煤液化技术的发展和化学工程挑战-研究生讲座

,COALLIQUEFACTIONTECHNOLOGIES-DevelopmentinChinaandChallengesinCRE,BeijingUniversityofChemicalTechnologyOct.27,2009,Outline,HistoryandtechnicalanalysisDevelopmentsinChinaChallengesinChemicalReactionEngineering,HistoryandTechnicalAnalysis,Coal,H/C=0.8,gasolinedieselH/C2,PrincipleChemistryinCoalLiquefaction(CL),DiscoveryandEarlyDevelopments,FriedrichBergiusInventedDCLin1913,NobelPrize1931-facilitiesinmanycountriesin1940s-4.23Mt/yinGermany,/nobel_prizes/chemistry/laureates/1931/bergius-bio.html,History,SASOLplantsatSecunda,ICL-SasolTechnology(FT),1955-Sasol,SouthAfrica-LTFTandHTFTgasoline,dieseland100otherproducts-annualproduction:5Mtfuels&2.6Mtchemicals,History,ICL-LTFTTechnology,Fixedbed(Arge)SlurryPhase(SSBR),Investment100%25%catalystloading100%25%productivity100%500%(*basedonthesameid),2,500bbl/dslurryreactor,History,Source:AriGeertsema,UniversityofKentucky,LectureatMITJune29,2005J.GaoandD.Zhang,CoalLiquefactionTchnologies,2005,Source:AriGeertsema,UniversityofKentucky,LectureatMITJune29,2005J.GaoandD.Zhang,CoalLiquefactionTchnologies,2005,ICL-HTFTTechnology,Circulatingfluidizedbed(Synthol)Fix-fluidizedbed(SAS),investment100%49%energyconsumption100%41%thermalefficiency62%75%,11,000bbl/dSASreactor,History,DCLOverallDevelopments,History,AnalysisofDCLProcess,Coaltooil:requiresmanyhydrogenationsteps,Analysis,lackofcleardefinitionbetweenthetwooperationstechnicalcomparisonssuperficial,FundamentalChemistryofDCL,freeradicals,Analysis,SingleStageLiquefaction-TheNEDOLProcess,Coal,Catalyst,SlurryMaking,RecycleSolvent,RecycleHydrogen,Gases,LightDistillate,MiddleDistillate,HydrotreatedNaphtha,VacuumBottoms,VacuumDistillation,AtmosphericDistillation,SlurryReactor,SolventHydrogenation,Preheator,Separator,Separator,Separator,Hydrogen,H2,Analysis,Othersingle-stage:EDS,H-Coal,IGOR+,Pyrosol,BCL,LSE,TwoStageLiquefaction-TheHTIProcess,Hydrogen,Coal,Catalyst,SlurryMaking,Preheator,Reactor,Separator,AtmosphericDistillation,VacuumDistillation,RecycleHydrogen,Hydrotreator,Gases,OilProduct,OilProduct,Residue,Toluene,Toluene,RecycleSolvent,Separator,ExtractionTower,Reactor,Separator,400-440oC,17MPaultrafineFe,Analysis,Othertwo-stage:CTSL,Shenhua(w.solventhydrogenation),ATrendofDCLTechnology,CatalystslargesizenanosizeSolventuntreatedhydrogenatedPressure70MPa17MPaOilyield44%65%(1990s)Cost$50/bbl(1970s)50reactors,Simulationlab,ICL-FundamentalStudiesinCatalysis,DevelopmentsinChina,Fe(&Co)basedCatalystandCatalysis-Richchemical/physicalstructuresforbetterperformancesDispersion/spacingsupports:SiO2,Al2O3,ZrO2,TiO2Spacing/functionalpromoters:Cu,MnOx,MoOx,CaO,MgO,CrOx,PtAlkalipromoters-Structuresatdifferentstagesbyvarioustechniques(MES,XRD)EarlypreparationstagePrimitivesCalcinationsstageBulkstructureReduction/reactionstagesLeachingofbulkstructures-Informationoninteractionsofphases/componentsTPR/TPD/TPOforchemicalbehaviorsandkineticimplicationsTheoreticalcalculationstounderstandthegenesisofcatalysisReactiontestsuptopilotplantscale+SEMinformation,DevelopmentsinChina,Reactionstudies-EffectofSibinder,BeforereactionAfterreaction,ICL-FundamentalStudiesinCatalysis,DevelopmentsinChina,Mechanism-QuantumchemistryanalysisofFecatalyst,ICL-FundamentalStudiesinMechanism,DevelopmentsinChina,FTkinetics,Possiblemechanisms,Reliabledetailedmechanisms,LHHWtypekineticmodels,ICL-FundamentalStudiesinKinetics,DevelopmentsinChina,1970s-CatalystsandreactionbehaviorsChinaCoalResearchInstitute(CCRI),andUniversitiesandInstitutes1982-20020.1t/dIGORandNEDOL1980-2000Feasibilitystudies2002-FormationofShenhuaprocess0.1t/dBSUand0.2t/dcatalystPDU,DCL-History,CCRI,DevelopmentsinChina,Catalysts:mainlyFe-basedultra-fineordispersedReactionkineticsandmechanismmacrolevel,basedextractiondataBehaviorofcoalinslurryathighTswelling,pretreatmentPropertiesofstreamsdensity,surfacetension,viscosity,H2solubilityReactordesignandsimulationgas-liftreactor,cold/hottestsProductupgradingandresidueutilizationgasification,hydrogenation,pitchandcarbonmaterialsCo-processingwithotherlowvalueorganicsplastic,rubber,refiningresidue,biomass,DCL-FundamentalStudies,-Fe-based,varioustypesNano-sizeFeOOHfromFeSO4MoreactivethanFeS2andlessusageHigheroilyield,DevelopmentsinChina,DCL-FundamentalStudies,Catalystandcatalysis,FeOOHmadefromFeSO4,Autoclavedata,430oC,DevelopmentsinChina,DCL-FundamentalStudies,-Variousempiricalmodels,Reactionmechanismandkinetics,ParallelModel,DevelopmentsinChina,DCL-FundamentalStudies,-Gas-liftreactorHighinliquidvelocity&gashold-upNoneedforarecyclepumpSimpleinteriorcomponentsColdexperiments,modelsIntegralhydrodynamicmodelequationsEvaluationof6t/dPDU,Reactorandsimulation,SimulationstudyFromlefttoright:-Gasholdup-H2ingasphase-H2inliquidphase-Soliddistribution-Productdistribution-Temperature,Coldexperimentalsetup,DemonstrationandApplicationofCL,DevelopmentsinChina,Plantcapacity,Mt/y,3.0,2.0,1.0,0.0,Estimatedoperationdate,ICL,ICL,DCL,ICL,ICL,DCL,4.0,5.0,1Mt/yshenhua,0.16Mt/yYitia&Luan/SynfulesChina,ChallengesinChemicalReactionEngineering,ChallengesinICLTechnology,catalyticsynthesis,gasification&purification,productupgrading,products,ChallengesinCL,liquefaction,gasification,Productsupgrading,ChallengesinDCLTechnology,H2,ChallengesinCL,ConcludingRemarks,CL:oldtechnologies,revivinginrespondtovolatileoilsupplyICL:maturewithbetterunderstandingincatalysis,lacksinformationinchemicalreactionengineeringDCL:noindustrialpracticesince1950,limitedscientificandengineeringinformationineveryaspectsLargescaleCLtechnologiesarebeingpracticedinChinawithsupportfromfundamentalandappliesresearches-valuableexperiencea