LiminChen（陳禮敏）Tel:E-mail:Office:B4-505GreenEnergyAndEnvironmentalProtection1 ?Pollutionfromtraditionalenergy

PetroleumprocessingandutilizationCoalutilization

?Biomass

EnergyplantsThermochemicalconversionBiologicalconversion ?Solarenergy

Photovoltaicconversion

PhotothermalconversionPhotochemicalconversion

?Othergreenenergy:hydroenergy,wind,nuclear,

geothermalenergy,oceanenergy,naturalgashydrate

?Hydrogen

ProductionStorage&Utilization?Fuelcells:DMFC,lithiumionbatteryMainContents2Energy&EnvironmentalScienceChemSusC/energy.htmlReferenceEvaluationMethodAttendancepoints:10pointscreditwillbepossibleforperfectattendance.Presentation:40pointsFinalExam:Pointsearnedonthefinalexamwillbeproratedtoamaximumof“50"beforeassigningfinalgrades.3PollutionfromPetroleumUtilization4WorldEnergyConsumptionTrendsbySourceSources:History:EnergyInformationAdministration(EIA),InternationalEnergyAnnual,website5WorldEnergyconsumptionbySource6CO2emissionfromdifferentenergysource7Runningoutofoil??

Theconcernabout"runningoutofoil"arisesfrommisunderstandingthesignificanceofapetroleumindustrymeasurecalledtheReserves/Productionratio(R/P).Thismonitorstheproductionandexplorationinteractions.TheR/Pisbasedontheconceptof"proved"reservesoffossilfuels.Provedreservesarethosequantitiesoffossilfuelsthatgeologicalandengineeringinformationindicatewithreasonablecertaintycanberecoveredinthefuturefromknownreservoirsunderexistingeconomicandoperatingconditions.TheReserves/Productionratioistheprovedreservesquantitydividedbytheproductioninthelastyear,andtheresultwillbethelengthoftimethatthoseremainingprovedreserveswouldlastifproductionweretocontinueatthecurrentlevel.Itisimportanttonotetheeconomicandtechnologycomponentofthedefinitions,asthepriceofoilincreases(ornewtechnologybecomesavailable),marginalfieldsbecome"provedreserves".Weareunlikelyto"runout"ofoil,asmorefieldsbecomeeconomic.NotethatinvestmentinexplorationisalsolinkedtotheR/Pratio,andtheworldcrudeoilR/Pratiotypicallymovesbetween20-40years,howeverspecificnationalincentivestodiscoveroilcanextendthatrangeupward.8Runningoutofoil??CrudeOilProvedReservesR/PRatioMiddleEast89.4billiontonnes93.4yearUSA3.89.8yearsUSA-1995USGSdata10.933.0yearsTotalWorld137.343.0yearsCoalProvedReservesR/PRatioUSA240.56billiontonnes247yearsTotalWorld1,043.864235yearsNaturalGasProvedReservesR/PRatioUSA4.6trillioncubicmetres8.6yearsUSA-1995USGSdata9.117.0yearsTotalWorld141.066.4years.Onebillion=1x109.Onetrillion=1x1012.OnebarrelofArabianLightcrudeoil=0.158987m3and0.136tonnesUSGS:U.S.GeologicalSurvey9ChemicalConstitutionofPetroleumCrudeOilOrganicCompoundsHydrocarbons(C,H)MetalsHeteroatomCompounds(S,N,O)InorganicCompounds(Na+,Ca2+,Cl-)OrganicCompounds(Ni,V,Fe)10CrudeOilCrudeOilisamixtureofhydrocarbonscontainingamixtureof100,000to1,000,000differentcompounds

Boilingrangewellover1,000oF

Atthelowerendarethegaseoushydrocarbonsmethane(CH4)andethane(C2H6)andinorganicgasessuchashydrogensulfide(H2S)andcarbondioxide.Attheupperend,thematerialbecomesnon-volatileatabout1100°F(atmosphericequivalentboilingpoint)resinsandasphaltenescontainvaryingdegreessulfur,nitrogen,oxygen,andheavymetalssuchasvanadiumandnickel.

11HydrocarbonsEssentialcomponentsofpetroleumC,Hcompoundsbasedonquadrivalencyofcarbonatoms-Linkedbyasinglebond(alkanes)-Linkedbydoublebond -Alkenes-Linkedbyconjugateddoublebondsinringstructures -AromaticsCCSaturatedAliphaticHC(n-alkanesorn-paraffins)-StraightchainsofCatomseachwith2,3Hatoms(exceptCH4)generalformula:CnH2n+2CH3-(CH2)n-CH3:Ex)n-pentane:CH3-CH2-CH2-CH2-CH3CCC12AlkanesBoilingpointanddensityincreasewithincreasing#ofCatomsEffectismuchmorepronouncedatlowC#’sBranchedAlkanes(iso-alkanes)-BranchinginthecarbonchainCCCCCCCC-Boilingpt.ofn-alkanes>Bpt.ofiso-alkaneswiththesame#ofCB.P>B.P-duetomolecularinteractionsanddispersionforcesIsomers:compoundsthathavethesamechemicalformula,butdifferentstructuresdifferentchemicalandphysicalproperties13IsomersofAlkanesThisistheprincipalreasonforthemolecularcomplexityofpetroleum-especiallyinthehigherboilingregion.Alkylgroups:Alkaneminusahydrogenatom= Alkylradical(R?)Ex)CH4CH3?:methylradicalgroupC2H6C2H5?:ethylradicalgroup#CAtoms:5#Isomers:3#CAtoms:8#Isomers:18#CAtoms:18#Isomers:60,523#CAtoms:40#Isomers:6,200,000,000,000Iso-octane(anisomerofn-octane)2,2,4-trimethylpentaneCCCCCCCC**i-alkaneshavehighoctane#:e.g.,Octane#of2,2,4-TMP=100n-alkaneshavelowoctane#:e.g.,Octane#ofn-heptane=01234514SaturatedCyclicHC(cycloparaffinsornaphthenes)Cyclicstructures(orrings)inallorpartofskeletone.g.cyclohexaneMisleading2-DrepresentationActuallynon-planarstructures-Generalformulaforsingleringcompounds: CnH2nBoilingpointsanddensitiesofcycloalkanes>boilingpointsofn-alkanesforthesame#ofC

UnsaturatedAliphaticHC(alkenesorolefins)

-Littleornoolefinsincrudeoils -producedbyrefineryoperationsForexample:ethylene(H2C=CH2)andpropylene(H2C=CH-CH3); petrochemicalfeedstocks15AromaticHydrocarbonsCyclicandpolyunsaturatedhydrocarbons-ConjugateddoublebondsBenzeneAlkylaromaticsTolueneCH3CH3CH3Xylene(meta)orthoparaBTX:ImportantpetrochemicalfeedstocksAromaticcompoundshave

highoctanenumbers,butcontentingasolineislimitedbyenvironmentalregulations--healtheffectsduetohightoxicity16PolyaromaticHydrocarbons(PAH)orPolynuclearAromatics(PNA)

Aromatichydrocarbonscontainingmorethanonering,commonlycontainingmorethantworingsNaphthaleneAnthracenePhenanthrenePyreneassociatedwithenvironmentalandhealthproblems-toxiccompoundsdeactivatecatalystsviacokingreactionsHydroaromaticsofnaphtenoaromatics-PartiallysaturatedPAH;e.g.tetralin(tetrahydronaphthalene)-strongHdonors17HeteroatomCompoundsSulfurCompounds–mostproblematicS+H2SSCH3CH3shieldingpreventsremovalofSulfurSulfidesR-S-R R-S-S-R(disulfides) *canbereadilyremoved+H218HeteroatomCompoundsNitrogenCompounds–twokinds

1)NeutralNH2)BasicNquinoline*neutralizesacidicsites,therebydestroyingcatalyticactivitycarbazole19HeteroatomCompoundsOxygenCompoundsCOHOCarboxylicOHPhenolic*BothcouldcausecorrosionproblemsMetalCompoundsPorphyrins–mostcommonorganometalliccompounds --metalatoms(Ni,V,Fe)atthecenterofcagestructures --useHtosaturatestructureandbreakbondstoreleasemetalatoms20PropertiesofCrudeOilI. PhysicalProperties A.?API B.Viscosity C.PourPoint D.FlashPoint E.VaporPressure F.CarbonResidue G.SaltContent H.Metals I.SedimentandWater J.Acidity K.SulfurII. SpecificationofCrudeOilIII. TBPDistillationIV. Specificationand EnvironmentalRegulationsV. OctaneNumber21PhysicalPropertiesSG

APIAPIH2O=10CrudeOils-API~10-50 *mostcommonly20-45BecauseofthisinverserelationshipbetweenAPIandSG(specificgravity)thereisadesireforhighAPIcrudeoilforhighdistillateyield(e.g.,gasoline,diesel,andjetfuel).(ASTMD-287)60°FASTM:AmericanSocietyforTestingandMaterials22PhysicalPropertiesViscosity–ASTMD-2983flowproperties,resistancetoflowPourPoint(PP)–ASTMD-97temperatureatwhichoilceasestoflow -PP~waxinessofoil(n-paraffin) PPn-paraffinsFlashPoint(°F)–ASTMD-93temperatureabovewhichtheoilwillspontaneouslyigniteVaporPressure(°F)–ASTMD-323alsoknownas(Reid–RVP)Truevaporpressureusually5-9%>RVP23OtherPropertiesofOilsCarbonResidue-solidresidue(%wt)remainingafterheatingtocoking temperatures Twotests: 1)ASTMD-524RamsbottomCarbon 2)ASTMD-189ConradsonCarbonConradsonCarbonResidue(CCR)foulingcatalystdeactivation–cokingpropensityCCRAsphalteneSaltcontent–ASTMD-3230lbNaCl/1000bbldesaltingisnecessarybecauseNaClcontent>10lbs/1000bblleadstocorrosion!24OtherPropertiesofOilsMetals–EPAmethod3040Ni,V,Ag,Hg,Na,CacatalystdeactivationV>2ppminfueloilscorrosionproblemsSediment&Water–ASTMD-96inorganicparticlesoperationalproblemsAcidity–ASTMD-664titrationw/KOHSulfur–ASTMD-129,1266,1552,2622

sourcrudesS>0.5wt%

sweetcrudesS<0.5wt%25SpecificationofCrudeOil

APIgravitySulfur,wt%PourPoint,FAcidNumber,mgKOH/gViscosityat100°F,cstCharacterizationfactorKUOP,KW26ReportedasTBPyields,vol%ButanesandlighterLightgasoline 55-175FLightnaphtha 175-300FHeavynaptha 300-400FKerosene 400-500FAtmosphereGasOil 500-650FLt.VacuumGasOil 650-800FHvy.VacuumGasOil 800-1000FVacuumResidue > 1000FTrueBoilingPointDistillation(TBP)27SpecificationsandEnvironmentalRegulationsGasoline-octanenumber-resistancetoignitionbycompression 87–RegularCR:9 89–Plus 93–Super CR:12SparkIgnitionEngineKnock-Spontaneousignitionoffuel (higheroctanegasreduces engineknock)CompressionratioDiesel–cetanenumber(ASTMD-613)easeofignitionwhencompressedwithair.CompressionIgnition28OctaneNumberR:ResearchOctane(ASTM2699)M:MotorOctane(ASTM-2700)OctaneNumber:R+M 2Octanemeasuredbycomparingperformanceofgasolinetobinarymixtureof: n-heptane(0) 2,2,4-trimethylpentane(100)*GasolinedistilledstraightfromcrudeoilhasanO.N.of~40ControlO.N.withadditivessuchas:1)TEL(tetraethyllead)

-leadedgasoline(phasedout) 2)Oxygenates29ProductsDesiredProductsandImportantProperties: 1)Fuel–heatingvalue

2)Gasoline–octanenumber(87-93)increasecompressionratiowhile preventing“knocking”-increasespower. -aromatics(benzene) -leadedfuelTEL(tetraethyllead)*However,Pbpoisonsthecatalystincatalyticconverter soleadwasremoved.Pbistoxic.Pbhadbeenaddedto increaseoctanenumber. -sulfur -vaporpressure 3)Solvents–purity(boilingpoint) 4)Diesel–cetane(hexadecaneC16H34) Cetanenumberdetermineseaseofignitionundercompression -sulfur30Products 5)Heating/FuelOils–heatingvalue -viscosity -sulfurandnitrogen 6)LubeOil–viscosity -thermalsensitivity -purity 7)Asphalt–asphaltenecontent -bindingproperties 8)HeavyFuelOils–heatingvalue -sulfurandmetals 9)Coke a)Fuel–volatilematter(ignitability) -Sandmetals b)Material–crystallinity -Sandmetals31ObjectivesinRefiningCrudeOilRefiningProcessProducts:1)Fuels2)Petrochemicals3)MaterialsChemicalConstitutionPhysicalPropertiesSeparationConversionFinishingSupportSpecificationsOverallObjective:Convertcrudeoilintodesiredproductsinaneconomicallyfeasibleandenvironmentallyacceptablemanner!32RefineryEnvironmentalEconomicFutureProspectsProductsDemandforgasoline&Dieselincreasing*sulfurandmetalcontenthasbeenincreasingwiththeheaviercrudeoilsbeingcollectedinrecenttimes

futureprospects: -catalysts -newprocesses -modeling*20millionbarrelsisconsumedintheU.S.perday(1barrel=42U.S.gal)*60%ofoilisimported33SimpleRefineryFlowGasolineLPGJetFuel&DieselAsphaltCokeFuelOilDistillationDewaxingDeasphaltingCatalyticCrackingAlkylationReformingDelayedCokingDesaltingHydrotreatmentCrudeOilSulfurRecoveryHydrogenProductionSeparationFinishingConversionSupportLightEndsUnitHydrocrackingVisbreakingBlending34FutureTrendsinPetroleumRefiningProductslate:-gasoline/dieselOverallenergydemandstructureGeopolitics°radingqualityofcrudeoilAlternativefeeds-oilsand-naturalgas-coalMorestrictregulationson-transportationfuels-refineryoperationsNewrefiningtechnologies-processes-catalystsOthertechnol.-fuelcellNeedforMoreFlexibleandVersatileRefinery

35CrudeTrendsinU.S.Source:F.Self,E.Ekholm,andK.Bowers,RefiningOverview-Petroleum,ProcessesandProducts,AIChE,2000.(ROPPP)36USEPATier2RegulationsonFuelsU.S.EPA’sTier2gasolinesulfurruleandrecentlyadopteddieselrulingwillbothhaveadramaticeffectontheU.S.refiningindustry.Newgasolinesulfurregulationswillrequiremostrefinerstomeeta30ppmsulfuraveragewithan80ppmcapforbothconventionalandrefor