第八讲劣质重油深加工工艺.

第八讲劣质重油深加工工艺I、重质油加工技术选择II、重质油加氢工艺1、超稠油（重油）集输对重油改质的重大需求•稠油管输对粘度要求严格•稠油船运与管输对安定性要求严格•稠油储存对稳定性要求严格2、劣质渣油深加工对技术的依赖•高金属重油（＞200ppm)•高残炭（＞17％）•高粘度（＞1000cst,100℃)I、重油深加工技术选择一、劣质重油深加工首选工艺-热加工3、重油加工技术的选择（示意图）05101520重油催化热加工加氢处理加氢处理残炭%010100200Ni+Vppm重油深加工工艺渣油原料性质难度RFCC焦化固定床沸腾床悬浮床Ni+V，PPm残碳，m%硫，m%√√√√√2570.5易加工×√√√√7015不难√√&?√√70～20015稍难√×√√200～800难加工★×?800极难3、重油加工技术的选择4、脱碳工艺对重油原料的适应性强•美国自1994年起,减压渣油的深加工基本上围绕延迟焦化配套相应精制系统(“Since1994,allresidueupgradingintheUSAhasbeenbasedondelayedcoking”).•目前美国、加拿大和委内瑞拉都在大力发展延迟焦化工艺。•到2002年大部分流化焦化和灵活焦化装置停产或半停产。•我国在大力发展渣油延迟焦化技术和加氢技术。5、渣油深加工发展趋势•原油偏重、劣质资源所占份额越来越大•RFCC向FCC技术回归趋势（汽柴油质量要求提高）•VRDS和ARDS对原料的残炭和金属含量要求严格，建造与操作费用很高•我国重整原料和烯烃裂解原料不足•我国加氢的氢源不足（石脑油制氢）•提高柴汽比的需要6、我国延迟焦化发展动力7、我国延迟焦化发展趋势•1931年美国建立了第一套工业装置•目前最大装置：770万吨（Sincor，委内瑞拉）•世界最大在建：1200万吨（Suncor，加拿大)•我国最大：430万吨（中海油－惠州）•我国延迟焦化加工规模进展•2000年（1850万吨/年）；•2003年（～3000万吨/年），•目前（12000万吨）。8、延迟焦化工艺制约因素突出问题：.液收较低结焦“焦粉”淤堵弹丸焦9、目前我国延迟焦化存在问题焦化液收偏低、生焦率偏高石油焦质量不高（粉焦、弹丸焦、粘焦）操作周期偏短（3～12月，停工一天损失100万元）目前运转的装置大都不能适应劣质稠油渣油（残炭20)的加工DeepConversionOptionsHYDROGENADDITIONFIXEDBEDHydrocracking/HDSResidfiningARDS/VRDSFLUIDIZEDBEDLC-finingUOPAurabonSLURRYBUBBLEHDHPLUS™/SHPVCCCANMETMOVINGBEDShellHDM/HYCONCARBONREJECTIONDelayedCockingFlexicokingFluidCokingRFCCVisbreakingHydroVisbreakingCONC.CARBONANDREMOVALSDAGasificationH-OilCASH(CVX)EST(ENI)•OldTechnology•LowLiquidYield.•HighCokeYield.•LowInvestment.•ReadyforCommercialApplication•HighConversion.•SuitablefortheOrinocoBeltCrudes•HigherInvestment.•CommercialTechnologies•LessConversion.•LimiteduseOrinocoBeltCrudes•HigherInvestment.DelayedcokingcanprocessVRfromVenezuelaultra-heavyoil/oilsandbitumenwithtechnicalandeconomicadvantage.RFCCrequiredthelimitofthefeedstockthatcarbonresidue,Ni/Vcontentisbelow8%,10ppmrespectively.Fixed-bedhydrogenationrequiresthelimitsoffeedstocksthatcarbonresidue,(V+Ni)contentbelow20%,200ppmrespectively.Ebullated-bedhydrocrackingusedforhandlingCanadaoilsandbitumenresiduefordecades.ProcessingTechnologychallengesDelayedCoking-AdvancesTotalcapacityofdelayedcokingunitsamountingto32%;residueprocessingcapacityreachedto0.3billiont/aintheworldand90milliont/ainChina.MoreresiduesareprocessedinUSrefineries.duringthepast10years:APIdropped1°andsulfurcontentincreased0.27%cokingcapacityinUSincreased0.27Mt/a.DelayedCoking-AdvancesLowpressure,ultra-lowrecycleratiotechnologyLargerCokeDrumsappliedNewtechnologyforcokerfurnacefoulingcontrolChampion:usinganti-foulanttoreducefurnacecokingeffectively.Example:UnitinDelekTexasTylerrefinerywentthrough500daycontinuousrun,totalestimatedsavingmorethan2Million$/a.DelayedCokingOperationRunlengthsareupto5yearswithoutages/partialoutagesforfurnacedecokingCycletimesare18hoursorlessMostunitsarebeingdesignedtominimizeoperatorattendanceonthestructuretoimprovesafetyEbullated-bedhydrocrackingEbullated-bedadvantage:CatalystinreactoriscontinuouslyaddedandremovedfromthereactorEbullated-bedhydrocrackingprocessLC-FiningH-OilEbullated-bedhydrocrackingcatalystART:50%Criterion、Albemarle:50%Appliedinupgrading/processingofultra-heavycrudeoilandoilsandbitumenThefirstunitinoilsandimprovementplantstartedupin1988ReactorforhydrocrackingEbullated-bedFixed-bed(Ni+V)contentinfeed,×10-6700200Carbonresidueinfeed，%20~2520ItemsH-OilLC-FiningOperatingconditionsTemperature/℃415~440410~440Pressure/MPa13.5~21.011.0~18.0Hydrogenpartialpressure/MPa—7.5~12.5Catalystspacevelocity/h-10.4~1.3on-lineaddition/withdrawal/(kg•m-3)0.35~2.1PerformanceResidueconversionrate(v),%45~8555~80HDS(w),%65~8260~85HDN(w),%25~45-Carbonresidueconversionrate(w),%45~7540~70HDM(w),%65~9065~88Hydrogenconsumption/(m3•m-3)130~300135~300Operatingconditionandperformanceofebullated-bedhydrocrackingprocessEbullated-bedhydrocrackingHightemperature:operationtemperatureisalmostthesamewithend-of-runtemperatureoffixedbedresiduehydrogenationHighpressure:Tostabilizeoperation,maintainhydrogenpartialpressureatoutletofreactor.Highhydrogenconsumption:ForVRconvertedandcontaminatesremoval.Ebullated-bedhydrocrackingNewgenerationcatalystImprovingprocesstoincreaseimpuritiesremovalrateandcapacityIntegratingebullated-bedhydrocrackingunitwithdownstreamunittoreduceinvestmentandoperatingcostAdvancesSlurry-bedhydrocracking-ESTESTfromENI:Pilotexperimentcompletedinan1200BPSDindustrialdemonstrationunitatTarantorefinery.Eni'sSannazzarorefinerywillhostthefirstfullscaleESTindustrialplant(20000BPSD).ReactconditionsTemperaturehigherthan410℃16MpapressureConversionlevelproperlycontrolledtoavoidasphaltenesprecipitationHDM,HDS,HDN,HDCCRCatalystMobasedcatalystfinelydispersedintheliquidphase(afewthousandsofppm)SolutionisextremelysimpleandrelativelycheapSlurry-bedhydrocracking-ESTFlowschemeforESTEffluentsfractionated:C1-C2gas,LPG,AGO,VGO,bottomproductBottomproductfedintosolventdeasphaltingunittorecoverDAODOAmixedwithfreshfeedandreprocessedSlurry-bedhydrocracking-ESTFeedHCGasNaphthaAGOVGOC3DAOSCOYield（w），%10.37.833.535.612.8API/º4.360.031.718.015.227.0S（w），%5.30.140.751.381.440.94N（w），×10-638007283133293522