08 Hydroprocessing

Hydroprocessing:Hydrotreating &Hydrocracking
Chapters7&9
JohnJechura jjechura@mines.edu
Updated:August13,2015
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
EIA,Jan.1,2015database,publishedJune2015
http://www.eia.gov/petroleum/refinerycapacity/
U.S.RefineryImplementationofHydrocracking
EIA,Jan.1,2015database,publishedJune2015
http://www.eia.gov/petroleum/refinerycapacity/
Purpose
Hydrotreating
Removeheteroatoms&saturatecarbon
carbonbonds
Sulfur,nitrogen,oxygen,&metals
removed
Olefinic &aromaticbondssaturated
Minimalcracking
Minimalconversion 10%to20%typical
Productssuitableforfurtherprocessingor
finalblending
Hydrocracking
Severeformofhydroprocessing
Breakcarboncarbonbonds
Drasticreductionofmolecularweight
Reduceaveragemolecularweight&produce
higheryieldsoffuelproducts
50%+conversion
Productsmoreappropriatefordieselthan
gasoline
Reforming,catalyticcracking,
hydrocracking
http://www.kbr.com/Newsroom/Publications/Brochures/Hydropr
ocessingTechnology.pdf
TypicalHydrogenUsage
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
CharacteristicsofPetroleumProducts
Hydrotreating:justenoughconversiontoremoveundesirableatoms;
hydrogenadditionforatomremoval
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
CharacteristicsofPetroleumProducts
Hydrocracking:hydrogenadditiontominimizecokeformation
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,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
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
TotalDistillateHydrotreater
http://www.totalpetrochemicalsusa.com/press_room/press_releases_dc
pphotos.asp
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
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
25
SaturationofBenzeneinGasoline
Strategiesforreductionofbenzeneingasoline
Reducebenzeneprecursorsinfeedtoreformer
Hydrotreat/saturatebenzeneinappropriateboilingrangefraction
Typicalprocessingstrategy
Separate&hydrotreat narrowcut
C6fractionfromrestoffeedstock
Saturatethearomatics&olefins
ofthetreatedstream
RetaintheolefinsintheC5 and
thearomatics&olefinsofthe
C7+fractions
Blendproductbackintothe
strippedfeedstock
GTCTechnologyprocessflow
26
SaturationofBenzeneinGasoline
UOPsBenSatTM processcanbeusedonalight
reformerstream
Upto30vol%benzeneinfeed
Norecyclegas
Norecyclecompressor
Norecyclecompressionpowerrequirements
Longcatalystlife
Highcatalystselectivity
Pros&cons
NoincreaseinRVP
Mildvolumetricswelling,+1to+6vol%
Doloseoctanerating
27
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

28
29
Hydrocracking
Purpose:processgasoiltobreakcarboncarbonbondsoflargearomatic
compounds&removecontaminants
Hydrogenation(additionofhydrogen)
Cracking(carboncarbonscission)ofaromaticbonds
Intenttocreatemiddledistillateproducts,notgasolinerangeproducts
30
HydrocrackerYieldExample
Example
31
HydrocrackerYieldTrends
Figure7.4
Startovercrackingtheheavynaphtha
fractionwhenthelightnaphthayieldsgets
above25vol%.
32
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]
33
HydrocrackingFeeds
Typicalfeeds
Catcrackercycleoil
Highlyaromaticwithsulfur,smallring&polynucleararomatics,catalystfines;usuallyhas
highviscosity
Hydrocrackedtoformhighyieldsofjetfuel,kerosene,diesel,&heatingoil
Gasoilsfromvisbreaker
Aromatic
Gasoilfromthedelayedcoker
Aromatic,olefinic,withsulfur
Usuallymoreeconomicaltorouteatmospheric&vacuumgasoilstothecat
crackertoproduceprimarilygasoline&somediesel
34
GasOilHydrocrackerFeed
Hydrocrackingdoesabetterjobofprocessingaromaticringswithoutcoking
thancatalyticcracking
Hydrogenusedtohydrogenatepolynucleararomatics(PNAs)
Reducesfrequencyofaromaticcondensation
Hydrocrackingnotasattractiveasdelayedcokingforresidshighinresins,
asphaltenes&heteroatomcompounds
Heteroatoms&metalsprevalentinresins&asphaltenespoisonhydroprocessing
catalysts
Highconcentrationsofresins&asphalteneswillstillultimatelycoke
FeedslimitedtoaConradsonCarbonNumber(CCR)of8wt%
Feedsrequirehighpressures&largeamountsofhydrogen
35
GasOilHydrocrackerProducts
Hydrocrackingprimarilytomakedistillates
InUShydrocrackingnormallyaspecializedoperationusedtooptimizecatalyticcracker
operation
InUScatcrackingpreferredtomakegasolinefromheavierfractions
Hydrocrackingcapacityisonlyabout8%ofthecrudedistillationcapacity
Notallrefinerieshavehydrocrackers
Intentistominimizetheproductionofheavyfueloil
Lightendsareapproximately5%ofthefeed.
Middledistillates(kerosene,jetfuel,diesel,heatingoil)stillcontainuncracked
polynucleararomatics
Allliquidfractionsarelowinsulfur&olefins
36
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
37
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

38
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/
39
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/
40
SupplementalSlides
Installedcosts
Hydroprocessing objectives
Hydrotreating &hydrocrackingtechnologyproviders
Hydrogenconsumptioninhydrotreating &hydrocracking
Reactorchoicebasedonseverityofoperations
Otherhydrocrackingconfigurations
41
Hydrotreating InstalledCost
Includes
Productfractionation.
Completepreheat,reaction,and
hydrogencirculationfacilities.
Sufcientheatexchangetocoolproducts
toambienttemperature.
Centralcontrolsystem.
Initialcatalystcharge.
Excludes
Feedfractionation.
Makeuphydrogengeneration.
Sulfurrecoveryfromoffgas.
Coolingwater,system,andpowersupply.
PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
42
Hydrocrackervs.FCCInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost
PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
43
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
Hydrocracking
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
44
HydrotreatingTechnologies
Provider
CDTECH
ChevronLummusGlobalLLC
DuPont
HaldorTopsoeA/S
UOP
Axens
GTCTechnology
UOP
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
45
HydrocrackingTechnologies
Provider
Axens
DuPont
HaldorTopsoeA/S
ShellGlobalSolutions
UOP
ExxonMobilResearch&Engineering
Axens
Features
Hydrocracking
Hydrocracking.ISOCRACKING
Hydrocracking
Hydrocracking
Hydrocracking
Hydrocracking
Hydrocracking,moderatepressure.MPHC
Hydrocracking,resid
Hydrocracking,residue.HOilOC
46
HydrogenConsumptioninHydrotreating
Chemicalconsumptionduetohydrogenationreactions
Crackingreactionsofcarboncarbonbondsminimalinhydrotreating,evenduring
aromaticsaturation
Olefinicbondseasiertosaturatethanaromaticbonds
Straightrunstockshaveessentiallyzeroolefins
Hydrogenislostinequilibriumwithlightgases
Amountissignificant &maydoubleamountrequiredforsulfurremoval
Hydrogenabsorbedinliquidproducts
Usuallysmallcomparedtosulfurremovalneeds 1lb/bbl
Hydrogenremovedwithpurgegas
Usedtomaintainahighpurityofhydrogen lightendsdilutethehydrogen
concentration
Usuallysmallcomparedtosulfurremovalneeds
47
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)
48
Severityofoperations
Hydrocracking solutionssqueezemoreULSDfromheavyends
E.Benazzi,J.Bonnardot,F.Morel,HydrocarbonProcessing,November2009
49
SingleStageHydrocracking withHDS1st Step
PetroleumRefineryProcessEconomics,2nd ed.,
RobertE.Maples,Figure141,2000
50
UOPTwoStageUnicrackingProcess
http://www.uop.com/hydrocrackingunicrackingstage/
51
UOPsHyCycleUnicrackingTM Process
http://www.uop.com/objects/Hycycle.pdf
52

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Hydroprocessing:Hydrotreating &Hydrocracking

Haldo Topse processflow

Incremental Yield [bpd]

Catalyticdewaxing bedwithinanexistinghydrotreating unit

Combinedhydrotreating &catalyticdewaxing units

Kaes's Hydrocracker Example

Incremental Yield [bpd]

Haldo Topse processflow

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

SingleStageHydrocracking withHDS1st Step

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