JohnJechura jjechura@mines.

edu
Hydroprocessing:Hydrotreating &Hydrocracking
Chapters7&9
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphalting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
2
Purpose
Hydrotreating
Removeheteroatoms&saturate
carboncarbonbonds
Sulfur,nitrogen,oxygen,&metals
removed
Olefinic &aromaticbondssaturated
Minimalcracking
Minimalconversion 10%to20%typical
Productssuitableforfurtherprocessing
orfinalblending
Reforming,catalyticcracking,
hydrocracking
Hydrocracking
Severeformofhydroprocessing
Breakcarboncarbonbonds
Drasticreductionofmolecularweight
Reduceaveragemolecularweight&
producehigheryieldsoffuelproducts
50%+conversion
Productsmoreappropriatefordiesel
thangasoline
3
TypicalHydrogenUsage
4
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
CharacteristicsofPetroleumProducts
5
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Hydrocracking:hydrogenadditiontominimizecokeformation
CharacteristicsofPetroleumProducts
6
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
Hydrotreating:justenoughconversiontoremoveundesirableatoms;
hydrogenadditionforatomremoval
HydroprocessingTrends
Hydrogenisubiquitousinrefinery&expectedtoincrease
Produceshigheryields&upgradethequalityoffuels
Thetypicalrefineryrunsatahydrogendeficit
Ashydroprocessing becomesmoreprevalent,thisdeficitwillincrease
Ashydroprocessing progressesinseverity,thehydrogendemandsincreasedramatically
Drivenbyseveralfactors
Increaseduseofhydrodesulfurization forlowsulfurfuels
Heavier&highersulfurcrudes
Reductionindemandforheavyfueloil
MorecompleteprotectionofFCCUcatalysts
Demandforhighqualitycoke
Increasedproductionofdiesel
7
SourcesofHydrogeninaRefinery
Byproductfromotherprocesses
CatalyticReformer
Mostimportantsourceofhydrogenforthe
refiner
Continuouslyregeneratedreformer:90vol%
Semicontinuouslyregeneratedreformer:80vol%
FCCUOffgas
5vol%hydrogenwithmethane,ethane&
propane
Severalrecoverymethods(canbecombined)
Cryogenic
Pressureswingadsorption(PSA)
Membraneseparation
Manufactured
SteamMethaneReforming(SMR)
Mostcommonmethodofmanufacturing
hydrogen
90 95vol%typicalpurity
Gasification/PartialOxidation
Producesynthesisgas(syngas)
Hydrogenrecovery
Pressureswingadsorption(PSA)
Membraneseparation
Moreexpensivethansteamreformingbutcan
uselowqualitybyproductstreams
8
HydroprocessingCatalysts
Hydrotreating
Desiredfunction
Cobaltmolybdenum sulfurremoval&olefin
saturation
Nickelmolybdenum nitrogenremoval&
aromaticsaturation
Reactorconfiguration
Downflow fixedbed temperaturetocontrol
finalsulfurcontent
Firstbedmayguardbedfornickel&vanadium
o Cheapercatalysts
o 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
9
ReactorBedConfigurations
10
PetroleumRefiningProcesses
J.G.Speight&B.zm
MarcelDekker,Inc.,2002,pg.452
Slurryphasehydrocrackingpossiblesolutiontorefining
margins,M.Motaghi &A.Subramanian,Hydrocarbon
Processing,February2011
Phillips66Hydroprocessing Statistics
11
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphalting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
12
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
13
YieldEstimates
Difficultpartlybecauseconversionoffeedstockisrelativelylow
Liquidproductsgenerallyhavegravity+1API
Overallvolumetypicallyincreases
Generalrelationshipofhydrogenrequiredvs.sulfurcontent
14
0
40
80
120
160
200
240
280
320
360
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
WeightPercentSulfurinFeed
S
C
F
B

o
f

H
y
d
r
o
g
e
n
PetroleumRefiningProcesses,
byJamesSpeight&Baki Ozum,MarcelDekker,2002
TypicalProcessParameters
15
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
http://www.eia.doe.gov/oiaf/servicerpt/ulsd/figd3.html
PetroleumRefiningProcesses,
byJamesG.Speight&Baki zm,MarcelDekker,Inc.,2002
SupplementedbypersonalconversationwithBartCarpenter
LHSV=ReactantLiquidHourlySpaceVelocity
=Liquidvolumetricflow volumecatalyst
SulfurDistributionvs.BoilingPointLCOFeedstock
16
GeneralEffectsofProcessVariables
Reactorinlettemperature&pressure
Increasingtemperatureincreaseshydrogenationbutdecreasesthenumberofactive
catalystsites
Temperaturecontrolisusedtooffsetthedeclineincatalystactivity
Increasingpressureincreaseshydrogenpartialpressure&increasestheseverityof
hydrogenation
Recyclehydrogen
Requirehighconcentrationofhydrogenatreactoroutlet
Hydrogenamountismuchmorethanstoichiometric
Highconcentrationsrequiredtopreventcokelaydown&poisoningofcatalyst
Particularlytruefortheheavierdistillatescontainingresinsandasphaltenes
Purgehydrogen
Removeslightends&helpsmaintainhighhydrogenconcentration
17
NaphthaHydrotreating
Naphthahydrotreated primarilyforsulfurremoval
Mostlymercaptans (RSH)&sulfides(RSR')
Somedisulfides(RSSR'),&thiophenes (ringstructures)
Mostcommoncatalystcobaltmolybdenumonalumina
Chemicalhydrogenconsumptiontypically50to250scf/bbl
Fordesulfurizationcontainingupto1wt%sulfur 70to100scf/bbl
Significantnitrogen&sulfurremoval 250scf/bbl
18
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
19
Haldo Topse processflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
DistillateHydrotreating
Ingeneral,allliquiddistillatestreams
containsulfurcompoundsthatmust
beremoved
Saturateolefinsindieseltoimprove
thecetane number
Hydrogenationatthehighpressure
producessmallamountsofnaphtha
fromhydrocracking
Requiredtogetattheembedded
sulfur
Dieselhydrotreater stabilizerwill
haveanuppersidestream draw
producingthenaphthawhichis
recycledtomotorgasoline
processing
20
BillingsULSDUnit
DistillateHydrotreatingProcess
Reactortypicallyat800F
Hydrogenrecyclestartsat2,000
scf/bbl;consumption100to400
scf/bbl
Conditionshighlydependentupon
feedstock
Distillate(jetfuel&diesel)with85%
95%sulfurremoval
300psig
hydrogenconsumption200 300
scf/bbl
Saturationofdieselforcetane number
improvement
over800scf/bblhydrogen
upto1,000psig
21
Haldo Topse processflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
BoilingPointRangesforProducts
22
Kaes's Example Distillate Hydrotreating Problem
-
500
1,000
1,500
2,000
2,500
3,000
0 100 200 300 400 500 600 700 800
BPT [F]
I
n
c
r
e
m
e
n
t
a
l

Y
i
e
l
d

[
b
p
d
]
35-Treated.Distillate
31-Liquids
27-Off.Gas
1-fresh.charge
19,145 bpd Sour Distillate Feed
18,292 bpd Treated Distillate
GasOilHydrotreating
Catalyticcrackerfeedstocks(atmosphericgasoil,lightvacuumgasoil,solventdeasphalting
gasoil)hydrotreatedseverely
Sulfurremoval
Openingofaromaticrings
Removalofheavymetals
Desulfurizationofgasoilcanbeachievedwitharelativelymodestdecompositionof
structures
Gasoilscanbecontaminatedwithresins&asphaltenes
Depositedinhydrotreater
Requirecatalystreplacementwithashorterrunlengththandeterminedbydeactivation
Guardchambermaybeinstalledtoprolongbedlife
Nickelmolybdenumcatalystsystemforseverehydrotreating
Gasoilunitsmoreexpensivebecauseofmoreintensivehydrogenation
Quench
Multistageflash
Morecomplexstrippers
23
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
24
ChevronLummus GlobalLLCprocessflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
Hydrotreating InstalledCost
Includes
Productfractionation.
Completepreheat,reaction,and
hydrogencirculationfacilities.
Sufcientheatexchangetocoolproducts
toambienttemperature.
Centralcontrolsystem.
Initialcatalystcharge.
Excludes
Feedfractionation.
Makeuphydrogengeneration.
Sulfurrecoveryfromoffgas.
Coolingwater,system,andpowersupply.
25
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
SaturationofBenzeneinGasoline
Strategiesforreductionofbenzeneingasoline
Reducebenzeneprecursorsinfeedtoreformer
Hydrotreat/saturatebenzeneinappropriateboilingrangefraction
Typicalprocessingstrategy
Separate&hydrotreat narrowcut
C6fractionfromrestoffeedstock
Saturatethearomatics&olefins
ofthetreatedstream
RetaintheolefinsintheC5 and
thearomatics&olefinsofthe
C7+fractions
Blendproductbackintothe
strippedfeedstock
26
GTCTechnologyprocessflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
SaturationofBenzeneinGasoline
UOPsBenSat
TM
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
Combinedhydrotreating &dewaxing
28
Catalyticdewaxing bedwithinanexistinghydrotreating unit
Combinedhydrotreating &catalyticdewaxing units
Ref:Considercatalyticdewaxing asatooltoimprovedieselcoldflowproperties,
Rakoczy &Morse,HydrocarbonProcessing,July2013
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphalting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
29
Hydrocracking
Purpose:processgasoiltobreakcarboncarbonbondsoflargearomatic
compounds&removecontaminants
Hydrogenation(additionofhydrogen)
Cracking(carboncarbonscission)ofaromaticbonds
Intenttocreatemiddledistillateproducts,notgasolinerangeproducts
30
HydrocrackerYieldExample
31
Example
HydrocrackerYieldTrends
Figure7.4
Startovercrackingtheheavynaphtha
fractionwhenthelightnaphthayieldsgets
above25vol%.
32
BoilingPointRangesforHydroprocessingProducts
Kaes's Hydrocracker Example
-
100
200
300
400
500
600
700
0 100 200 300 400 500 600 700 800 900 1000 1100 1200
BPT [F]
I
n
c
r
e
m
e
n
t
a
l

Y
i
e
l
d

[
b
p
d
]
14
21
20-OffGas
1-oil.feed
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
Aromaticringshydrogenated
tocycloparaffins
(naphthenes)
Carboncarbonbonds
cleavedtoopenaromatic&
cycloparaffins (naphthenes)
rings
Heteroatoms formhydrogen
sulfide,ammonia,water,
hydrogenchloride
37
Isomerization Reactions
Isomerization provides
branchingofalkylgroupsof
paraffins andopeningof
naphthenicrings
CondensationReactions.
Suppressedbyhydrogen
SingleStageHydrocracking
Feedstockhydrotreated toremove
sulfur,nitrogen,oxygencomponents
Guardreactorstoremovemetals
Temperatures660 800F
Mayraisetemperature0.1 0.2
o
Fper
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
Haldo Topse processflow
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
Hydrocrackervs.FCCInstalledCost
HydrocrackerstendtobemoreexpensivethanFCCs
50,000bpddistillateFCC $150millioninstalledcost
50,000bpd@2000scf/bbl $350millioninstalledcost
39
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
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)
40
Ref:http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/
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
41
Ref:http://www.refinerlink.com/blog/Value_Hydrocrackers_US_Refining/
SupplementalSlides
Hydroprocessing objectives
U.S.refineryhydrocrackingimplementations
Hydrotreating &hydrocrackingtechnologyproviders
Hydrogenconsumptioninhydrotreating &hydrocracking
Reactorchoicebasedonseverityofoperations
Otherhydrocrackingconfigurations
42
HydroprocessingObjectives
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
43
HandbookofPetroleumRefiningProcesses,3
rd
ed.
Ed.RobertA.Meyers,McGrawHill,2004
U.S.RefineryImplementationofHydrocracking
44
Top 10 Hydrocrackers & Top 10 Hydrocrackers w/o FCCs
EIA,Jan.1,2013database,publishedJune2013
http://www.eia.gov/petroleum/refinerycapacity/
HydrotreatingTechnologies
45
Provider Features
CDTECH Hydrotreating.CDHydro &CDHDS
ChevronLummusGlobalLLC Hydrotreating.ISOTREATING
DuPont Hydrotreating
HaldorTopsoeA/S Hydrotreating
UOP Hydrotreating
Axens Hydrotreating,diesel
GTCTechnology Hydrotreating,pyrolysisgasoline
UOP Hydrotreating/desulfurization.SelectFining
ChevronLummusGlobalLLC HydrotreatingRDS/VRDS/UFR/OCR
Axens Hydrotreatingresid
Axens Hydrodearomatization.2stageHDS/HAD
HydrocrackingTechnologies
46
Provider Features
Axens Hydrocracking
ChevronLummusGlobalLLC Hydrocracking.ISOCRACKING
DuPont Hydrocracking
HaldorTopsoeA/S Hydrocracking
ShellGlobalSolutions Hydrocracking
UOP Hydrocracking
ExxonMobilResearch&Engineering Hydrocracking,moderatepressure.MPHC
ChevronLummusGlobalLLC Hydrocracking,resid
Axens Hydrocracking,residue.HOil
OC
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
SulfurconvertedtoH
2
S
NitrogenconvertedtoNH
3
OxygenconvertedtoH
2
O
Organicchloridesconvertedto
HCl
Saturationofcarboncarbon
bonds
Olefinssaturatedtoformlight
hydrocarbons.
Consumptionstoichiometric
onehydrogenmoleculeadded
foreachdoublebond
Aromaticringshydrogenated
tocycloparaffins(naphthenes).
Severeoperation hydrogen
consumptionstrongfunctionof
complexityofthearomatics
Isomerizationreactions
generallynotpresent
Metalsdepositeddirectlyon
thecatalysts
Excessmetalsreducecatalyst
activity&promote
dehydrogenation(produces
coke&hydrogen)
48
Crackingofcarboncarbon
bonds
Severeoperation hydrogen
consumptionstrongfunction
ofcomplexityofthearomatics
Hydrogenmixedwithproducts
Equilibriumwithlightgases
Significant maydouble
amountrequiredforsulfur
removal
Absorbedinliquidproducts
Usuallysmallcomparedto
hydrogenusedforsulfur
removal
Lostwithpurgegas
Severityofoperations
49
Hydrocracking solutionssqueezemoreULSDfromheavyends
E.Benazzi,J.Bonnardot,F.Morel,HydrocarbonProcessing,November2009
SingleStageHydrocracking withHDS1
st
Step
50
PetroleumRefineryProcessEconomics,2
nd
ed.,
RobertE.Maples,Figure141,2000
UOPTwoStageUnicrackingProcess
51
http://www.uop.com/hydrocrackingunicrackingstage/
UOPsHyCycleUnicracking
TM
Process
52
http://www.uop.com/objects/Hycycle.pdf