Hydroprocessing:Hydrotreating &Hydrocracking

Chapters7&9

JohnJechura jjechura@mines.edu
Updated:July8,2014

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

U.S.RefineryImplementationofHydrotreating
Top 10 Refinery Capacity & Selected Small Refineries

EIA,Jan.1,2013database,publishedJune2013
http://www.eia.gov/petroleum/refinerycapacity/
3

U.S.RefineryImplementationofHydrocracking
Top 10 Hydrocrackers & all Hydrocrackers w/o FCCs

EIA,Jan.1,2013database,publishedJune2013
http://www.eia.gov/petroleum/refinerycapacity/
4

Purpose
Hydrotreating
Removeheteroatoms&saturate
carboncarbonbonds
Sulfur,nitrogen,oxygen,&metals
removed
Olefinic &aromaticbondssaturated

Minimalcracking
Minimalconversion 10%to20%
typical
Productssuitableforfurtherprocessing
orfinalblending

Hydrocracking
Severeformofhydroprocessing
Breakcarboncarbonbonds
Drasticreductionofmolecularweight

Reduceaveragemolecularweight&
producehigheryieldsoffuelproducts
50%+conversion
Productsmoreappropriatefordiesel
thangasoline

Reforming,catalyticcracking,
hydrocracking

TypicalHydrogenUsage

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

CharacteristicsofPetroleumProducts

Hydrocracking:hydrogenadditiontominimizecokeformation
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

CharacteristicsofPetroleumProducts

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

HydroprocessingTrends
Hydrogenisubiquitousinrefinery&expectedtoincrease
Produceshigheryields&upgradethequalityoffuels

Thetypicalrefineryrunsatahydrogendeficit
Ashydroprocessing becomesmoreprevalent,thisdeficitwillincrease
Ashydroprocessing progressesinseverity,thehydrogendemandsincreasedramatically

Drivenbyseveralfactors
Increaseduseofhydrodesulfurization forlowsulfurfuels
Heavier&highersulfurcrudes
Reductionindemandforheavyfueloil
MorecompleteprotectionofFCCUcatalysts
Demandforhighqualitycoke
Increasedproductionofdiesel

SourcesofHydrogeninaRefinery
Byproductfromotherprocesses

Manufactured

CatalyticReformer

SteamMethaneReforming(SMR)

Mostimportantsourceofhydrogenforthe
refiner
Continuouslyregeneratedreformer:90vol%
Semicontinuouslyregeneratedreformer:80vol%

FCCUOffgas
5vol%hydrogenwithmethane,ethane&
propane
Severalrecoverymethods(canbecombined)

Mostcommonmethodofmanufacturing
hydrogen
90 95vol%typicalpurity

Gasification/PartialOxidation
Producesynthesisgas(syngas)
Hydrogenrecovery

Cryogenic

Pressureswingadsorption(PSA)

Pressureswingadsorption(PSA)

Membraneseparation

Membraneseparation

Moreexpensivethansteamreformingbutcan
uselowqualitybyproductstreams

10

HydroprocessingCatalysts
Hydrotreating
Desiredfunction
Cobaltmolybdenum sulfurremoval&olefin
saturation
Nickelmolybdenum nitrogenremoval&
aromaticsaturation

Reactorconfiguration
Downflow fixedbed temperaturetocontrol
finalsulfurcontent
Firstbedmayguardbedfornickel&vanadium
o

Cheapercatalysts

Mostremovalofhetereo atomsin
subsequentbeds

Selectivecatalystsforsulfurremovalwithout
olefinsaturation
Maintaininghighoctanerating

Hydrocracking
Crystallinesilicaaluminabasewithrareearth
metalsdepositedinthelattice
Platinum,palladium,tungsten,and/ornickel
Rareearthmetalstypicallymixtureoflanthanum,
cerium,andotherminorquantities
Acidfunctionpromotesthecracking

Feedstockmustfirstbehydrotreated
Catalystsdeactivate&cokeformsevenwith
hydrogenpresent
Hydrocrackersrequireperiodicregenerationof
thefixedbedcatalystsystems
Channelingcausedbycokeaccumulationamajor
concern
Cancreatehotspotsthatcanleadtotemperature
runaways

Reactorconfiguration
Fixedbed typicalforgasoilhydrocracking
Expandedcirculatingbedorslurry proposedfor
resid hydrocracking

11

ReactorBedConfigurations

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

Slurryphasehydrocrackingpossiblesolutiontorefining
margins,M.Motaghi &A.Subramanian,Hydrocarbon
Processing,February2011

12

13

Hydrodesulfurization
Sulfur
Sulfurconvertedtohydrogensulfide(H2S)
Addedhydrogenbreakscarbonsulfurbonds&saturatesremaininghydrocarbonchains

Formofsulfurbonds
Sulfurinnaphthagenerallymercaptans(thiols)&sulfides
Inheavierfeeds,moresulfurasdisulphides&thiophenes

Lightends
Heavierdistillatesmakemorelightendsfrombreakingmorecomplexsulfurmolecules

Unsaturatedcarboncarbonbonds
Olefinssaturated onehydrogenmoleculeaddedforeachdoublebond
Olefinsprevalentincrackedstreams cokerorvisbreakernaphtha,catalyticcrackercycleoil,catalyticcracker
gasoline

Aromaticringshydrogenatedtocycloparaffins(naphthenes)
Severeoperation
Hydrogenconsumptionstrongfunctionofcomplexityofthearomatics
prevalentinheavydistillatehydrotreating,gasoilhydrotreating,hydrocracking

Selectivecatalystsavailableforhydrotreatingcatgasolineforsulfurremovalbutnotsaturateolefins
Maintainhighoctaneratings

14

YieldEstimates
Difficultpartlybecauseconversionoffeedstockisrelativelylow
Liquidproductsgenerallyhavegravity+1API
Overallvolumetypicallyincreases

Generalrelationshipofhydrogenrequiredvs.sulfurcontent
360
320
280

SCFBofHydrogen

240
200
160
120
80
40
0
0.2

0.4

0.6

0.8

1.0

1.2

1.4

1.6

1.8

2.0

WeightPercentSulfurinFeed

PetroleumRefiningProcesses,
byJamesSpeight&Baki Ozum,MarcelDekker,2002
15

TypicalProcessParameters

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

PetroleumRefiningProcesses,
byJamesG.Speight&Baki zm,MarcelDekker,Inc.,2002
SupplementedbypersonalconversationwithBartCarpenter

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

LHSV=ReactantLiquidHourlySpaceVelocity
=Liquidvolumetricflow volumecatalyst
16

SulfurDistributionvs.BoilingPointLCOFeedstock

17

GeneralEffectsofProcessVariables
Reactorinlettemperature&pressure
Increasingtemperatureincreaseshydrogenationbutdecreasesthenumberofactive
catalystsites
Temperaturecontrolisusedtooffsetthedeclineincatalystactivity
Increasingpressureincreaseshydrogenpartialpressure&increasestheseverityof
hydrogenation

Recyclehydrogen
Requirehighconcentrationofhydrogenatreactoroutlet
Hydrogenamountismuchmorethanstoichiometric
Highconcentrationsrequiredtopreventcokelaydown&poisoningofcatalyst
Particularlytruefortheheavierdistillatescontainingresinsandasphaltenes

Purgehydrogen
Removeslightends&helpsmaintainhighhydrogenconcentration

18

NaphthaHydrotreating
Naphthahydrotreated primarilyforsulfurremoval
Mostlymercaptans (RSH)&sulfides(RSR')
Somedisulfides(RSSR'),&thiophenes (ringstructures)

Mostcommoncatalystcobaltmolybdenumonalumina
Chemicalhydrogenconsumptiontypically50to250scf/bbl
Fordesulfurizationcontainingupto1wt%sulfur 70to100scf/bbl
Significantnitrogen&sulfurremoval 250scf/bbl

19

NaphthaHydrotreatingProcess
Reactortypicallyat200psig&
700F
Temperatureincreasesto
compensatefordecreaseincatalyst
activity

Liquidspacevelocity~2perhour
Hydrogenrecycle~2,000scf/bbl
Acidgasremovalmaynotbe
directlyincorporatedintorecycle
gasloop
Overheadvaporfromfractionator to
saturatesgasplanttorecoverlight
hydrocarbons&removeH2S

Productfractionation
Pentane/hexaneoverheadeitherto
blendingorisomerization
Bottomstoreformer

Haldo Topse processflow

2011RefiningProcessesHandbook
HydrocarbonProcessing,2011

20

DistillateHydrotreating
Ingeneral,allliquiddistillatestreams
containsulfurcompoundsthatmust
beremoved

Saturateolefinsindieseltoimprove
thecetane number

Hydrogenationatthehighpressure
producessmallamountsofnaphtha
fromhydrocracking
Requiredtogetattheembedded
sulfur
Dieselhydrotreater stabilizerwill
haveanuppersidestream draw
producingthenaphthawhichis
recycledtomotorgasoline
processing

BillingsULSDUnit

21

DistillateHydrotreatingProcess
Reactortypicallyat800F
Hydrogenrecyclestartsat2,000
scf/bbl;consumption100to400
scf/bbl

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

22

BoilingPointRangesforProducts
Kaes's Example Distillate Hydrotreating Problem
19,145 bpd Sour Distillate Feed
18,292 bpd Treated Distillate
3,000
35-Treated.Distillate
31-Liquids

2,500

27-Off.Gas

Incremental Yield [bpd]

1-fresh.charge
2,000

1,500

1,000

500

100

200

300

400

500

600

700

800

BPT [F]

23

GasOilHydrotreating
Catalyticcrackerfeedstocks(atmosphericgasoil,lightvacuumgasoil,solventdeasphalting
gasoil)hydrotreatedseverely
Sulfurremoval
Openingofaromaticrings
Removalofheavymetals

Desulfurizationofgasoilcanbeachievedwitharelativelymodestdecompositionof
structures

Gasoilscanbecontaminatedwithresins&asphaltenes
Depositedinhydrotreater
Requirecatalystreplacementwithashorterrunlengththandeterminedbydeactivation
Guardchambermaybeinstalledtoprolongbedlife

Nickelmolybdenumcatalystsystemforseverehydrotreating
Gasoilunitsmoreexpensivebecauseofmoreintensivehydrogenation
Quench
Multistageflash
Morecomplexstrippers

24

GasOilHydrotreatingProcess
Normallytworeactorbeds
controltemperaturerise

Hydrogenpartialpressurerelated
toringsaturation&amountof
sulfur

Forlowringsaturation300psigmay
besufficient
1,200psigwillconvert25%ring
saturation&somewhatlessthan
95%sulfurremoval
Pressuresashighas1,500psigcan
achievesaturationof30%of
aromaticrings

Hydrogenabsorptionof300

scf/bblcouldgiveabout80%
sulfurremoval&onlyrequire300
psig
Noringsaturationatthesemild
conditions
ChevronLummus GlobalLLCprocessflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011

25

Hydrotreating InstalledCost
Includes
Productfractionation.
Completepreheat,reaction,and
hydrogencirculationfacilities.
Sufficientheatexchangetocoolproducts
toambienttemperature.
Centralcontrolsystem.
Initialcatalystcharge.

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

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
26

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
27

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

28

CatalyticDewaxing ofMiddleDistillates
Improvecoldflowproperties
Clariant SelectiveHydrocrackingProcess
Selectivelycracksnormalparaffins duetosizeof
zeolitepores
Configurations
Standalone
Incorporatewithinexistinghydrotreating unit

Catalyticdewaxing bedwithinanexistinghydrotreating unit

Combinedhydrotreating &dewaxing

Ref:Considercatalyticdewaxing asatooltoimprovedieselcoldflowproperties,
Rakoczy &Morse,HydrocarbonProcessing,July2013

Combinedhydrotreating &catalyticdewaxing units

29

30

Hydrocracking
Purpose:processgasoiltobreakcarboncarbonbondsoflargearomatic
compounds&removecontaminants
Hydrogenation(additionofhydrogen)
Cracking(carboncarbonscission)ofaromaticbonds

Intenttocreatemiddledistillateproducts,notgasolinerangeproducts

31

HydrocrackerYieldExample

Example
32

HydrocrackerYieldTrends
Figure7.4
Startovercrackingtheheavynaphtha
fractionwhenthelightnaphthayieldsgets
above25vol%.

33

BoilingPointRangesforHydroprocessingProducts

Kaes's Hydrocracker Example

700
14
21

600

20-OffGas

Incremental Yield [bpd]

1-oil.feed
500

400

300

200

100

100

200

300

400

500

600

700

800

900

1000

1100

1200

BPT [F]

34

HydrocrackingFeeds
Typicalfeeds
Catcrackercycleoil
Highlyaromaticwithsulfur,smallring&polynucleararomatics,catalystfines;usuallyhas
highviscosity
Hydrocrackedtoformhighyieldsofjetfuel,kerosene,diesel,&heatingoil

Gasoilsfromvisbreaker
Aromatic

Gasoilfromthedelayedcoker
Aromatic,olefinic,withsulfur

Usuallymoreeconomicaltorouteatmospheric&vacuumgasoilstothecat
crackertoproduceprimarilygasoline&somediesel

35

GasOilHydrocrackerFeed
Hydrocrackingdoesabetterjobofprocessingaromaticringswithoutcoking
thancatalyticcracking
Hydrogenusedtohydrogenatepolynucleararomatics(PNAs)
Reducesfrequencyofaromaticcondensation

Hydrocrackingnotasattractiveasdelayedcokingforresidshighinresins,
asphaltenes&heteroatomcompounds
Heteroatoms&metalsprevalentinresins&asphaltenespoisonhydroprocessing
catalysts
Highconcentrationsofresins&asphalteneswillstillultimatelycoke

FeedslimitedtoaConradsonCarbonNumber(CCR)of8wt%
Feedsrequirehighpressures&largeamountsofhydrogen

36

GasOilHydrocrackerProducts
Hydrocrackingprimarilytomakedistillates
InUShydrocrackingnormallyaspecializedoperationusedtooptimizecatalyticcracker
operation
InUScatcrackingpreferredtomakegasolinefromheavierfractions

Hydrocrackingcapacityisonlyabout8%ofthecrudedistillationcapacity
Notallrefinerieshavehydrocrackers

Intentistominimizetheproductionofheavyfueloil
Lightendsareapproximately5%ofthefeed.
Middledistillates(kerosene,jetfuel,diesel,heatingoil)stillcontainuncracked
polynucleararomatics

Allliquidfractionsarelowinsulfur&olefins

37

Hydrocracking Chemistry
Crackingreactions
Saturatedparaffins cracked
toformlowermolecular
weightolefins&paraffins
Sidechainscrackedoffsmall
ringaromatics(SRA)&
cycloparaffins (naphthenes)
Sidechainscrackedoffresins
&asphaltenes leaving
thermallystablepolynuclear
aromatics(PNAs)
Butcondensation
(dehydrogenation)also
occursifnotlimitedby
hydrogenation

Hydrogenationreactions
Exothermicgivingoffheat
Hydrogeninsertedto
saturatenewlyformed
moleculefromaromatic
cracking
Olefinsaresaturatedtoform
lighthydrocarbons,
especiallybutane

Isomerization Reactions
Isomerization provides
branchingofalkylgroupsof
paraffins andopeningof
naphthenicrings

CondensationReactions.
Suppressedbyhydrogen

Aromaticringshydrogenated
tocycloparaffins
(naphthenes)
Carboncarbonbonds
cleavedtoopenaromatic&
cycloparaffins (naphthenes)
rings
Heteroatoms formhydrogen
sulfide,ammonia,water,
hydrogenchloride
38

SingleStageHydrocracking
Feedstockhydrotreated toremove
sulfur,nitrogen,oxygencomponents
Guardreactorstoremovemetals

Temperatures660 800F
Mayraisetemperature0.1 0.2oFper
daytooffsetlossofcatalystactivity

Pressures1,200 2,000psig
Raisingpressureincreasesconversion

Hydrogen
Highhydrogenrecycletominimize
coking

Consumption
Lowpressure mildseverity 1,000
2,000scf/bbl
Highpressure highseverity 2,000
3,000scf/bbl

Haldo Topse processflow

2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
39

Hydrocrackervs.FCCInstalledCost

HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
40

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

Valueofgasoilhydrocrackers
Volumeexpansionthroughhydrogensaturation&bycrackinglargermoleculesinto
smallerones
Yieldalargeamountofdistillateproductscomparedtogasolineproducts
Haveflexibilitytoshiftabout10%betweentheseproducts
FurtheradjustmentscanbemanagedbychangingfractionationoperationsHydrocracker
distillateproductiongoodqualityforjet&dieselfuel

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

41

ValueofHydrocrackersinU.S.Refining
Marketfactors
IncrementalcostofhydrogendecreasingbecauseofthesurplusofnaturalgasinNorth
America(fromshaleformations)
Regionalsupply&demandbalanceofgasoils
InNorthAmericagasoilspricerelativetotheincrementaldispositiontoaFCCU
o

Bettermarginstofeedhydrocrackerstomakedistillatevs.feedFCCUtomakegasoline

Usedtohavemarginsof$10perbbl feedstock,nowinthe$15to$20perbbl range

Downsidesofhydrocrackers
Highhydrogenconsumption
Highenergyconsumption
Highcapitalrequirements
Highcatalystcosts
Highmaintenancecosts
Ref:http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/

42

SupplementalSlides
Phillips66capacities
Hydroprocessing objectives
Hydrotreating &hydrocrackingtechnologyproviders
Hydrogenconsumptioninhydrotreating &hydrocracking
Reactorchoicebasedonseverityofoperations
Otherhydrocrackingconfigurations

43

Phillips66Hydrotreating Statistics

U.S.informationfromEIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/

44

Phillips66HydrocrackingStatistics

U.S.informationfromEIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/

45

HydroprocessingObjectives
Feedstocks
Naphthas

DesiredProducts
Catalyticreformerfeed
LPG
Atmosphericgasoils Diesel
Jet
Ethylenefeedstock
Naptha
Vaccumgasoils
LSFO
FCCfeed
Diesel
Kerosene/jet
Naptha
LPG
Ethylenefeedstock
Lubeoilbasestock

Residuum

LSFO
FCCfeedstock
Cokerfeedstock
Diesel

ProcessObjectives
RemovalofS,N,&olefins
Hydrocracking
RemovalofS,aromatics,&nparaffins
RemovalofS&aromatics
Removalofaromatics
Hydrocracking
RemovalofS
RemovalofS,N,&metals
RemovalofS&aromatics
Hydrocracking
RemovalofS&aromatics
Hydrocracking
Hydrocracking
Hydrocracking
Removalofaromatics
Hydrocracking
RemovalofS,N,&aromatics
Hydrocracking
RemovalofS
RemovalofS,N,CCR,&metals
RemovalofS,CCR,&metals
Hydrocracking

HandbookofPetroleumRefiningProcesses,3rd ed.
Ed.RobertA.Meyers,McGrawHill,2004

46

HydrotreatingTechnologies

Provider
CDTECH
ChevronLummusGlobalLLC
DuPont
HaldorTopsoeA/S
UOP
Axens
GTCTechnology
UOP
ChevronLummusGlobalLLC
Axens
Axens

Features
Hydrotreating.CDHydro &CDHDS
Hydrotreating.ISOTREATING
Hydrotreating
Hydrotreating
Hydrotreating
Hydrotreating,diesel
Hydrotreating,pyrolysisgasoline
Hydrotreating/desulfurization.SelectFining
HydrotreatingRDS/VRDS/UFR/OCR
Hydrotreatingresid
Hydrodearomatization.2stageHDS/HAD

47

HydrocrackingTechnologies

Provider
Axens
ChevronLummusGlobalLLC
DuPont
HaldorTopsoeA/S
ShellGlobalSolutions
UOP
ExxonMobilResearch&Engineering
ChevronLummusGlobalLLC
Axens

Features
Hydrocracking
Hydrocracking.ISOCRACKING
Hydrocracking
Hydrocracking
Hydrocracking
Hydrocracking
Hydrocracking,moderatepressure.MPHC
Hydrocracking,resid
Hydrocracking,residue.HOilOC

48

HydrogenConsumptioninHydrotreating
Chemicalconsumptionduetohydrogenationreactions
Crackingreactionsofcarboncarbonbondsminimalinhydrotreating,evenduring
aromaticsaturation
Olefinicbondseasiertosaturatethanaromaticbonds
Straightrunstockshaveessentiallyzeroolefins

Hydrogenislostinequilibriumwithlightgases
Amountissignificant &maydoubleamountrequiredforsulfurremoval

Hydrogenabsorbedinliquidproducts
Usuallysmallcomparedtosulfurremovalneeds 1lb/bbl

Hydrogenremovedwithpurgegas
Usedtomaintainahighpurityofhydrogen lightendsdilutethehydrogen
concentration
Usuallysmallcomparedtosulfurremovalneeds

49

HydrogenConsumption&Loss
Heteroatomcarbonbonds
broken&saturated
Createslightends
Heavierdistillatesmakemore
lightendsfrombreakingmore
complexmolecules

SulfurconvertedtoH2S
NitrogenconvertedtoNH3
OxygenconvertedtoH2O
Organicchloridesconvertedto
HCl

Saturationofcarboncarbon
bonds
Olefinssaturatedtoformlight
hydrocarbons.
Consumptionstoichiometric
onehydrogenmoleculeadded
foreachdoublebond

Aromaticringshydrogenated
tocycloparaffins(naphthenes).
Severeoperation hydrogen
consumptionstrongfunctionof
complexityofthearomatics

Isomerizationreactions
generallynotpresent

Metalsdepositeddirectlyon
thecatalysts

Crackingofcarboncarbon
bonds
Severeoperation hydrogen
consumptionstrongfunction
ofcomplexityofthearomatics

Hydrogenmixedwithproducts
Equilibriumwithlightgases
Significant maydouble
amountrequiredforsulfur
removal

Absorbedinliquidproducts
Usuallysmallcomparedto
hydrogenusedforsulfur
removal

Lostwithpurgegas

Excessmetalsreducecatalyst
activity&promote
dehydrogenation(produces
coke&hydrogen)
50

Severityofoperations

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

51

SingleStageHydrocracking withHDS1st Step

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

52

UOPTwoStageUnicrackingProcess

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

53

UOPsHyCycleUnicrackingTM Process

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

54