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Hydroprocessing:

Hydrotreating &
Hydrocracking
Chapters7&9
Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas


Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates


Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

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U.S.RefineryImplementationofHydrotreating

EIA,Jan.1,2017database,publishedJune2017
http://www.eia.gov/petroleum/refinerycapacity/

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U.S.RefineryImplementationofHydrocracking

EIA,Jan.1,2017database,publishedJune2017
http://www.eia.gov/petroleum/refinerycapacity/

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Purpose

Hydrotreating Hydrocracking
Removeheteroatoms&saturate Severeformofhydroprocessing
carboncarbonbonds Breakcarboncarbonbonds
Sulfur,nitrogen,oxygen,&metals Drasticreductionofmolecularweight
removed Reduceaveragemolecularweight&
Olefinic &aromaticbondssaturated producehigheryieldsoffuel
Minimalcracking products
Minimalconversion 10%to20% 50%+conversion
typical Productsmoreappropriatefordiesel
Productssuitableforfurther thangasoline
processingorfinalblending
Reforming,catalyticcracking,
hydrocracking

http://www.kbr.com/Newsroom/Publications/Brochures/HydroprocessingTechnology.pdf

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ExampleHydrogenUsage

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

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CharacteristicsofPetroleumProducts

Hydrocracking:hydrogenadditiontominimizecokeformation

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

Updated:July5,2017
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CharacteristicsofPetroleumProducts

Hydrotreating:justenoughconversiontoremoveundesirable
atoms;hydrogenadditionforatomremoval
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000

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Hydroprocessing Trends

Hydrogenisubiquitousin Drivenbyseveralfactors
refinery&expectedto Increaseduseof
increase hydrodesulfurization forlow
Produceshigheryields& sulfurfuels
upgradethequalityoffuels Heavier&highersulfurcrudes
Reductionindemandforheavy
Thetypicalrefineryrunsata fueloil
hydrogendeficit Morecompleteprotectionof
Ashydroprocessing becomes FCCUcatalysts
moreprevalent,thisdeficitwill Demandforhighqualitycoke
increase Increasedproductionofdiesel
Ashydroprocessing progressesin
severity,thehydrogendemands
increasedramatically

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SourcesofHydrogeninaRefinery

Byproductfromotherprocesses Manufactured
CatalyticReformer SteamMethaneReforming(SMR)
Mostimportantsourceofhydrogen Mostcommonmethodof
fortherefiner manufacturinghydrogen
Continuouslyregeneratedreformer: 90 95vol%typicalpurity
90vol% Gasification/PartialOxidation
Semicontinuouslyregenerated Producesynthesisgas(syngas)
reformer:80vol%
Hydrogenrecovery
FCCUOffgas o Pressureswingadsorption(PSA)
5vol%hydrogenwithmethane,
o Membraneseparation
ethane&propane
Moreexpensivethansteam
Severalrecoverymethods(canbe
reformingbutcanuselowqualityby
combined)
productstreams
o Cryogenic
o Pressureswingadsorption(PSA)
o Membraneseparation

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Hydroprocessing Catalysts

Hydrotreating Hydrocracking
Desiredfunction Crystallinesilicaaluminabasewithrareearthmetals
Cobaltmolybdenum sulfurremoval&olefin depositedinthelattice
saturation Platinum,palladium,tungsten,and/ornickel
Nickelmolybdenum nitrogenremoval&aromatic Rareearthmetalstypicallymixtureoflanthanum,
saturation cerium,andotherminorquantities
Reactorconfiguration Acidfunctionpromotesthecracking
Downflow fixedbed temperaturetocontrolfinal Feedstockmustfirstbehydrotreated
sulfurcontent
Catalystsdeactivate&cokeformsevenwithhydrogen
Firstbedmayguardbedfornickel&vanadium present
o Cheapercatalysts Hydrocrackersrequireperiodicregenerationofthe
o Mostremovalofhetereo atomsinsubsequent fixedbedcatalystsystems
beds Channelingcausedbycokeaccumulationamajor
Selectivecatalystsforsulfurremovalwithoutolefin concern
saturation Cancreatehotspotsthatcanleadtotemperature
Maintaininghighoctanerating runaways
Reactorconfiguration
Fixedbed typicalforgasoilhydrocracking
Expandedcirculatingbedorslurry proposedforresid
hydrocracking
Hydroprocessing catalysts
https://grace.com/catalystsandfuels/enus/art
hydroprocessingcatalysts

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ReactorBedConfigurations

PetroleumRefiningProcesses
J.G.Speight&B.zm
MarcelDekker,Inc.,2002,pg.452

Samplepackingofcatalystontopofsupports
ModelpreparedbyEnterpriseProducts

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Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas


Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates


Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
Hydrodesulfurization

Sulfur Unsaturatedcarboncarbonbonds
Sulfurconvertedtohydrogensulfide Olefinssaturated onehydrogen
(H2S) moleculeaddedforeachdoublebond
Addedhydrogenbreakscarbonsulfur Olefinsprevalentincrackedstreams
bonds&saturatesremaininghydrocarbon cokerorvisbreaker naphtha,catalytic
chains crackercycleoil,catalyticcrackergasoline
Formofsulfurbonds Aromaticringshydrogenatedto
Sulfurinnaphthagenerallymercaptans cycloparaffins(naphthenes)
(thiols)&sulfides Severeoperation
Inheavierfeeds,moresulfuras Hydrogenconsumptionstrongfunctionof
disulphides &thiophenes complexityofthearomatics
Lightends prevalentinheavydistillatehydrotreating,
Heavierdistillatesmakemorelightends gasoilhydrotreating,hydrocracking
frombreakingmorecomplexsulfur
molecules Selectivecatalystsforhydrotreatingcat
gasolineforsulfurremovalbutnot
saturateolefins
Maintainhighoctaneratings

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Hydrodesulfurization Chemistry

H2 required&finalhydrocarbonproductsdependentonpositionofsulfurinmolecule
CH3CH2CH2CH2CH2CH2CH2CH2SH+H2 CH3CH2CH2CH2CH2CH2CH2CH3 +H2S

CH3CH2CH2CH2CH2SCH2CH2CH3 +2H2 CH3CH2CH2CH2CH3 +CH3CH2CH3 +H2S


SaturationofmoleculespossiblebecauseofhighH2concentrations
CH3CH2CH2CH=CHCH2CH2CH3+H2CH3CH2CH2CH2CH2CH2CH2CH3
Ultralowsulfurlevelsdifficult
Complexstructures
+4H2CH3CH2CH2CH3+H2S

Mercaptan reversion
CH3CH2CH2CH2CH2CH2CH=CH2+H2SCH3CH2CH2CH2CH2CH2CH2CH2SH

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YieldEstimates

Difficulttogeneralizebecauseconversionoffeedstockisrelativelylow
Liquidproductsgenerallyhavevolume&gravityincrease typically+1oAPI
Generalrelationshipofhydrogenrequiredvs.sulfurcontent
Naphtha: (scf/bbl H2)=191 (wt%sulfur) 30.7
Middledistillates: (scf/bbl H2)=110.7 (wt%sulfur)+10.2 (%desulfurized) 659.0

PetroleumRefineryProcessEconomics,2nd ed., FundamentalsofPetroleumRefining,


RobertE.Maples,2000 byFahim,AlSahhaf,&Elkilani ,Elsevier,2010

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TypicalProcessParameters

http://www.eia.doe.gov/oiaf/servicerpt/ulsd/figd3.html

PetroleumRefiningProcesses,
byJamesG.Speight&Baki zm,MarcelDekker,Inc.,2002 LHSV=ReactantLiquidHourlySpaceVelocity
SupplementedbypersonalconversationwithBartCarpenter =Liquidvolumetricflow volumecatalyst

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SulfurDistributionvs.BoilingPointLCOFeedstock

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GeneralEffectsofProcessVariables

Reactorinlettemperature&pressure
Increasingtemperatureincreaseshydrogenationbutdecreasesthenumberofactivecatalyst
sites
Temperaturecontrolisusedtooffsetthedeclineincatalystactivity
Increasingpressureincreaseshydrogenpartialpressure&increasestheseverityof
hydrogenation

Recyclehydrogen
Requirehighconcentrationofhydrogenatreactoroutlet
Hydrogenamountismuchmorethanstoichiometric
Highconcentrationsrequiredtopreventcokelaydown&poisoningofcatalyst
Particularlytruefortheheavierdistillatescontainingresinsandasphaltenes

Purgehydrogen
Removeslightends&helpsmaintainhighhydrogenconcentration

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NaphthaHydrotreating

Naphthahydrotreated primarilyforsulfurremoval
Mostlymercaptans (RSH)&sulfides(RSR')
Somedisulfides(RSSR'),&thiophenes (ringstructures)
Mostcommoncatalystcobaltmolybdenumonalumina
Chemicalhydrogenconsumptiontypically50to250scf/bbl
Fordesulfurizationcontainingupto1wt%sulfur 70to100scf/bbl
Significantnitrogen&sulfurremoval 250scf/bbl
Ultralowsulfurlevelsdifficultbecauseof

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NaphthaHydrotreating Process

Reactortypicallyat200psig&700oF
Temperatureincreasesto
compensatefordecreaseincatalyst
activity

Liquidspacevelocity~2perhour
Hydrogenrecycle~2,000scf/bbl
Acidgasremovalmaynotbedirectly
incorporatedintorecyclegasloop
Overheadvaporfromfractionatorto
saturatesgasplanttorecoverlight
hydrocarbons&removeH2S
Haldo Topse processflow
2011RefiningProcessesHandbook
Productfractionation HydrocarbonProcessing,2011

Pentane/hexaneoverheadeitherto
blendingorisomerization
Bottomstoreformer

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DistillateHydrotreating

Ingeneral,allliquiddistillatestreams
containsulfurcompoundsthatmust
beremoved
Saturateolefinsindieseltoimprove
thecetane number
Hydrogenationatthehighpressure
producessmallamountsofnaphtha
fromhydrocracking
Requiredtogetattheembedded
sulfur
Dieselhydrotreater stabilizerwill
haveanuppersidestream draw TotalDistillateHydrotreater
http://www.totalpetrochemicalsusa.com/press_room/press_releases_dcpphotos.asp
producingthenaphthawhichis
recycledtomotorgasolineprocessing

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Copyright2017JohnJechura(jjechura@mines.edu)
DistillateHydrotreating Process

Reactortypicallyat800oF
Hydrogenrecyclestartsat2,000
scf/bbl;consumption100to400
scf/bbl
Conditionshighlydependentupon
feedstock
Distillate(jetfuel&diesel)with85%
95%sulfurremoval
300psig
hydrogenconsumption200 300
scf/bbl
Saturationofdieselforcetane Haldo Topse processflow
2011RefiningProcessesHandbook
numberimprovement HydrocarbonProcessing,2011
over800scf/bbl hydrogen
upto1,000psig

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BoilingPointRangesforProducts
19,145 bpd Sour Distillate Feed
18,292 bpd Treated Distillate
3,000

35-Treated.Distillate
31-Liquids
2,500
27-Off.Gas
1-fresh.charge
Incremental Yield [bpd]

2,000

1,500

1,000

500

-
0 100 200 300 400 500 600 700 800
BPT [F]
Basedonexampleproblemin:
RefineryProcessModeling,APracticalGuidetoSteadyStateModelingofPetroleumProcesses,1st ed.
GeraldKaes,AthensPrintingCompany,02004

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GasOilHydrotreating

Catalyticcrackerfeedstocks (atmospheric Gasoilscanbecontaminatedwithresins


gasoil,lightvacuumgasoil,solvent &asphaltenes
deasphalting gasoil)hydrotreated Depositedinhydrotreater
severely Requirecatalystreplacementwitha
Sulfurremoval shorterrunlengththandeterminedby
Openingofaromaticrings deactivation
Removalofheavymetals Guardchambermaybeinstalledto
prolongbedlife
Desulfurizationofgasoilcanbeachieved
witharelativelymodestdecomposition Nickelmolybdenumcatalystsystemfor
ofstructures severehydrotreating
Gasoilunitsmoreexpensivebecauseof
moreintensivehydrogenation
Quench
Multistageflash
Morecomplexstrippers

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Copyright2017JohnJechura(jjechura@mines.edu)
GasOilHydrotreating Process

Normallytworeactorbeds control
temperaturerise
Hydrogenpartialpressurerelatedtoring
saturation&amountofsulfur
Forlowringsaturation300psigmaybe
sufficient
1,200psigwillconvert25%ring
saturation&somewhatlessthan95%
sulfurremoval
Pressuresashighas1,500psigcan
saturate30%ofaromaticrings

Hydrogenabsorptionof300scf/bbl
ChevronLummus GlobalLLCprocessflow
couldgiveabout80%sulfurremoval& 2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
onlyrequire300psig
Noringsaturationatthesemild
conditions

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SaturationofBenzeneinGasoline

Strategiesforreductionofbenzeneingasoline
Reducebenzeneprecursorsinfeedtoreformer
Hydrotreat/saturatebenzeneinappropriateboilingrangefraction

Typicalprocessingstrategy
Separate&hydrotreat narrowcut
C6fractionfromrestoffeedstock
Saturatethearomatics&olefins
ofthetreatedstream
RetaintheolefinsintheC5 and
thearomatics&olefinsofthe
C7+fractions

Blendproductbackintothe
strippedfeedstock

GTCTechnologyprocessflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011

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SaturationofBenzeneinGasoline

UOPsBenSatTM processcanbeusedona
lightreformerstream
Upto30vol%benzeneinfeed
Norecyclegas
Norecyclecompressor
Norecyclecompressionpowerrequirements
Longcatalystlife
Highcatalystselectivity
Pros&cons
NoincreaseinRVP
Mildvolumetricswelling,+1to+6vol%
Doloseoctanerating

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CatalyticDewaxing ofMiddleDistillates

Improvecoldflowproperties
Clariant SelectiveHydrocrackingProcess
Selectivelycracksnormalparaffins duetosize
ofzeolitepores
Configurations
Catalyticdewaxing bedwithinanexisting
Standalone hydrotreating unit
Incorporatewithinexistinghydrotreating unit
Combinedhydrotreating &dewaxing

Ref:Considercatalyticdewaxing asatooltoimprovedieselcoldflowproperties,
Rakoczy &Morse,HydrocarbonProcessing,July2013 Combinedhydrotreating &catalyticdewaxing units

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Gases

Polymer- Sulfur
ization Plant
Sulfur

LPG
Sat Gas
Gas Plant

Butanes Fuel Gas


Alkyl
Feed LPG
Alkylation

Gas Polymerization
Separation & Naphtha
Stabilizer Isom-
erization
Light Naphtha
Alkylate
Aviation
Isomerate
Gasoline
Automotive
Gasoline
Reformate
Naphtha Solvents
Heavy Naphtha
Hydro-
Naphtha Reforming
treating Naphtha
Atmospheric
Distillation

Jet Fuels
Kerosene
Crude
Desalter Kerosene
Oil
Distillate Cat Solvents
AGO Hydro-
Naphtha Distillate
cracking Treating &
Hydro-
Blending
Heating Oils
treating
Gas Oil Fluidized
Cat Diesel
LVGO Hydro- Catalytic
treating Cracking Distillates
Vacuum
Distillation
Fuel Oil
HVGO
Cycle Oils
Residual
Fuel Oils
DAO
Solvent
Deasphalting SDA
Coker Asphalts
Bottoms
Naphtha Naphtha

Visbreaking Heavy Distillates


Fuel Oil
Coker Bottoms
Vacuum Gas
Lube Oil Lubricant
Residuum Oil
Solvent Greases
Dewaxing
Waxes
Waxes
Coking Light Coker
Gas Oil

Coke

Updated:July5,2017
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Hydrocracking

Purpose:processgasoiltobreakcarboncarbonbondsoflarge
aromaticcompounds&removecontaminants
Hydrogenation(additionofhydrogen)
Cracking(carboncarbonscission)ofaromaticbonds
Intenttocreatemiddledistillateproducts,notgasolinerange
products

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HydrocrackerYieldExample

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HydrocrackerYieldTrends

Figure7.4
Startovercrackingtheheavynaphtha
fractionwhenthelightnaphthayields
getsabove25vol%.

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BoilingPointRangesforHydroprocessing Products

700

14
600 21
20-OffGas
1-oil.feed
500

Incremental Yield [bpd]


400

300

200

100

-
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
BPT [F]

Basedonexampleproblemin:
RefineryProcessModeling,APracticalGuidetoSteadyStateModelingofPetroleumProcesses,1st ed.
GeraldKaes,AthensPrintingCompany,02004

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HydrocrackingFeeds

Typicalfeeds
Catcrackercycleoil
Highlyaromaticwithsulfur,smallring&polynuclear aromatics,catalystfines;
usuallyhashighviscosity
Hydrocrackedtoformhighyieldsofjetfuel,kerosene,diesel,&heatingoil
Gasoilsfromvisbreaker
Aromatic
Gasoilfromthedelayedcoker
Aromatic,olefinic,withsulfur

Usuallymoreeconomicaltorouteatmospheric&vacuumgasoils
tothecatcrackertoproduceprimarilygasoline&somediesel

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GasOilHydrocrackerFeed

Hydrocrackingdoesabetterjobofprocessingaromaticrings
withoutcokingthancatalyticcracking
Hydrogenusedtohydrogenatepolynuclear aromatics(PNAs)
Reducesfrequencyofaromaticcondensation
Hydrocrackingnotasattractiveasdelayedcokingforresids highin
resins,asphaltenes &heteroatomcompounds
Heteroatoms&metalsprevalentinresins&asphaltenes poison
hydroprocessing catalysts
Highconcentrationsofresins&asphaltenes willstillultimatelycoke
FeedslimitedtoaConradson CarbonNumber(CCR)of8wt%
Feedsrequirehighpressures&largeamountsofhydrogen

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GasOilHydrocrackerProducts

Hydrocrackingprimarilytomakedistillates
InUShydrocrackingnormallyaspecializedoperationusedtooptimize
catalyticcrackeroperation
InUScatcrackingpreferredtomakegasolinefromheavierfractions
Hydrocrackingcapacityisonlyabout8%ofthecrudedistillation
capacity
Notallrefinerieshavehydrocrackers
Intentistominimizetheproductionofheavyfueloil
Lightendsareapproximately5%ofthefeed.
Middledistillates(kerosene,jetfuel,diesel,heatingoil)stillcontain
uncracked polynuclear aromatics
Allliquidfractionsarelowinsulfur&olefins
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HydrocrackingChemistry

Crackingreactions Hydrogenationreactions IsomerizationReactions


Saturatedparaffins cracked Exothermicgivingoffheat Isomerizationprovides
toformlowermolecular Hydrogeninsertedto branchingofalkylgroups
weightolefins&paraffins saturatenewlyformed ofparaffins andopeningof
Sidechainscrackedoff moleculefromaromatic naphthenicrings
smallringaromatics(SRA) cracking
&cycloparaffins Olefinsaresaturatedto CondensationReactions
(naphthenes) formlighthydrocarbons, Suppressedbyhydrogen
Sidechainscrackedoff especiallybutane
resins&asphaltenes Aromaticrings
leavingthermallystable hydrogenatedto
polynucleararomatics cycloparaffins
(PNAs) (naphthenes)
Butcondensation Carboncarbonbonds
(dehydrogenation) cleavedtoopenaromatic
alsooccursifnot &cycloparaffins
limitedby (naphthenes)rings
hydrogenation HeteroatomsformH2S,
NH3,H2O,HCl

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SingleStageHydrocracking

Feedstockhydrotreated toremovesulfur,
nitrogen,oxygencomponents
Guardreactorstoremovemetals

Temperatures660 800oF
Mayraisetemperature0.1 0.2oFperday
tooffsetlossofcatalystactivity

Pressures1,200 2,000psig
Raisingpressureincreasesconversion

Hydrogen
Highhydrogenrecycletominimizecoking
Consumption
Lowpressure mildseverity 1,000 2,000
scf/bbl
Highpressure highseverity 2,000 Haldo Topse processflow
2011RefiningProcessesHandbook
3,000scf/bbl HydrocarbonProcessing,2011

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ReactorConfiguration

Actualconfigurationmayhavemultiplevesselsand/orcatalystzones
Dependentonexpected
feedstocks
Exampleshowsseparate
vesselsforremoval
ofmetals,heteroatoms,
&cracking
Mulitiple zonesinthe
Pretreatreactortofocus
onsulfur&nitrogen
removal

ModifiedFig.9
Unlocknextlevelhydrocrackerflexibilityintodaysturbulentmarkets
Baric,Kang,&Orzeszko
HydrocarbonProcessing,September2016

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ValueofHydrocrackersinU.S.Refining

Since2007U.S.oilrefiningfocushasbeen
maximizingdistillateproductionattheexpense
ofgasolineproduction
U.S.gasolineconsumptionhasbeendecreasing
U.S.&worldwidedieselconsumptioncontinuing
torise

Valueofgasoilhydrocrackers
Volumeexpansionthroughhydrogensaturation&bycrackinglargermoleculesintosmaller
ones
Yieldalargeamountofdistillateproductscomparedtogasolineproducts
Haveflexibilitytoshiftabout10%betweentheseproducts
FurtheradjustmentscanbemanagedbychangingfractionationoperationsHydrocrackerdistillate
productiongoodqualityforjet&dieselfuel

Productshaveverylowimpurities(i.e.sulfur,metals,etc) goodforblendinginto
finishedproductpoolsorforreprocessingindownstreamunits(i.e.reformers)
Ref:http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/

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ValueofHydrocrackersinU.S.Refining

Marketfactors
IncrementalcostofhydrogendecreasingbecauseofthesurplusofnaturalgasinNorth
America(fromshaleformations)
Regionalsupply&demandbalanceofgasoils
InNorthAmericagasoilspricerelativetotheincrementaldispositiontoaFCCU
o Bettermarginstofeedhydrocrackerstomakedistillatevs.feedFCCUtomakegasoline
o Usedtohavemarginsof$10perbbl feedstock,nowinthe$15to$20perbbl range

Downsidesofhydrocrackers
Highhydrogenconsumption
Highenergyconsumption
Highcapitalrequirements
Highcatalystcosts
Highmaintenancecosts

Ref:http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/

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Summary

Updated:July5,2017
Copyright2017JohnJechura(jjechura@mines.edu)
Summary

Hydrotreating &hydrocrackingareoppositeextremesofthe
generalhydroprocessing
Hydrotreating Hydrocracking
Breakonlythosebondsthatallow Breakcarboncarbonbondsto
removalofundesiredatoms createsmallermolecules
(sulfur,nitrogen,.) Productshaveessentiallyzero
Higher severityrequiredtomeet sulfur feedmustbeseverely
ultralowsulfurproductspecs hydrotreated toprotectcracking
Canalsousetocontrolwax catalysts
formationtendencies Productsarehighlysaturated
Willtendto makesomesmaller goodjet&diesel,poorgasoline
moleculesduetopositonofsulfur Goodcetane numbers,poor
infeedstockmolecule octanenumbers
Highseverityhydrotreating actslikemild hydrocracking

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SupplementalSlides

Updated:July5,2017
Copyright2017JohnJechura(jjechura@mines.edu)
Hydroprocessing Objectives

Feedstocks DesiredProducts ProcessObjectives


Naphthas Catalyticreformerfeed RemovalofS,N,&olefins
LPG Hydrocracking
Atmosphericgasoils Diesel RemovalofS,aromatics,&nparaffins
Jet RemovalofS&aromatics
Ethylenefeedstock Removalofaromatics
Naptha Hydrocracking
Vaccumgasoils LSFO RemovalofS
FCCfeed RemovalofS,N,&metals
Diesel RemovalofS&aromatics
Hydrocracking
Kerosene/jet RemovalofS&aromatics
Hydrocracking
Naptha Hydrocracking
LPG Hydrocracking
Ethylenefeedstock Removalofaromatics
Hydrocracking
Lubeoilbasestock RemovalofS,N,&aromatics
Hydrocracking
Residuum LSFO RemovalofS
FCCfeedstock RemovalofS,N,CCR,&metals
Cokerfeedstock RemovalofS,CCR,&metals
Diesel Hydrocracking
HandbookofPetroleumRefiningProcesses,3rd ed.
Ed.RobertA.Meyers,McGrawHill,2004

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Hydrotreating InstalledCost

Includes
Productfractionation.
Completepreheat,reaction,andhydrogen
circulationfacilities.
Sufcientheatexchangetocoolproductsto
ambienttemperature.
Centralcontrolsystem.
Initialcatalystcharge.

Excludes
Feedfractionation.
Makeuphydrogengeneration.
Sulfurrecoveryfromoffgas.
Coolingwater,system,andpowersupply.

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007

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Hydrocrackervs.FCCInstalledCost

HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
50,000bpd@2000scf/bbl $350millioninstalledcost CRCPress,2007

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Hydrotreating Technologies

Provider Features

Axens Hydrotreating:diesel;resid;hydrodearomatization (2stageHDS/HAD)

CDTECH Hydrotreating:CDHydro &CDHDS

ChevronLummus GlobalLLC Hydrotreating:ISOTREATING,RDS/VRDS/UFR/OCR

DuPont Hydrotreating

GTCTechnology Hydrotreating,pyrolysisgasoline

Haldor Topsoe A/S Hydrotreating

UOP Hydrotreating;Hydrotreating/desulfurization(SelectFining)

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HydrocrackingTechnologies

Provider Features

Axens Hydrocracking;Resid hydrocracking(HOilOC)

ChevronLummus GlobalLLC Hydrocracking(ISOCRACKING);Resid hydrocracking

DuPont Hydrocracking

ExxonMobilResearch& Hydrocracking,moderatepressure(MPHC)
Engineering
Haldor Topsoe A/S Hydrocracking

ShellGlobalSolutions Hydrocracking

UOP Hydrocracking

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Hydrotreating HydrogenConsumption

Chemicalconsumptionduetohydrogenationreactions
Crackingreactionsofcarboncarbonbondsminimalinhydrotreating,evenduring
aromaticsaturation
Olefinic bondseasiertosaturatethanaromaticbonds
Straightrunstockshaveessentiallyzeroolefins

Hydrogenislostinequilibriumwithlightgases
Amountissignificant&maydoubleamountrequiredforsulfurremoval
Hydrogenabsorbedinliquidproducts
Usuallysmallcomparedtosulfurremovalneeds 1lb/bbl
Hydrogenremovedwithpurgegas
Usedtomaintainahighpurityofhydrogen lightendsdilutethehydrogen
concentration
Usuallysmallcomparedtosulfurremovalneeds

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HydrocrackingHydrogenConsumption&Loss
Heteroatomcarbonbonds Saturationofcarboncarbonbonds Crackingofcarboncarbon
broken&saturated Olefinssaturatedtoformlight bonds
Createslightends hydrocarbons. Severeoperation
Heavierdistillates Consumptionstoichiometric hydrogenconsumption
makemorelight onehydrogenmolecule strongfunctionof
endsfrombreaking addedforeachdoublebond complexityofthearomatics
morecomplex Aromaticringshydrogenatedto Hydrogenmixedwithproducts
molecules cycloparaffins (naphthenes). Equilibriumwithlightgases
SulfurconvertedtoH2S Severeoperation Significant may
Nitrogenconvertedto hydrogenconsumption doubleamount
NH3 strongfunctionof requiredforsulfur
Oxygenconvertedto complexityofthearomatics removal
H2O Isomerizationreactionsgenerally Absorbedinliquidproducts
Organicchlorides notpresent Usuallysmall
convertedtoHCl Metalsdepositeddirectlyonthe comparedto
catalysts hydrogenusedfor
Excessmetalsreduce sulfurremoval
catalystactivity&promote Lostwithpurgegas
dehydrogenation(produces
coke&hydrogen)

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Severityofoperations

Hydrocracking solutionssqueezemoreULSDfromheavyends
E.Benazzi,J.Bonnardot,F.Morel,HydrocarbonProcessing,November2009

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SingleStageHydrocrackingwithHDS1st Step

PetroleumRefineryProcessEconomics,2nd ed.,
RobertE.Maples,Figure141,2000

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UOPTwoStageUnicrackingProcess

http://www.uop.com/hydrocrackingunicrackingstage/

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UOPsHyCycle UnicrackingTM Process

http://www.uop.com/objects/Hycycle.pdf

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