催化的先进原理

Advancedprinciplesofcatalysis

ChapterOne：CatalysisandCatalystsYongdanLiDepartmentofCatalysisScienceandTechnologyCatalyticphenomenonOneofthemostimportantnaturalphenomenaLifeprocessesWithoutcatalysis,lifeisnotpossibleNaturalProcessesAcidandbaseprocessesActiveapplicationofcatalysisFermentationSO2+1/2O2SO3待月西厢下迎风户半开月移花影动疑是玉人来

2001CATTECH5,2DéfinitiondelacatalyseBeaucoupdecorpsontlapropriétéd’exercersurd’autrescorpsuneactiontrèsdifférentedel’affinitéchimique.Parcetteaction,ilsconduisentàladécompositiondescorpsetàlaformationdenouveauxcomposés,quiontunecompositiondanslaquelleilsn’entrentpas.Cettenouvellepuissance,inconnuejusqu’alors,quel’ontrouveàlafoisdanslanatureorganiqueetinorganique,jel’appelleraipuissancecatalytique.J’appelleraiaussicatalyseladécompositiondescorpsparcetteforceJönsJakobBerzelius(1836)Uncatalyseurestunesubstancequichangelavitessed’uneréactionchimiquesansquelui-mêmeapparaissedanslesproduitsWilhelmOstwald(1895)Basedontheobservationsofstarchtosugarinthepresenceofacid,combustionofhydrogenonplatinumanddecompositionofhydrogenperoxideinwatersolutionswithmetalions,etc.

Acatalystisasubstancethatselectivelytransformsreactantsintoproducts,throughanuninterruptedandrepeatedcycleofelementarystepsinwhichthecatalystparticipateswhilebeingregeneratedinitsoriginalformattheendofeachcycleduringthelifeofthecatalyst.M.Boudart,PerspectivesinCatalysis(J.M.ThomasandK.I.Zamaraev,Eds)Blackwell,Oxford,1992,p.183DefinitionofCatalysisW.OstwaldP.SabatierRPIRP*RP190019001925IntermédiaireinstableSiteactifW.OstwaldP.SabatierH.S.TaylordélocaliséephysiquelocaliséechimiquelocaliséechimiqueMichelChePresentedonthe“WorkshopforBuildinguptheCoreCoursesinIndustrialCatalysis”,Tianjin,August,2005DefinitionofCatalysis

Acatalystisa

substance

that

increasesthe

rate

atwhichachemicalreactionapproaches

equilibrium

withoutitselfbecoming

permanently

involvedinthereaction.JamesT.RichardsonPrinciplesofCatalystDevelopmentPlenumPress,NewYorkandLondon,1989

一个催化剂是一种物质，它增加一个化学反应达到平衡的速率，但它本身不永久的牵涉在反应中。PropertyActivelyinvolvedinthereactionItisareactantContactaction---NoremotesuperpowerFollowallchemicallawsIncreasetherateofapproachingequilibriumCannotchangethermodynamicequilibriumNotpermanentlyinvolvedOnesitecatalyzethereactionofmanymoleculesinasequentialmannerDefinitionofCatalysisN2

＋3H2

2NH3Activationenergyforgasphasereactionashighas57kcal/moleCatalyticpathwayH22HaN22NaNa+HaNHaNHa+Ha(NH2)a(NH2)a+Ha(NH3)a(NH3)aNH3Adsorptionofnitrogenisratelimitingstepwithanactivationenergyof12kcal/mole。At500oCincreasetherateofreactionby1013times！Example－AmmoniasynthesisOperatingconditions:-T: aslowas78Kandashighas1500K-P: aslowas10-9andashighas103bar-reactantsingasphase-reactantsinpolarornonpolarsolvents-withorwithoutassistanceofphotons,radiationorelectrontransferatelectrodes-withpuremetalsasunreactiveasgoldorasreactiveassodium-withmulticomponentandmultiphaseinorganiccompoundsandacidicorganicpolymers-atsitetimeyieldsaslowas10-5s-1(oneturnoverperday)andashighas109s-1(gaskineticcollisionrateat10bar)RangeofCatalyticReactionsMichelChePresentedonthe“WorkshopforBuildinguptheCoreCoursesinIndustrialCatalysis”,Tianjin,August,2005Fourkeypointsofthedefinition

1Chemicalequilibriumcannotbechanged

ChemicalequilibriumdependsonlyonthestateofsystemthermodynamicfunctionsGr,Hr,andKrdependsonlyonthestartandendstateCatalystcanonlyacceleratethereactionswithGr<0Gr0canbeusedtojudgeifareactionhappensornotTable1.Criteriaforthefeasibilityofareaction

Gr0Feasibility1.<-10kcal/moleHighequilibriumconversion2.0to-10kcal/moleFairlyhighconversion3.0to10kcal/molePossibleinspecialconditions4.>10kcal/moleNonfeasibleWhatis∆G?WhatisGr?WhatisGr0

?Fourkeypointsofthedefinition

2Catalystacceleratesforwardandbackwardreactionsinthesametimeandwithsameratio

Chemicalequilibriumconstantisnotchanged

Agoodcatalystfortheforwardreactionisalsoagoodcatalystforthebackwardreaction

HydrogenationanddehydrogenationAmmoniaSynthesis

Catalystisaspeciesinthereactionsystem,thuscontributestothethermodynamicstateofthesystem

3AcatalysthasselectivityNormallyasystemhasmanypossiblereactionsAcatalystacceleratesonespecificreactionAcatalystisareactantItinteractswithotherreactantsbychemicalreactionsItsactivitydependsonthechemicalstateofitselfExamplesHCOOHH2O+COAl2O3CatalystHCOOHH2+CO2MetalcatalystCO+H2

methanemethanation

mixedhydrocarbonsF-TsynthesisMethanolMixedalcoholsMixedoxygenatedcompoundsFourkeypointsofthedefinition

4Acatalysthaslimitedlife

NotpermanentlyinvolvedHighlyactivematerialLoseactivityformanyreasonsIt’sachemicalsubstanceItundergoesnaturalinvolvement

DeactivationisaslowprocessComparedtomolecularreactionFourkeypointsofthedefinitionPropertyofcatalystActivity

HighreactionrateisdesirableHigheroutput,smallerreactorvolumeispreferredLowreactiontemperatureandlowpressurearefavoredHighyieldEasyoperationSlowdeactivationBetterselectivity

Selectivity

HighyieldofpurposeproductControlofdeactivationHighoutputforindustrialprocess

Deactivationandlife

TimedependentyieldDecideoperationmodeandeconomicalbenefitsImportantpropertyofacatalystCatalysisCatalyticphenomenonAsciencecoveringcatalysisanditstechnology

IndustrialcatalysisdisciplineCatalysisscience,commercialapplicationofcatalysisandrelatedreactionengineering

Subdisciplinesofindustrialcatalysis

HomogeneouscatalysisMechanism:ligandexchangereactionHomogeneouscatalystHomogeneouscatalysisSeveraldefinitions

Heterogeneouscatalysis

HeterogeneoussystemMechanism:surfaceadsorptionandreactionInterfacialprocessesareimportantNoneedforcatalystseparationwithreactantsWidelyusedinindustrySuitableforlargescaleproduction

HeterogeneouscatalystSeveraldefinitions

EnzymaticcatalysisBioactivecatalyst

Likehomogeneouscatalyst

VeryhighspecificactivityVeryhighselectivity

Bioactivematerial

EnzymecatalystEnzymecatalysis

Contentsofthiscourse

PrinciplesofheterogeneouscatalysisPrinciplesofheterogeneouscatalystsProcessneedtoheterogeneouscatalystsSeveraldefinitionsProcessTechnologyShape,size,pores,mechanicalpropertyKinetics,selectivityMass,heatandmomentumtransferStabilityandlifeReactionengineering,optimization,massandheattransferSyntheticchemistry,Engineeringsciences,Catalysis,Transfer,Interface,PhysicsandMaterialsscienceParticleReactorIntrinsicprocessApplicationNewprocessMaxyieldMinconsumptionEasyoperationMaterial,structure,mechanism,microscopicdynamicsActivesitesSupportingknowledgeMultiscaleandmultidisciplinarynatureofindustrialcatalysisAnexample

-powergenerationfromcoalItisnotjustchemistryYoucannotignorethetechnologyShapesofrealcatalystsPhenomenaincatalyticreactorsContributionsofcatalyticsciencetohumansocietyKeytechsin20century,whichchangedthelifeofhumanAmmoniasynthesisPetroleumprocessingPolymerizationEnvironmentalcleanuptechsFuelcellsKeytechschangingthelifeofhuman

FuelcelltechnologyHydrogenenergysystemhighperformancefuelKeytechsawaitingbreakthroughandwillchangethelife

PhotostimulateddecompositionofwaterLiquefactionofcoalNaturalgasupgradingEnvironmentalissuesCatalysislookstothefutureNationalAcademyPressWashingon,D.C.1992•2001:W.S.Knowles/H.Kagan,R.Noyori,K.B.Sharpless(Nobel/WolfPrize2001)forchirallycatalysedhydrogenation/oxidation....HistoricaloverviewofcatalytictechnologyTable1,HistoryofdevelopmentofcatalyticprocessesYearProcessCatalyst1750H2SO4leadchamberprocessNO/NO21870SO2oxidationPt1880Deaconprocess(Cl2fromHCl)ZnCl2-CuCl21885Clausprocess(H2SandSO2toS)bauxite1900fathydrogenationNimethanefromsyngasNi1910coalLiquefactionFeupgradingcoalliquidsWS2ammoniasynthesis(Haber-Bosch)Fe/KNH3oxidationtonitricacidPt1920methanolsynthesis(highpressureprocess)Zn,CroxideFischer-TropschsynthesispromotedFe,CoSO2oxidationV2O5acetaldehydefromacetyleneHg2+/H2SO41930catalyticcracking(fixedbed,Houdry)claysEthaneepoxidationAgpolyethylenechlorideperoxidePolyethylene(lowdensity,ICI)peroxideoxidationofbenzenetomaleicanhydrideValkylationHF/H2SO41940hydroformylation,alkenetoaldehydeCocatalyticreforming(gasoline)Ptcyclohexaneoxidation(nylon66production)CobenzenehydrogenationtocyclohexaneNi,PtSyntheticrubber,SBRBNRButylrubberLi,peroxideperoxideAl1950polyethylene(highdensity)Ziegler-NattaPhillipsTiCrpolypropeneZiegler-NattaTipolybutadieneZiegler-NattaTi,Co,Nihydrodesulfiding(HDS)Co,MosulfidesnaphtaleneoxidationtophthalicanhydrideV,MooxidesethyleneoxidationtoacetaldehydePd,Cup-xyleneoxidationtoterephtalicacideCo,MnethyleneoligomerizationAl(Et)31960buteneoxidationtomaleicanhydrideV,Poxidesacrylonitrileviaammoxidationofpropene(Sohio)Bi,Mooxidespropeneoxidationtoacrolein/acrylicacidBi,MooxidesxyleneshydroisomerisationPtpropenemetathesisW,Mo,ReadiponitrileviabutadienehydrocyanizationNiimprovedreformingcatalystsPt,Re/Al2O3improvedcrackingcatalystsZeolitesaceticacidfromMeOH(carbonylation)CovinylchlorideviaetheneoxyclorinationCuchlorideetheneoxidationtovinylacetatePd/Cuo-xyleneoxidationtophthalicanhydrideV,TioxidespropeneoxidationtopropeneoxideMohydrocrackingNi-W/Al2O3HTwater-gasshiftprocessFe2O3/Cr2O3/MgOLTwater-gasshiftprocessCuO/ZnO/Al2O31970methanolsynthesis(lowpressure,ICI)Cu-Zn-AloxideaceticacidfromMeOH(carbonylation,lowpressureprocess,Monsanto)Rhimprovedprocessforxyleneisomerizationzeolite-alkenesviaetheneoligomerization/isomerization/metathesis(SHOP)Ni,MoimprovedhydroformylationRhautoexhaustgascatalystsPt/RhL-DOPA(Monsanto)Rhcyclooctenamer(metathesis)WhydroisomerizationPt/zeoliteselectivereductionofNO(withNH3)V2O5/TiO21980gasolinefrommethanolprocess(Mobil)zeolitevinylacetatefromethaneandaceticacidPdmethylacetate(carboxylation)Rhmethylacrylateviat-butanoloxidationMooxidesimprovedcoalliqueficationCo,MosulfidesdieselfuelfromsyngasK,Na1990polyketon(fromCOandethenePd主要参考书TE624.4/G2

催化过程的化学(美)盖茨(Gates,B.C.)等著徐晓等译

盖茨B.C.著O643.3/D64

催化作用原理导论邓景发编著

邓景发编著O643.3/S34

多相催化中的传质(美)C.N.塞脱菲尔特著陈诵英译

萨特菲尔德(Satterfield,C.N.)著TQ426/L94

工业催化原理李玉敏编著

李玉敏编著TQ032/W96-1

绿色催化过程与工艺王延吉,赵新强编著

王延吉编著O643.3C357-1

Catalysis:principlesandapplications/editors,B.Viswanathan,S.Sivasanker,A.V.Ramaswamy

Viswanathan,B.O647K81-1

Surfacescience:foundationsofcatalysisandnanoscience/KurtW.Kolasinski

Kolasinski,Kurt.XX(345755.2)

Materialconceptsinsurfacereactivityandcatalysis/HenryWise,JacquesOudar

Wise,Henry,1919-TQ032H143

Industrialcatalysis:apracticalapproach/JensHagen

Hagen,Jens.主要参考书O64K52v.6

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