绿色能源与环境保护Lecture1

LiminChen（陈礼敏）Tel-mail:liminchenOffice:B4-505,GreenEnergyAndEnvironmentalProtection,PollutionfromtraditionalenergyPetroleumprocessingandutilizationCoalutilizationBiomassEnergyplantsThermochemicalconversionBiologicalconversionSolarenergyPhotovoltaicconversionPhotothermalconversionPhotochemicalconversionOthergreenenergy:hydroenergy,wind,nuclear,geothermalenergy,oceanenergy,naturalgashydrateHydrogenProductionStoragepetrochemicalfeedstocks,AromaticHydrocarbons,Cyclicandpolyunsaturatedhydrocarbons-Conjugateddoublebonds,Benzene,Alkylaromatics,Toluene,CH3,Xylene(meta),ortho,para,BTX:Importantpetrochemicalfeedstocks,Aromaticcompoundshavehighoctanenumbers,butcontentingasolineislimitedbyenvironmentalregulations-healtheffectsduetohightoxicity,PolyaromaticHydrocarbons(PAH)orPolynuclearAromatics(PNA),Aromatichydrocarbonscontainingmorethanonering,commonlycontainingmorethantworings,Naphthalene,Anthracene,Phenanthrene,Pyrene,associatedwithenvironmentalandhealthproblems-toxiccompoundsdeactivatecatalystsviacokingreactions,Hydroaromaticsofnaphtenoaromatics,-PartiallysaturatedPAH;e.g.tetralin(tetrahydronaphthalene)-strongHdonors,HeteroatomCompounds,SulfurCompoundsmostproblematic,+H2S,CH3,CH3,shieldingpreventsremovalofSulfur,SulfidesR-S-RR-S-S-R(disulfides)*canbereadilyremoved,+H2,HeteroatomCompounds,NitrogenCompoundstwokinds1)Neutral,2)Basic,quinoline,*neutralizesacidicsites,therebydestroyingcatalyticactivity,carbazole,HeteroatomCompounds,OxygenCompounds,Carboxylic,Phenolic,*Bothcouldcausecorrosionproblems,MetalCompounds,Porphyrinsmostcommonorganometalliccompounds-metalatoms(Ni,V,Fe)atthecenterofcagestructures,-useHtosaturatestructureandbreakbondstoreleasemetalatoms,PropertiesofCrudeOil,I.PhysicalPropertiesA.APIB.ViscosityC.PourPointD.FlashPointE.VaporPressureF.CarbonResidueG.SaltContentH.MetalsI.SedimentandWaterJ.AcidityK.Sulfur,II.SpecificationofCrudeOilIII.TBPDistillationIV.SpecificationandEnvironmentalRegulationsV.OctaneNumber,PhysicalProperties,SGAPI,APIH2O=10,CrudeOils-API10-50*mostcommonly20-45,BecauseofthisinverserelationshipbetweenAPIandSG(specificgravity)thereisadesireforhighAPIcrudeoilforhighdistillateyield(e.g.,gasoline,diesel,andjetfuel).,(ASTMD-287),60F,ASTM:AmericanSocietyforTestingandMaterials,PhysicalProperties,ViscosityASTMD-2983flowproperties,resistancetoflow,PourPoint(PP)ASTMD-97temperatureatwhichoilceasestoflow-PPwaxinessofoil(n-paraffin)PPn-paraffins,FlashPoint(F)ASTMD-93temperatureabovewhichtheoilwillspontaneouslyignite,VaporPressure(F)ASTMD-323alsoknownas(ReidRVP)Truevaporpressureusually5-9%RVP,OtherPropertiesofOils,CarbonResidue-solidresidue(%wt)remainingafterheatingtocokingtemperaturesTwotests:1)ASTMD-524RamsbottomCarbon2)ASTMD-189ConradsonCarbonConradsonCarbonResidue(CCR)foulingcatalystdeactivationcokingpropensity,CCRAsphaltene,SaltcontentASTMD-3230lbNaCl/1000bbldesaltingisnecessarybecauseNaClcontent10lbs/1000bblleadstocorrosion!,OtherPropertiesofOils,MetalsEPAmethod3040Ni,V,Ag,Hg,Na,CacatalystdeactivationV2ppminfueloilscorrosionproblems,Sediment&WaterASTMD-96inorganicparticlesoperationalproblems,AcidityASTMD-664titrationw/KOH,SulfurASTMD-129,1266,1552,2622sourcrudesS0.5wt%sweetcrudesS1000F,TrueBoilingPointDistillation(TBP),SpecificationsandEnvironmentalRegulations,Gasoline-octanenumber-resistancetoignitionbycompression87RegularCR:989Plus93SuperCR:12,SparkIgnition,EngineKnock-Spontaneousignitionoffuel(higheroctanegasreducesengineknock),Compressionratio,Dieselcetanenumber(ASTMD-613)easeofignitionwhencompressedwithair.,CompressionIgnition,OctaneNumber,R:ResearchOctane(ASTM2699)M:MotorOctane(ASTM-2700),OctaneNumber:R+M2,Octanemeasuredbycomparingperformanceofgasolinetobinarymixtureof:n-heptane(0)2,2,4-trimethylpentane(100),*GasolinedistilledstraightfromcrudeoilhasanO.N.of40,ControlO.N.withadditivessuchas:1)TEL(tetraethyllead)-leadedgasoline(phasedout)2)Oxygenates,Products,DesiredProductsandImportantProperties:1)Fuelheatingvalue2)Gasolineoctanenumber(87-93)increasecompressionratiowhilepreventing“knocking”-increasespower.-aromatics(benzene)-leadedfuelTEL(tetraethyllead)*However,Pbpoisonsthecatalystincatalyticconvertersoleadwasremoved.Pbistoxic.Pbhadbeenaddedtoincreaseoctanenumber.-sulfur-vaporpressure3)Solventspurity(boilingpoint)4)Dieselcetane(hexadecaneC16H34)Cetanenumberdetermineseaseofignitionundercompression-sulfur,Products,5)Heating/FuelOilsheatingvalue-viscosity-sulfurandnitrogen6)LubeOilviscosity-thermalsensitivity-purity7)Asphaltasphaltenecontent-bindingproperties8)HeavyFuelOilsheatingvalue-sulfurandmetals9)Cokea)Fuelvolatilematter(ignitability)-Sandmetalsb)Materialcrystallinity-Sandmetals,ObjectivesinRefining,CrudeOil,RefiningProcess,Products:1)Fuels2)Petrochemicals3)Materials,ChemicalConstitution,PhysicalProperties,SeparationConversionFinishingSupport,Specifications,OverallObjective:,Convertcrudeoilintodesiredproductsinaneconomicallyfeasibleandenvironmentallyacceptablemanner!,Refinery,Environmental,Economic,FutureProspects,Products,Demandforgasoline&Dieselincreasing,*sulfurandmetalcontenthasbeenincreasingwiththeheaviercrudeoilsbeingcollectedinrecenttimesfutureprospects:-catalysts-newprocesses-modeling,*20millionbarrelsisconsumedintheU.S.perday(1barrel=42U.S.gal)*60%ofoilisimported,SimpleRefineryFlow,FutureTrendsinPetroleumRefining,Productslate:-gasoline/dieselOverallenergydemandstructure,CrudeTrendsinU.S.,Source:F.Self,E.Ekholm,andK.Bowers,RefiningOverview-Petroleum,ProcessesandProducts,AIChE,2000.(ROPPP),USEPATier2RegulationsonFuels,U.S.EPAsTier2gasolinesulfurruleandrecentlyadopteddieselrulingwillbothhaveadramaticeffectontheU.S.refiningindustry.Newgasolinesulfurregulationswillrequiremostrefinerstomeeta30ppmsulfuraveragewithan80ppmcapforbothconventionalandreformulatedgasolinebyJanuary1,2006.Thenewon-roaddieselregulationspecifiesaper-gallonsulfurcapof15ppmeffectiveJune1,2006.,NewProcessesforLow-SulfurFuels,ProcessDesignforUltra-LowSulfurFuelNewandmoreactiveandmoreselectivecatalystsforexistingHDSprocesses.NovelprocessingschemethatdoesnotdependonHDS.ExamplesofNewProcessingApproaches:Reactiveadso