Professional Documents
Culture Documents
Hydrotreating &
Hydrocracking
Chapters7&9
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
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
Coke
Updated:July5,2017
2
Copyright2017JohnJechura(jjechura@mines.edu)
U.S.RefineryImplementationofHydrotreating
EIA,Jan.1,2017database,publishedJune2017
http://www.eia.gov/petroleum/refinerycapacity/
Updated:July5,2017
3
Copyright2017JohnJechura(jjechura@mines.edu)
U.S.RefineryImplementationofHydrocracking
EIA,Jan.1,2017database,publishedJune2017
http://www.eia.gov/petroleum/refinerycapacity/
Updated:July5,2017
4
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
5
Copyright2017JohnJechura(jjechura@mines.edu)
ExampleHydrogenUsage
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
Updated:July5,2017
6
Copyright2017JohnJechura(jjechura@mines.edu)
CharacteristicsofPetroleumProducts
Hydrocracking:hydrogenadditiontominimizecokeformation
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
Updated:July5,2017
7
Copyright2017JohnJechura(jjechura@mines.edu)
CharacteristicsofPetroleumProducts
Hydrotreating:justenoughconversiontoremoveundesirable
atoms;hydrogenadditionforatomremoval
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
Updated:July5,2017
8
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
9
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
10
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
11
Copyright2017JohnJechura(jjechura@mines.edu)
ReactorBedConfigurations
PetroleumRefiningProcesses
J.G.Speight&B.zm
MarcelDekker,Inc.,2002,pg.452
Samplepackingofcatalystontopofsupports
ModelpreparedbyEnterpriseProducts
Updated:July5,2017
12
Copyright2017JohnJechura(jjechura@mines.edu)
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
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
Coke
Updated:July5,2017
13
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
Updated:July5,2017
14
Copyright2017JohnJechura(jjechura@mines.edu)
Hydrodesulfurization Chemistry
H2 required&finalhydrocarbonproductsdependentonpositionofsulfurinmolecule
CH3CH2CH2CH2CH2CH2CH2CH2SH+H2 CH3CH2CH2CH2CH2CH2CH2CH3 +H2S
Mercaptan reversion
CH3CH2CH2CH2CH2CH2CH=CH2+H2SCH3CH2CH2CH2CH2CH2CH2CH2SH
Updated:July5,2017
15
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
TypicalProcessParameters
http://www.eia.doe.gov/oiaf/servicerpt/ulsd/figd3.html
PetroleumRefiningProcesses,
byJamesG.Speight&Baki zm,MarcelDekker,Inc.,2002 LHSV=ReactantLiquidHourlySpaceVelocity
SupplementedbypersonalconversationwithBartCarpenter =Liquidvolumetricflow volumecatalyst
Updated:July5,2017
17
Copyright2017JohnJechura(jjechura@mines.edu)
SulfurDistributionvs.BoilingPointLCOFeedstock
Updated:July5,2017
18
Copyright2017JohnJechura(jjechura@mines.edu)
GeneralEffectsofProcessVariables
Reactorinlettemperature&pressure
Increasingtemperatureincreaseshydrogenationbutdecreasesthenumberofactivecatalyst
sites
Temperaturecontrolisusedtooffsetthedeclineincatalystactivity
Increasingpressureincreaseshydrogenpartialpressure&increasestheseverityof
hydrogenation
Recyclehydrogen
Requirehighconcentrationofhydrogenatreactoroutlet
Hydrogenamountismuchmorethanstoichiometric
Highconcentrationsrequiredtopreventcokelaydown&poisoningofcatalyst
Particularlytruefortheheavierdistillatescontainingresinsandasphaltenes
Purgehydrogen
Removeslightends&helpsmaintainhighhydrogenconcentration
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
NaphthaHydrotreating
Naphthahydrotreated primarilyforsulfurremoval
Mostlymercaptans (RSH)&sulfides(RSR')
Somedisulfides(RSSR'),&thiophenes (ringstructures)
Mostcommoncatalystcobaltmolybdenumonalumina
Chemicalhydrogenconsumptiontypically50to250scf/bbl
Fordesulfurizationcontainingupto1wt%sulfur 70to100scf/bbl
Significantnitrogen&sulfurremoval 250scf/bbl
Ultralowsulfurlevelsdifficultbecauseof
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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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
Updated:July5,2017
23
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
24
Copyright2017JohnJechura(jjechura@mines.edu)
GasOilHydrotreating
Updated:July5,2017
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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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
SaturationofBenzeneinGasoline
UOPsBenSatTM processcanbeusedona
lightreformerstream
Upto30vol%benzeneinfeed
Norecyclegas
Norecyclecompressor
Norecyclecompressionpowerrequirements
Longcatalystlife
Highcatalystselectivity
Pros&cons
NoincreaseinRVP
Mildvolumetricswelling,+1to+6vol%
Doloseoctanerating
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
29
Copyright2017JohnJechura(jjechura@mines.edu)
Gases
Polymer- Sulfur
ization Plant
Sulfur
LPG
Sat Gas
Gas Plant
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
Coke
Updated:July5,2017
30
Copyright2017JohnJechura(jjechura@mines.edu)
Hydrocracking
Purpose:processgasoiltobreakcarboncarbonbondsoflarge
aromaticcompounds&removecontaminants
Hydrogenation(additionofhydrogen)
Cracking(carboncarbonscission)ofaromaticbonds
Intenttocreatemiddledistillateproducts,notgasolinerange
products
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
HydrocrackerYieldExample
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
HydrocrackerYieldTrends
Figure7.4
Startovercrackingtheheavynaphtha
fractionwhenthelightnaphthayields
getsabove25vol%.
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
BoilingPointRangesforHydroprocessing Products
700
14
600 21
20-OffGas
1-oil.feed
500
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
Updated:July5,2017
34
Copyright2017JohnJechura(jjechura@mines.edu)
HydrocrackingFeeds
Typicalfeeds
Catcrackercycleoil
Highlyaromaticwithsulfur,smallring&polynuclear aromatics,catalystfines;
usuallyhashighviscosity
Hydrocrackedtoformhighyieldsofjetfuel,kerosene,diesel,&heatingoil
Gasoilsfromvisbreaker
Aromatic
Gasoilfromthedelayedcoker
Aromatic,olefinic,withsulfur
Usuallymoreeconomicaltorouteatmospheric&vacuumgasoils
tothecatcrackertoproduceprimarilygasoline&somediesel
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
GasOilHydrocrackerProducts
Hydrocrackingprimarilytomakedistillates
InUShydrocrackingnormallyaspecializedoperationusedtooptimize
catalyticcrackeroperation
InUScatcrackingpreferredtomakegasolinefromheavierfractions
Hydrocrackingcapacityisonlyabout8%ofthecrudedistillation
capacity
Notallrefinerieshavehydrocrackers
Intentistominimizetheproductionofheavyfueloil
Lightendsareapproximately5%ofthefeed.
Middledistillates(kerosene,jetfuel,diesel,heatingoil)stillcontain
uncracked polynuclear aromatics
Allliquidfractionsarelowinsulfur&olefins
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
HydrocrackingChemistry
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
ReactorConfiguration
Actualconfigurationmayhavemultiplevesselsand/orcatalystzones
Dependentonexpected
feedstocks
Exampleshowsseparate
vesselsforremoval
ofmetals,heteroatoms,
&cracking
Mulitiple zonesinthe
Pretreatreactortofocus
onsulfur&nitrogen
removal
ModifiedFig.9
Unlocknextlevelhydrocrackerflexibilityintodaysturbulentmarkets
Baric,Kang,&Orzeszko
HydrocarbonProcessing,September2016
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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/
Updated:July5,2017
41
Copyright2017JohnJechura(jjechura@mines.edu)
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/
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
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SupplementalSlides
Updated:July5,2017
Copyright2017JohnJechura(jjechura@mines.edu)
Hydroprocessing Objectives
Updated:July5,2017
46
Copyright2017JohnJechura(jjechura@mines.edu)
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
Updated:July5,2017
47
Copyright2017JohnJechura(jjechura@mines.edu)
Hydrocrackervs.FCCInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
50,000bpd@2000scf/bbl $350millioninstalledcost CRCPress,2007
Updated:July5,2017
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Hydrotreating Technologies
Provider Features
DuPont Hydrotreating
GTCTechnology Hydrotreating,pyrolysisgasoline
UOP Hydrotreating;Hydrotreating/desulfurization(SelectFining)
Updated:July5,2017
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Copyright2017JohnJechura(jjechura@mines.edu)
HydrocrackingTechnologies
Provider Features
DuPont Hydrocracking
ExxonMobilResearch& Hydrocracking,moderatepressure(MPHC)
Engineering
Haldor Topsoe A/S Hydrocracking
ShellGlobalSolutions Hydrocracking
UOP Hydrocracking
Updated:July5,2017
50
Copyright2017JohnJechura(jjechura@mines.edu)
Hydrotreating HydrogenConsumption
Chemicalconsumptionduetohydrogenationreactions
Crackingreactionsofcarboncarbonbondsminimalinhydrotreating,evenduring
aromaticsaturation
Olefinic bondseasiertosaturatethanaromaticbonds
Straightrunstockshaveessentiallyzeroolefins
Hydrogenislostinequilibriumwithlightgases
Amountissignificant&maydoubleamountrequiredforsulfurremoval
Hydrogenabsorbedinliquidproducts
Usuallysmallcomparedtosulfurremovalneeds 1lb/bbl
Hydrogenremovedwithpurgegas
Usedtomaintainahighpurityofhydrogen lightendsdilutethehydrogen
concentration
Usuallysmallcomparedtosulfurremovalneeds
Updated:July5,2017
51
Copyright2017JohnJechura(jjechura@mines.edu)
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)
Updated:July5,2017
52
Copyright2017JohnJechura(jjechura@mines.edu)
Severityofoperations
Hydrocracking solutionssqueezemoreULSDfromheavyends
E.Benazzi,J.Bonnardot,F.Morel,HydrocarbonProcessing,November2009
Updated:July5,2017
53
Copyright2017JohnJechura(jjechura@mines.edu)
SingleStageHydrocrackingwithHDS1st Step
PetroleumRefineryProcessEconomics,2nd ed.,
RobertE.Maples,Figure141,2000
Updated:July5,2017
54
Copyright2017JohnJechura(jjechura@mines.edu)
UOPTwoStageUnicrackingProcess
http://www.uop.com/hydrocrackingunicrackingstage/
Updated:July5,2017
55
Copyright2017JohnJechura(jjechura@mines.edu)
UOPsHyCycle UnicrackingTM Process
http://www.uop.com/objects/Hycycle.pdf
Updated:July5,2017
56
Copyright2017JohnJechura(jjechura@mines.edu)