PMI培训资料课件：Hydrogenation Technology

Hydrogenation

TechnologyHydrotreating

Utilization

Throughoutthe

RefineryHydrogenationTechnology

forMaximumProductValueHydrotreating

is

growing

in

importance

asproductspecifications

become

more

stringent。随着产品规格的日益严格，加氢精制将扮演日益重要的角色。

UOP

6517G-2High

value

products

from

difficult

feedsmeans

increased

profits

for

you

Hydrocracking

is

the

technology

of

choice

for

converting

heavy

feeds

to

high

quality

products;Flowschemeandcatalystcanbetailoredfortheproject

to

maximize

product

value.将重质化原料转变为高质量产品加氢裂化技术是一个理想的选择。合适的流程和催化剂能最大化产品价值。HydrogenationTechnology

forMaximumProductValueUOP

6517G-2High

value

products

from

difficult

feedsmeans

increased

profits

for

you加氢是炼油化工中最重要的技术之一。Hydrogenationisoneofthemostimportanttechnologiesintherefiningandchemicalindustry.原油重质化、劣质化将驱动加氢技术的发展和应用。Highdensityandpoorqualityofcrudeoilswilldrivethedevelopmentandapplicationofthehydrogenationtechnology.HydrogenationTechnology

forMaximumProductValueUOP

6517G-2High

value

products

from

difficult

feedsmeans

increased

profits

for

you日益严格的环保要求将促使加氢装置在炼油化工中发挥更大的作用。Increasinglystringentenvironmentalrequirementswillpushhydrogenationunitstoplayagreaterroleinthepetrochemicalandrefiningindustry.炼厂加工低利润将不断驱使加氢技术向低成本和高附加值方向发展。Lowprofitsofrefinerieswillcontinuetopushthedevelopmentofthehydrogenationtechnologytowardsalowcostandhighvalue-addeddirection.1.3MMTAKeroseneHTUnit ART1020130万吨/年煤油加氢装置 ART 2.2MMTADieselHTUnit SEI;RIPP1030220万吨/年柴油加氢装置 SEI；

RIPP2.2MMTAHydrocrackingUnitUOP1040220万吨/年加氢裂化装置

UOP

0.6MMTAgasseparationunit

LPEC1041

60万吨/年气体分离

LPEC2#Complexunitsincluding:2#联合装置包括：炼油二部在PMB项目的作用：作用主要体现在两个方面：1、对上游装置生产的煤油、柴油进行产品精制，生产出符合标准的航煤和柴油产品。2、平衡全厂蜡油，通过加氢裂化技术，将常减压蜡油、焦化蜡油，转化成满足重整进料要求的重石脑油产品，满足生产石油对二甲苯产品对原料的需求。炼油二部在PMB项目的作用：常减压装置所生产的航煤组分，供航煤加氢装置，生产出合格的军、民两用的航空煤油产品。常减压装置柴油组分和灵活焦化所生产的柴油组分包括（少量灵活焦化石脑油组分）供柴油加氢装置加工，生产出符合欧Ⅴ标准的柴油产品。物料互供：炼油二部在PMB项目的作用：一部常减压装置生产的蜡油组分和四部灵活焦化装置所生产的蜡油组分供加氢裂化装置加工，生产出合格的重石脑油产品、轻石脑油产品和少量的液化气组分，重石脑油产品送往下游芳烃重整装置生产PX原料。轻石脑油产品送往三部轻烃异构化装置进行加工，生产高辛烷值汽油调和组分。加氢裂化液化气、重整液化气、轻烃回收液化气和焦化液化气进入气分装置加工，生产出合格的精丙烯产品、异丁烷产品和液化气产品送往储运进行产品销售。加氢装置所需原料氢气全部来自于三部PSA装置。炼油二部进出物料示意框图HydrotreatingHydrotreatingorcatalytichydrogentreatingremovesobjectionablematerialsfrompetroleumfractionsbyselectivelyreactingthesematerialswithhydrogeninareactoratrelativelyhightemperaturesatmoderatepressures.加氢精制就是在一定的温度和压力下，通过氢气与石油馏分中的杂质有选择的反应，从而脱出杂质。Theseobjectionablematerialsinclude,butarenotsolelylimitedto,sulfur,nitrogen,olefins,andaromatics.那些杂质包括硫、氮、烯烃、芳烃等。BriefIntroductionoftheHydrogenationTechnology

Thelightermaterialssuchasnaphthaaregenerallytreatedforsubsequentprocessingincatalyticreformingunits,andtheheavierdistillates,rangingfromjetfueltoheavyvacuumgasoils,aretreatedtomeetstrictproductqualityspecificationsorforuseasfeedstockselsewhereintherefinery.轻组分如石脑油通常被处理后用于重整，更重的馏分范围从喷气燃料至重瓦斯油被加氢处理后来满足产品质量要求或被用于其他装置作原料。Hydrotreatingisalsousedforupgradingthequalityofatmosphericresidsbyreducingtheirsulfurandorgano-metallicslevel.加氢精制通过降低硫和有机金属含量来改善常压渣油性质。Manyoftheproductqualityspecificationaredrivenbyenvironmentalregulationsthatarebecomingmorestringenteveryyear.

许多产品质量标准由于环境法规的要求，变的日益严格。Hydrotreatersaredesignedforandrunatavarietyofconditionsdependingonmanyfactorssuchastypeoffeed,desiredcyclelength,expectedqualityoftheproductsbutingeneraltheywilloperateatthefollowingrangeofconditions:加氢精制装置设计及运行条件取决于多种因素：原料、运行周期、产品质量，通常操作条件：LHSV(liquidhourlyspacevelocity)—0.2to8.0,H2circulation—(50–675Nm3/m3),H2PP(Hydrogenpartialpressure)—200–2,000psia(14–138bars)andSORtemperaturesrangingbetween550and700◦F(290–370◦C),withthelowerlimitsrepresentingminimumoperatingconditionsfornaphthahydrotreatingandthehighervaluesshowingoperatingconditionsusedforhydrotreatingatmosphericresids.液时空速：0.2-8.0；氢油比50-675Nm3/m3；氢分压：200–2,000psia(14–138bars)和初期温度范围550-700◦F(290–370◦C)，下限操作条件针对石脑油加氢，上限操作条件针对渣油加氢。Untilabout1980,hydrotreatingwasalicensedtechnologybeingofferedbyafairlylargenumberofcompanies.至到大约1980年，加氢精制专利技术由众多公司提供。Inthepast30years,hydrotreatingcatalystshavebecomecommoditiesandtheprocesshasbeenofferedwithoutlicensingfees.在过去的30年中，加氢精制催化剂已变成商品，工艺技术提供不再需要专利许可费。Thecommonobjectivesandapplicationsofhydrotreatingarelistedbelow：加氢精制的目的：

Naphtha(catalyticreformerfeedpretreatment)—toremovesulfur,nitrogen,andmetalsthatotherwisewouldpoisondownstreamnoblemetalreformingcatalysts.石脑油（催化重整预加氢原料）-脱除硫、氮、金属否则将会造成下游重整贵金属催化剂中毒。Keroseneanddiesel—toremovesulfurandtosaturateolefinsandsomeofthearomatics,resultinginimprovedpropertiesofthestreams(kerosenesmokepoint,dieselcetanenumberordieselindex)aswellasstoragestability.煤油和柴油-脱除硫、饱和烯烃和部分芳烃，改善产品性质（航煤烟点，柴油十六烷值或十六烷指数）和储存安定性。Lubeoil—toimprovetheviscosityindex,color,andstabilityaswellasstoragestability润滑油-改善粘度指数，颜色，安定性和储存安定性。FCCfeed—toimproveFCCyields,reducecatalystusageandstackemissions催化裂化原料-改善催化裂化产率，降低催化剂用量和烟气排放。Resids—toprovidelowsulfurfueloilstoeffectconversionand/orpretreatmentforfurtherconversiondownstream.渣油-提供低硫燃料油和影响下游加工转化率。

OVERVIEWAccordingtotheoverallprocessarrangementofthewholeplantofthePMBPetrochemicalProject,anew1.3MMT/Akerosenehydrogenationunitistobebuilt.TheunitemploysART’scatalystandLPEC’shydrogenationdesulfurizationprocesstechnology,andusesstraight-runkerosenefromthecrudeoilunitasfeedstock.Theimpuritiesinthefeedstock,suchassulfur,mercaptanandnitrogen,areremovedbyusinghydrogenandcatalysttoreducetheacidityofkerosene,improvecolorandproducesatisfactoryjetfuelproduct.根据PMB总流程安排，新建一套130万吨/年煤油加氢精制装置，采用ART和LPEC的加氢工艺技术，以常减压的直馏煤油为原料，在氢气以及催化剂的作用下脱除原料中的硫、硫醇、氮等杂质，降低煤油酸值，改善颜色，生产符合要求喷气燃料。

1.3MMTAKeroseneHTUnit1020130万吨/年煤油加氢装置 The‘hydrotreatingprocess’hasseveraldifferentapplications(e.g.desulfurization,olefinsaturation,denitrogenation,etc)andisusedforavarietyofpetroleumfractionsfromnaphthaallthewaytoatmosphericresidue,mostlyunitshavethesameflowscheme.加氢精制工艺有多种用途（如:脱硫、脱氮、烯烃饱和），应用于石脑油至常压渣油等各种馏分，大部分装置都采用相同的流程。ThisisshownveryschematicallyinFigure-1.原则示意图见图-1。

Flowschemes工艺流程

TheBruneiJetfuelstandardTheBruneiJetfuelstandard

Overview

AccordingtothegeneralprocedureofthePMBpetrochemicalproject,asetof2200KTAdieselhydrorefiningunitisrequiredtobeestablished,withstraight-runkerosene,straight-rundieselaswellascokinggasolineandcokingdieselasitsmaterials,anditsmainproductionofrefineddieselcontainingsuperlowsulfurwhichcontentisnogreaterthan10ppmanditsby-productofsmallamountofnaphtha.TheunitadoptstheliquidphasedieselhydrogenationtechnologyjointlydevelopedbySEIandRIPP.根据PMB石化项目总流程规划，建一套220万吨/年柴油加氢精制装置,以直馏煤油、直馏柴油和焦化汽油、焦化柴油为原料，生产硫含量不大于10PPm的超低硫精制柴油、副产少量石脑油。本装置SEI与RIPP开发的连续液相柴油加氢技术.

10302.2MMTADieselHTUnit 1030220万吨/年柴油加氢装置

核心是加氢催化剂的技术进步..CatalystsHydrotreatingcatalystsarehighsurfaceareamaterialsconsistingofanactivecomponentandapromoter,whichareuniformlydispersedonasupport.Thecatalystsupportisnormallygammaalumina(γ-Al2O3),sometimeswithsmallamountsofsilicaorphosphorousadded,whichispreparedinsuchawaysoastogiveahighsurfaceareaandanappropriateporestructure.Theactivecomponentisnormallymolybdenumsulfide,Formolybdenumcatalystsbothcobalt(CoMo)andnickel(NiMo)areusedaspromoters.Theacidityofthesupport(whichisprovidedbythesilica)canbeincreasedtoboostthecatalystactivityfor(hydro)crackingandisomerizationreactions.Hydrotreatingcatalystscomeindifferentsizesandshapesandvarydependingonthemanufacturer.Flowschemes工艺流程

Flowschemes工艺流程

液相加氢技术是近些年出现的一种新技术，采用液相反应，取消传统的氢气循环系统，将氢气溶解于原料油中，通过液体循环溶解足量的氢气，以满足加氢反应的需要。它为燃料油加氢提供了一种更加经济和简单的生产工艺。Liquidphasegenerationisanewtechnologyemergedinrecentyears.Iteliminatesthetraditionalrecyclehydrogensystemanddissolveshydrogeninthefeedoilandprovidesthehydrogennecessaryforthereactionthroughliquidrecycle,providingamoreeconomicalandsimplerfueloilhydrogenationprocess.杜邦公司于2007年8月从位于美国阿肯色州的技术开发公司-工艺动力学公司获取此项技术--IsoTherming，国内江苏实友最早引进采用此项柴油液相加氢技术，于2011年开工投产。DuPointacquiredIsoThermingtechnologyfromProcessDynamics,Inc.,atechnologydevelopmentfirmbasedinArkansas,USAinAugust2007.Shiyou(Yangzhou)ChemicalCo.,Ltd.firstintroducedthistechnologyinChinaanditsplantwasputintooperationin2011.随着杜邦公司近年在国内开展此项技术的推广，鉴于液相加氢技术在能耗、加工流程方面比常规滴流床加氢具有优势，LPEC和FRIPP开发了SRH液相循环加氢技术、SEI和RIPP开发的液相循环加氢技术（SLHT）。WithDuPoint’spromotionofthistechnologyinChinainrecentyearsandinviewofitsadvantagesinenergyconsumptionandprocessingprocesscomparedtotheconventionaltricklebedtechnology,LPECandFRIPPdevelopedSRH,SEIandRIPPdevelopedSLHT.目前国内在运行的液相加氢装置已有十多家，规模从30万吨/年至375万吨/年不等。TherearemorethantenliquidphasehydrogenationunitsunderoperationinChina,withcapacityrangingfrom300Kt/ato3.74Mt/a.杜邦为下流式液相加氢技术，SEI和RIPP在其工艺流程上作了改进，形成上流式连续液相加氢技术（SLHT）。SEIandRIPPdevelopedtheup-flowSLHTbyimprovingDuPoint’sdown-flowhydroprocessingtechnology.

装置特点Unitcharacteristics该装置采用SEI和RIPP共同开发的连续液相柴油加氢技术，催化齐采用石科院的RS-2100和RS-2200催化剂.ThisunitadoptsthecontinuousliquidphasedieselhydrogenationtechnologyjointlydevelopedbySEIandRIPPandthecatalystappliestheRS-2100andRS-2200catalystfromtheRIPP.为适应液相为连续相，气相为分散相的特点，反应器采用上流式。Inordertoadapttothecharacteristicsofcontinuousliquidphaseanddispersedvaporphase,thereactoremploystheup-flowstructure.反应器与热高压分离器集成设置为上流式反应/分离器。Thereactorhothighpressureseparatorisintegratedintotheup-flowreactor/separator.上流式反应/分离器的分离器部分底部设置循环油泵。

Thereisacirculatingoilpumpsetatthebottomoftheseparatorsectionfortheup-flowreactor/separator.Thereisacirculatingoilpumpsetatthebottomoftheseparatorsectionfortheup-flowreactor/separator.循环油全部在反应器入口注入反应器，补充氢气分床层注入反应器。

Allthecirculatingoilisinjectedintothereactorfromitsinlet,withthemake-uphydrogeninjectedintodifferentbeds.催化剂采有湿法硫化Thecatalystleverageswetsulfuration。

10402.2MMTAHydrocracking1040220万吨/年加氢裂化装置

OverviewInaccordancewithoverallplanningofprocessingflowpreparedforPMBproject,a2.2MMTAUnicrackingProcessUnit,whichisfedbymixedoilofstraight-rundieseloilandVGO,shouldbebuiltinordertoproduceheavynaphthaandsupplymaterialsforPXUnit.Onbasisofsingle-stagefull-circulationhydrocrackingtechnologyfromUOP,thishydrocrackingUnitcanhavereactionsuchdesulfurization,denitrogenation,hydrogenationsaturationandhydrocrackingtothefeedstockandhydrogenunderactionofcatalystathightemperatureandpressuresoasproducetheheavynaphthawhichconformstoreformingfeedstandard.ThelightnaphthaandLPGwillbealsoproducedatthebyproducts.根据PMB石化项目总加工流程的规划，建设一套220万吨/年加氢裂化装置，以直馏柴油和蜡油混合油为原料，主要生产重石脑油为PX装置供料。采用UOP的单段全循环加氢裂化技术，在高温高压下，将原料油和氢气在催化剂的作用下进行脱硫、脱氮、加氢饱和、加氢裂解等反应生产符合重整进料标准的重石脑油，同时副产轻石脑油和液化气.HydrocrackingHydrocrackingprocessbecomepopularbecauseofwiderangeoffeedstocks,highqualityproductswithhighyieldandconsiderableflexibilityofoperation.加氢裂化工艺由于原料范围广，产品质量好、液体收率高、生产灵活性大变得日益重要。Theprocessofhydrocrackingisusedtoproducelightoil,middledistillates,andfeedstockfordownstreampetrochemicalunits,thereforeitisaimportanttechnologyinfieldofmodernpetrochemicaltocombineoilrefineryandchemicalengineering.加氢裂化工艺是生产清洁燃料和优质化工原料的重要技术，是炼油与化工结合的核心。HydrocrackingHighly

selective

upgrading

of

vacuum

gas

oil

(VGO)to

high

value

transportation

fuels–

produceshighqualitykeroseneanddieselfromdifficultdistillatestreams利用劣质原料生产高质量煤油和柴油Produce

high

quality

Unconverted

Oil

(UCO)

forlube

base

oil

production

or

FCC

feedstock生产高质量的未转化油可用作润滑油基础油或催化原料–

Producequalifiedheavynaphthaasthefeedstockofreformer--生产高质量的重石脑油给重整做原料–

Can

handle

heavy

feeds能够处理劣质原料–

Selective

conversion可选择转化率–

Flexibility

to

produce

a

range

of

products可灵活生产不同产品1.2、HydrocrackingHydrocrackingisaversatilecatalyticrefiningprocessthatupgradespetroleumfeedstocksbyaddinghydrogen,removingimpurities,andcrackingtoadesiredboilingrange.加氢裂化是一种适应性较强的催化炼制过程通过加氢和脱除杂质来改善原料性质，裂化成合适的产品馏分。Hydrocrackingrequirestheconversionofavarietyoftypesofmoleculesandischaracterizedbythefactthattheproductsareofsignificantlylowermolecularweightthanthefeed.加氢裂化可以转化各种类型的分子，产品相对于原料，分子量有明显降低。Hydrocrackingfeedscanrangefromheavyvacuumgasoilsandcokergasoilstoatmosphericgasoils.Productsusuallyrangefromheavydieseltolightnaphtha.加氢裂化原料范围从重减压蜡油和焦化蜡油到常压柴油。通常产品范围从重柴油到轻石脑油。Hydrocrackersaredesignedforandrunatavarietyofconditionsdependingonmanyfactorssuchastypeoffeed,desiredcyclelength,expectedproductslatebutingeneraltheywilloperateatthefollowingrangeofconditions:liquidhourlyspacevelocity(LHSV)—0.5to2.0,H2circulation—(850–1,700Nm3/m3),H2PP—1,500to2,000psia(103–138bars),andSORtemperaturesrangingbetween675◦Fand725◦F(357–385◦C).加氢裂化的设计运行条件基于以下条件：原料性质，期望的运行周期，期望的产品构成，但通常操作条件：液时空速（LHSV）：0.5-2.0，氢油比：850–1,700Nm3/m3，氢分压：103–138bars，初期反应温度：357–385◦C

Hydrocrackingisparticularlywellsuitedtogeneratingproductsthatmeetorexceedallofthepresenttoughenvironmentalregulations.加氢裂化生产的产品可以满足目前最严格的环保要求。Flowschemes加氢裂化工艺流程

Variouslicensorshaveslightlydifferentnamesfortheirhydrocrackerflowschemes,butingeneral,themostcommonhydrocrackingprocessescanbeclassifiedinto：

各专利商在加氢裂化流程设置上略有不同，通常加氢裂化工艺流程可分为：1-stageoncethrough单程一次通过1-stagerecycle单程全循环2-stagerecycle两段全循环

ToFractionationH2

Recycle

GasScrubberSeparatorHTHCFigure-1SinglestageoncethroughPartialConversion(60-90%)SinglestageoncethroughFigure-1showsaschematicofasinglestage,once-throughhydrocrackingunit,whichisthesimplestconfigurationforahydrocracker.Thefeedmixeswithhydrogenandgoestothereactor.Theeffluentgoestofractionation,withtheunconvertedmaterialbeingtakenoutoftheunitasunconvertedmaterial.Thistypeofunitisthelowestcosthydrocrackingunit,canprocessheavy,highboilingfeedstocksandproduceshighvalueunconvertedmaterialwhichbecomesfeedstockforFCCunits,ethyleneplantsorlubeoilunits.Ingeneral,theconversionofthefeedstocktoproductsis60–70vol%,butcanrangeashighas90vol%.Partial

Conversion

(60-90%)Singlestageoncethrough

Increased

conversion

for

greater

diesel

yield

and

high

quality

UCO

Dieselmeetsstringentspecifications

KeroseneforJetA-1

UCOforlubesproductionorsteamcrackFeed

ToFractionationH2

Recycle

GasScrubberSeparatorHTHCFlow

Scheme

Can

Be

Tailored

to

Balance

Distillate

andUnconverted

Oil

Targets

Figure-1SinglestageoncethroughFull

Conversion

–

Single

Stage

Recycle

ToFractionationFeedH2Separator

Recycle

GasScrubberHTHCRecycle

UCOFigure-2SinglestagehydrocrackingunitwithrecycleThemostwidelyfoundhydrocrackingunitisthesinglestagewithrecycleinwhichtheunconvertedfeedissentbacktothereactorsectionforfurtherconversion.Itisthemosteffectivedesignfor100%(ornear100%)conversion.IncreasedconversionforgreaterdistillateornaphthayieldUCOrecycletoimproveproductselectivity

Two-Stage

Hydrocracking

1st

Stage

Reactors

FeedH2Separator

Recycle

GasScrubberHTHCHC

2nd

Stage

ReactorRecycle

UCO

UOP

6517G-8Figure-3TwostagehydrocrackingThetwostagehydrocrackingprocessconfigurationisalsowidelyused,especiallyforlargethroughputunits.

两段加氢裂化被广泛应用，特别是处理量较大的装置Intwostageunits,thehydrotreatingandsomecrackingtakesplaceinthefirststage.在两段流程中，加氢精制和部分裂化发生在一段。Theeffluentfromthefirststageisseparat