Szymanski,Infraredstructuralstudiesofzeoliteframeworks,in:E.M.Flanigen,L.B.Sand(Eds.),AdvancesinChemistrySeries,AmericanChemicalSociety,Washington,DC,1971,p.201.谢谢大家忍受我的山寨版口语Thankyouverymuchforyourtimeandpatience!Anyquestions？