gasoline upgrading: reforming, isomerization, &...
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GasolineUpgrading:Reforming,Isomerization,&AlkylationChapters10&11
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu) 2
Light Naphtha
CrudeOil Desalter
Atmospheric Distillation
Vacuum Distillation
Gas Separation &
Stabilizer
Solvent Deasphal-
ting
Coking
Visbreaking
Fluidized Catalytic Cracking
Hydro-cracking
NaphthaReforming
Isom-erization
Sat Gas Plant
Polymer-ization
Alkylation
NaphthaHydro-treating
Treating & Blending
Coke
Fuel Gas
LPG
Aviation Gasoline
Automotive GasolineSolvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
ResidualFuel Oils
Lubricant
Greases
Waxes
Asphalts
HeavyNaphtha
Kerosene
DistillateAGO
LVGO
HVGO
VacuumResiduum
CatDistillates
Gas Oil Hydro-treating
DAO
Isomerate
Gas
AlkylFeed
Alkylate
PolymerizationNaphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel OilBottoms
Distillates
DistillateHydro-treating
CatNaphtha
Cycle Oils
SDABottomsCokerNaphtha
HeavyCokerGasOil
Light CokerGas Oil
SulfurPlant Sulfur
Naphtha
Fuel Oil
SolventDewaxing
Lube Oil
Waxes
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
GasolineUpgrading
Purpose Increasethequalityoffeedstocksofthesame
boilingrangeasgasoline
Characteristics CatalyticReforming
Convertsnaphthenes toaromatics Produceshydrogen
Isomerization Rearrangesstraightchainstobranchedisomers Verylittlechangeinboilingpoints
Alkylation Useolefinsproducedinotherprocesses(primarily
FCCU) Produceisooctane Liquidacidcatalyst
Products Gasolineblendstocksofimprovedoctane
and/orvolatility
4
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
DependencyofOctaneonChemicalStructure
5
RON MON RON MONParaffins Naphthenesnbutane 94 89.6 cyclopentane 100 84.9isobutane 102 97.6 cyclohexane 82.5 77.2npentane 62 62.6 mcyclopentane 91.3 80ipentane 92 90.3 C7naphthenes 82 77nhexane 24.8 26 C8naphthenes 55 50C6monomethyls 76 73.9 C9naphthenes 35 302,2dimethylbutane 91.8 93.42,3dimethylbutane 105.8 94.3 Aromaticsnheptane 0 0 benzene 102.7 105C7monomethyls 52 52 toluene 118 103.5C7dimethyls 93.76 90 C8aromatics 112 1052,2,3trimethylbutane 112.8 101.32 C9aromatics 110 101noctane 15 20 C10aromatics 109 98C8monomethyls 25 32.3 C11aromatics 105 94C8dimethyls 69 74.5 C12aromatics 102 90C8trimethyls 105 98.8nnonane 20 20 Olefins/CyclicOlefinsC9monomethyls 15 22.3 nbutenes 98.7 82.1C9dimethyls 50 60 npentenes 90 77.2C9trimethyls 100 93 ipentenes 103 82ndecane 30 30 cyclopentene 93.3 69.7C10monomethyls 10 10 nhexenes 90 80C10dimethyls 40 40 ihexenes 100 83C10trimethyls 95 87 TotalC6cyclicolefins 95 80nundecane 35 35 totalC7d 90 78C11monomethyl 5 5 totalC8d 90 77C11dimethyls 35 35C11trimethyls 90 82 Oxygenatesndodecane 40 40 MTBE 115.2 97.2C12monomethyl 5 5 TAME 115 98C12dimethyls 30 30 EtOH 108 92.9C12trimethyls 85 80
DevelopmentofaDetailedGasolineCompositionBasedOctaneModelPrasenjeet Ghosh,Karlton J.Hickey,andStephenB.JaffeInd.Eng.Chem.Res. 2006,45,337345
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
DependencyofOctaneonChemicalStructure
6
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu) 7
Light Naphtha
CrudeOil Desalter
Atmospheric Distillation
Vacuum Distillation
Gas Separation &
Stabilizer
Solvent Deasphal-
ting
Coking
Visbreaking
Fluidized Catalytic Cracking
Hydro-cracking
NaphthaReforming
Isom-erization
Sat Gas Plant
Polymer-ization
Alkylation
NaphthaHydro-treating
Treating & Blending
Coke
Fuel Gas
LPG
Aviation Gasoline
Automotive GasolineSolvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
ResidualFuel Oils
Lubricant
Greases
Waxes
Asphalts
HeavyNaphtha
Kerosene
DistillateAGO
LVGO
HVGO
VacuumResiduum
CatDistillates
Gas Oil Hydro-treating
DAO
Isomerate
Gas
AlkylFeed
Alkylate
PolymerizationNaphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel OilBottoms
Distillates
DistillateHydro-treating
CatNaphtha
Cycle Oils
SDABottomsCokerNaphtha
HeavyCokerGasOil
Light CokerGas Oil
SulfurPlant Sulfur
Naphtha
Fuel Oil
SolventDewaxing
Lube Oil
Waxes
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
NaphthaReforming
Almosteveryrefineryintheworldhasareformer
Purposetoenhancearomaticcontentofnaphtha Feedstockstoaromaticscomplex Improvetheoctaneratingforgasoline
Manydifferentcommercialcatalyticreformingprocesses Hydroforming Platforming Powerforming Ultraforming Thermofor catalyticreforming
Primaryreactions Dehydrogenation
naphthenes aroma cs
Isomerization normalparaffins branchedisoparaffins
Hydrogenasbyproduct Ultimatelyusedinhydrotreating Catalyticreforming2ndtoFCCincommercial
importancetorefiners
Reformatedesirablecomponentforgasoline Highoctanenumber,lowvaporpressure,very
lowsulfurlevels,&lowolefinsconcentration USregulationsonlevelsofbenzene,aromatics,
&olefins Airqualityconcerns
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
U.S.RefineryImplementation
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EIA,Jan.1,2017database,publishedJune2017http://www.eia.gov/petroleum/refinerycapacity/
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
CharacteristicsofPetroleumProducts
10
Reforming:driveoffhydrogenforbettergasolinepropertiesw/ochangingsize
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Feedstocks &Products
Hydrotreated heavynaphthafeedstock Lightstraightrunnaphthatendstocracktobutanes&lighter Gasoilstreamstendtohydrocrack&depositcokeonthereformingcatalyst
Catalystisnoblemetal(e.g.platinum) verysensitivetosulfur&nitrogen Feedstockshydrotreated forsulfur&nitrogenremoval Controlofchloride&wateralsoimportant
Severity Highseverityusedtomaximizearomatics
SenttoBTXseparationforaromaticfeedstocks
Lowseverityusedforgasolineblendstocks
Producesthemajorityofthehydrogenusedforhydrotreating
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ReformingChemistry
Usesasolidcatalysttoconvertnaphthenestothecorrespondingaromatics&isomerizeparaffinicstructurestoisomericforms Bothreactionsleadtoamarkedincreaseinoctanenumber Bothreactionsleadtovolumeshrinkage
CorrelationspermittheuseofaPONAanalysisofthefeedforpredictionofyieldandqualityoftheproduct OriginallyfeedqualitiesmeasuredintermsofWatson"K"Factor aroughindicationofamountofparaffins
Aromaticslargelyuntouchedbyreactions
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IsomerizationCH3 CH3
CH2
CH3CH3
HydrocrackingCH2CH3 CH3
+ H2 +
CH3 CH3
+ 3 H2
Dehydrogenation
+ H2
Dehydrocyclization
CH3
CH3
CH3
CH3
+ H2
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ReformerYieldExample
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ReformerYieldTrends
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Note:YaxisisC5+gasolineyield
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
CombinedProductionTrends
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
BoilingPointRangesforProducts
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500
1,000
1,500
2,000
2,500
0 100 200 300 400 500 600
BPT [F]
Incr
emen
tal Y
ield
[b
pd
]
84-reformate77-Ovhd liquids75-Offgas1-Sour.naphtha
9,999 bpd Sour Naptha Feed8,314 bpd Reformate
Basedonexampleproblemin:RefineryProcessModeling,APracticalGuidetoSteadyStateModelingofPetroleumProcesses,1st ed.GeraldKaes,AthensPrintingCompany,02004
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
EffectsofProcessVariables
Primarycontrolforchangingconditionsorqualitiesisreactortemperature Normallyabout950oFatreactorinlet Mayberaisedfordecliningcatalystactivityortocompensateforlowerqualityfeedstock Higherreactortemperatureincreasesoctaneratingbutreducesyield&runlength
Designconsiderationsforimprovementinqualitywillincludepressure,recycleratio,reactorresidencetime,&catalystactivity Lowreactorpressureincreasesyield&octanebutincreasescokemake Increasedhydrogenpartialpressureduetohydrogenrecycle(hydrogentohydrocarbonratio)suppressescokeformation,hydrogenyield&octanegain,butpromoteshydrocracking Lowspacevelocityfavorsaromaticsformationbutalsopromotescrackingbyoperatingclosertoequilibriumconditions Higheractivitycatalystscostmorebutincreasesrunlengthsand/oryields
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
SpecificCatalyticReformingProcesses
Hydroforming Earlycyclicprocessusedtoproducetoluenefor
TNTduringWorldWarII Molybdenumoxideonaluminacatalyst Rapidcokingofthecatalyst,requiringacyclic
regenerationofreactorsabouteveryfourhours Timingmechanismusedforlawnsprinklersystems
usedtoswitchfromreformingtoregenerationservice
Reactorsystemincludedoneextra"swing"reactoro Facilitateperiodicremoval®enerationof
areactor
UOPSemiRegenerativePlatforming Lowplatinum Regenerationonceayear Madenaphthaoctaneimprovementaccessible
toallrefiners
UOPContinuousRegenerationofReformingCatalyst Movingbedprocess
Continuouslyregeneratingaportionofamovingbedofcatalysttoremovecoke&sustainactivity
Operatingpressuresloweredto50psig
Threereactorsstackedoneontopoftheother Gravityflowofthecatalystfromtoptobottom Reactantspassradiallythroughthecatalysttothe
innerconduitandthentothenextbed Modeofregenerationisproprietary probably
employsairoroxygenburningofthecokefollowedbyreduction&acidification
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
High&LowPressureReforming
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RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
UOPsCCRPlatformingTM Process
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http://www.uop.com/objects/CCR%20Platforming.pdf
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu) 21
Light Naphtha
CrudeOil Desalter
Atmospheric Distillation
Vacuum Distillation
Gas Separation &
Stabilizer
Solvent Deasphal-
ting
Coking
Visbreaking
Fluidized Catalytic Cracking
Hydro-cracking
NaphthaReforming
Isom-erization
Sat Gas Plant
Polymer-ization
Alkylation
NaphthaHydro-treating
Treating & Blending
Coke
Fuel Gas
LPG
Aviation Gasoline
Automotive GasolineSolvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
ResidualFuel Oils
Lubricant
Greases
Waxes
Asphalts
HeavyNaphtha
Kerosene
DistillateAGO
LVGO
HVGO
VacuumResiduum
CatDistillates
Gas Oil Hydro-treating
DAO
Isomerate
Gas
AlkylFeed
Alkylate
PolymerizationNaphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel OilBottoms
Distillates
DistillateHydro-treating
CatNaphtha
Cycle Oils
SDABottomsCokerNaphtha
HeavyCokerGasOil
Light CokerGas Oil
SulfurPlant Sulfur
Naphtha
Fuel Oil
SolventDewaxing
Lube Oil
Waxes
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
C4&C5/C6Isomerization
C4 isomerization ConvertnC4 toiC4 iC4moredesirableasalkylationfeedstock
C5/C6 Isomerization Improvetheoctaneratingofstraightrungasoline
Nparaffins isomerizedtobranchedisoparaffins WillalsoconvertanynC4 toiC4
HighRVP(about17psi) limitsitsuseingasolinepool
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
U.S.RefineryImplementation
23
EIA,Jan.1,2017database,publishedJune2017http://www.eia.gov/petroleum/refinerycapacity/
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
CharacteristicsofPetroleumProducts
24
Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
HistoryofIsomerization
AviationgasolineforWorldWarII Butaneisomerizationwasdevelopedtocreatetheneededisobutane feedstock Aluminumchloridecatalyst Manyoftheseunitswereshutdownafterthewar
TetraEthylLeadPhaseOutin1970s StraightRunGasoline(SRG)reliedonTELforoctaneimprovement ResearchOctaneNumber(RON)ofonly70
SRGmostlyparaffinicpentanes&hexaneswithsomeheptanes andoctanes
Isomerizationcouldprovideneededoctaneboost EquivalentIsoparaffins havehigherRON
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
C5/C6IsomerizationProcesses
Vaporphaseprocess Hydrogenusedtosuppressdehydrogenation&coking Highyields&highselectivitytohighoctaneisomericforms Providesmoderate(butimportant)contributiontothegasolinepool
Catalysttypes Chloridealuminacatalyst
Organicchloridedepositedonactivemetalsites
o HightemperaturetreatmentwithCCl4 Chloridessensitivetomoisture dryingoffeed&hydrogenmakeupessential
Acidiczeolitewithnoblemetalcatalyst Platinumcatalyst DoesnotrequireactivationbyHCl
Pros ReformingconditionsnotappropriatefortheparaffiniccomponentsinSRG Essentiallyzerobenzene,aromatics,&olefins Verylowsulfurlevels
Cons Highvaporpressure Moderateoctanelevels (R+M)/2only85
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
C5/C6Isomerization Feedstocks &Products
Lightestnaphthafeedstock(SRG)withpentanes,hexanes,&smallamountsofheptanes Feedoftendebutanized DebutanizedStraightRun
Sulfur&nitrogenmustberemovedsincecatalystsemployanacidsiteforactivity Merox Claytreating Hydrotreating
CommonforStraightRunGasoline&Naphthatobehydrotreated asonestream&thenseparated
Products Isoparaffins &cycloparaffins Smallamountsoflightgassesfromhydrocracking Unconvertedfeedstock
Increasedseverityincreasesoctanebutalsoincreasesyieldoflightends
Yieldsdependonfeedstockcharacteristics&productoctane Poorqualityfeedsmightyield85%orlessliquidproduct Goodfeedsmightyield97%liquidproduct
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationChemistry
Primaryreactionistoconvertnormalparaffins toisomericparaffins
Olefinsmayisomerizeandshiftthepositionofthedoublebond 1butenecouldshifttoamixtureofcis2butene&trans2butene
Cycloparaffins (naphthenes)mayisomerize&breaktheringforminganolefin Cyclobutane tobutene
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
EffectsofProcessVariables
Lowtemperature,moderatehydrogenpartialpressure,lowspacevelocitypromotelongrunlengths
Isomerizationyieldscontrolledbychemicalequilibrium Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&increasethefinalproductoctane
Temperatureprimaryprocesscontrolvariable Highertemperaturesincreaseprocessingseverity(includinghydrocracking)
Otherprocessvariables Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocrackingreactions Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongscatalystlife Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ProcessImprovements
Removingisopentane fromfeed&bypassreactor
Usemolecularsievestoremove&recyclenormalparaffins Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation
Sidedrawofnhexane,2methylpentane,3methylpentane&recycle Octaneapproaching92RON Suitableforblendingintopremiumatnooctanepenalty
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CompoundBoiling
Point[F] RON MON (R+M)/2Neopentane 49.1 85.5 80.2 82.9Isopentane 82.12 92.3 90.3 91.3nPentane 96.92 61.7 62.6 62.22,2Dimethylbutane 121.52 91.8 93.4 92.62,3Dimethylbutane 136.38 100.3 94.3 97.32Methylpentane 140.47 73.4 73.5 73.53Methylpentane 145.91 74.5 74.3 74.4nHexane 155.72 24.8 26.0 25.4
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationOptions
UOPsParIsom process
Nonchloridedaluminacatalyst regenerable &toleranttosulfur&water
Typicalproductoctanes81 87dependingonflowconfiguration&feedstockqualities
Typically97wt%yieldoffreshfeed
GTCTechnologysIsomalk2process
Optimizedforhighconversionratewithcloseapproachtothermalequilibrium
Produceupto93RONwithfullrecycle
Operates120oC 180oC(250oF 350oF)
Over98%massyield
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2011RefiningProcessesHandbookHydrocarbonProcessing,2011
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu) 32
Light Naphtha
CrudeOil Desalter
Atmospheric Distillation
Vacuum Distillation
Gas Separation &
Stabilizer
Solvent Deasphal-
ting
Coking
Visbreaking
Fluidized Catalytic Cracking
Hydro-cracking
NaphthaReforming
Isom-erization
Sat Gas Plant
Polymer-ization
Alkylation
NaphthaHydro-treating
Treating & Blending
Coke
Fuel Gas
LPG
Aviation Gasoline
Automotive GasolineSolvents
Jet Fuels
Kerosene
Solvents
Heating Oils
Diesel
ResidualFuel Oils
Lubricant
Greases
Waxes
Asphalts
HeavyNaphtha
Kerosene
DistillateAGO
LVGO
HVGO
VacuumResiduum
CatDistillates
Gas Oil Hydro-treating
DAO
Isomerate
Gas
AlkylFeed
Alkylate
PolymerizationNaphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel OilBottoms
Distillates
DistillateHydro-treating
CatNaphtha
Cycle Oils
SDABottomsCokerNaphtha
HeavyCokerGasOil
Light CokerGas Oil
SulfurPlant Sulfur
Naphtha
Fuel Oil
SolventDewaxing
Lube Oil
Waxes
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Alkylation&Polymerization
Processestomakegasolinecomponentsfrommaterialsthataretoolighttootherwisebeingasoline
Alkylation Formalongerchainhighlybranchedisoparaffin byreactinganalkylgroup(almostexclusivelyisobutane)withalightolefin(predominatelybutylene) Produceshighoctanegasoline
Polymerization Formationofveryshortchains Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctanenumber
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
U.S.RefineryImplementation
34
EIA,Jan.1,2016database,publishedJune2016http://www.eia.gov/petroleum/refinerycapacity/
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
CharacteristicsofPetroleumProducts
35
Alkylation:combinesmallmoleculesforgasolinewithgoodproperties
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
OlefinAlkylation&Polymerization
1920s&1930sothermethodsusedtoimprovegasolineoctane TetraEthylLeadinStraightRunGasoline Thermalreformingofnaphtha Thermalpolymerizationofolefinic lightendsto
hexenes,heptenes,&octenes
Inlate1930s&early1940s,alkylationofolefinswasdevelopedtoimprovetheoctaneofaviationgasoline VladimirIpatieffhaddiscoveredaluminum
chloridecatalysisin1932
FCCsignificantlyincreasedtheproductionoflightends HighconcentrationoftheC3,C4,&C5isomers,
botholefinic ¶ffinic Ledtodevelopmentofbothcatalytic
polymerization&alkylation
FollowingendoftheKoreanconflict(1953)refinersinvestigateduseoftheircatalyticpolymerizationandalkylationcapacityforproductionofhigheroctanemotorfuels Chicken&egg increasingoctaneproduction
capacity&higherperformanceenginesinautomobilesledtotheoctaneraceinmid1950s
Bothpolymerization&alkylationwereadapted alkylationbecamethedominantprocess
Bythe1960s,polymerizationunitswerebeingphasedout&newplantsutilizedalkylationtechnology
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
SulfuricAcidvs.HFAlkylation
SulfuricAcidAlkylation
Developedbyconsortiumofmajorrefiners&contractors AngloIranianOil,HumbleOil&Refining,Shell
Development,StandardOilDevelopment,&theTexasCompany
FirstunitatHumbleBaytownRefinery,1938 Manyalkylationplantswerebuiltatthesame
timeasthecatalyticcrackingunits OperatedduringWorldWarIIforaviation
gasolineproduction
Sulfuricacidalkylationrequiredaccesstoacidregenerationonalargescale Mostlocatedondeepwaterforbarge
transportofspentacidtoregenerationatacidplants&returnoffreshacid
EconomichandicapforinlandMidwesternrefineries
HFAcidAlkylation
SeparatelydevelopedbyPhillipsPetroleum&UOP HFcouldbereadilyregeneratedinalkylation
plantfacilities Noneedtotransportcatalystinlarge
quantitiesforregeneration
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Feedstocks &Products
Olefinic streamfromthecatalyticcracker Butylenepreferredolefin produceshighestoctanenumber&yields isobutane &isopentane canbereactedwiththeolefin Isopentane notusuallyusedsinceitisagoodgasolineblendstock
Highoctanenumber&lowvaporpressure
Catalyticcrackerfeedcontainssignificantsulfur Treatingunitoftenprecedesalkylationunit
Alkylatedesirablecomponentforhighperformanceautomotivefuels Veryhighoctaneindex(R+M)/2of95 Lowvaporpressure
Vaporpressureisadjustedforfinalboilingpoint
IBPadjustedforadditionofnormalbutane
Lowsulfurlevels Essentiallynoolefins,benzeneoraromatics
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
FeedstockConsiderations
OlefinFeed
Butylenepreferred Producesthehighestisooctanelevels ResultingResearchOctaneNumbersof9395
(withisobutane) RONandMONareaboutequalforalkylation Amountsofbutyleneconsumedperalkylate
producedisthelowest Sidereactionsarelimited
Propyleneworse Octanenumbersarelow(8992RON) Propylene&acidconsumptionarehigh
Penteneresultsaremixed Sidereactionsfrequent
Isoparaffin Feed
Excessisobutane required typicalvolumeratioofisobutane:olefin inthefeedis610 Limitedisobutane solubilityinacidphase Olefinsneedtobesurroundedbyisobutane
exposedtoacid ifnot,olefinswillpolymerizeinsteadofalkylate
Newerplantshavemultiinjection&vigorousmixingsystems Effectofisobutane isexpressedintermsof
concentrationinthereactionzone Isobutane:olefin ratiosmaintainedat10,000:1
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
C4Isomerization
UOPsButamerTM processisahighefficiency,costeffectivemeanstomeetisobutane demandsbyisomerizingnC4 toiC4
Equilibriumlimited LowtemperaturefavorsiC4 Highactivitychloridedaluminacatalystsused
HighselectivitytoiC4 byseparating&recyclingnC4 toextinction Oncethroughlowercapitalcost
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ProcessChemistryExamples
Isobutylene&isobutane form2,2,4trimethylpentane(isooctane)
Propylene&isobutaneform2,2dimethylpentaneasprimaryproductwith2,3&2,4dimethylpentaneassecondaryproducts
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C CH2
CH3
CH3
+ H+ C+
CH3
CH3
CH3
C+
CH3
CH3
CH3 CH
CH3
CH3
CH3 + H+CCH3
CH3
CH3 CH CH3
CH3
CH2+
Olefin Paraffin Product RON
Isobutylene Isobutane Isooctane 100
Propylene Isobutane
2,2dimethylpentane 92.8
2,3dimethylpentane 91.1
2,4dimethylpentane 88.0
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
AlkylationProcessChemistry
Acidcatalyzedalkylationcombinesisoparaffins &olefinstoformalkylate,highlybranchedalkanes Usuallyonlyisobutane isused Isopentane canbeagoodgasolineblendstockforwintergasoline
FriedelCraftsreaction Lewisacid(HForH2SO4)promotescarboniumiononatertiaryisoparaffin thatrapidlyreactswithanydoublebonditencounters(propylene,butylenes,orpentylenes)
Thereactioncarriedoutintheliquidphasewithanacid/reactantemulsionmaintainedatmoderatetemperatures
Propylene,butylene,&pentenesused butylenepreferred Highoctaneisooctanealkylateproduced Lowerreactantconsumption
Alkylationreactionshavecomplexmechanisms&mayproducemanydifferentvarieties
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
OperatingVariables&TheirEffects
Capacityexpressedintermsofalkylateproduct,notfeedcapacity
Mostimportantvariables Typeofolefin
Propylene,butylene,orpentene
Isobutane concentration isobutane:olefin ratio Olefininjection&mixing Reactiontemperature Catalysttype&strength
Criticalmeasuresforsuccess Alkylateoctanenumber Volumeolefin&isobutane consumedpervolumealkylateproduced
Degreeofundesirablesidereactions
Acidconsumption
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Isobutane/OlefinInjection&Mixing
Moreimportantinsulfuricacidsystems Acidviscosityatoperatingtemperatures
Provideoptimalreactionconditionsfortheveryfastreaction Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsiontodisperseolefinasrapidlyaspossible
Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefinintheemulsion Leadstolowerquality&higheracidconsumptionfromesterificationreactions
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ProcessConsiderationsSulfuricAcid HFAcid
ReactionTemperature
Increasingtemperaturesreducesoctanenumber
SulfuricAcidsystemsrunat45oF chilledwater,refrigeration,orautorefrigerationrequired
HFsystemsrunat95oF coolingwatersufficient
AcidStrength Consideredspentabout88wt%sulfuricacid
Normallykeptinrangeof86 92wt%.84%isminimum
Waterlowersacidactivity3 5timesasfastashydrocarbondiluents
HFwithwaterleadtocorrosion
Regeneration Acidregenerationonalargescale mostlocatedondeepwaterforbargetransportofspentacidtoregenerationatacidplant&returnoffreshacid
HFregeneratedonsitebydistillation onlysmallacidquantitiesformakeupneedbetransported
OtherConsiderations
Dominantprocessbut Smallerfootprint
Requiresextensiverecuperationofspentacid
UrbancommunityconcernstohazardsofHFescape1.
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1UnitedSteelworkersUnionCallsforIndustrywidePhaseoutofHydrogenFluorideinOilRefineryAlkylationUnitshttp://www.usw.org/media_center/releases_advisories?id=0207August31,2009
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Autorefrigerated ReactorSulfuricAcidAlkylation(EMRE)
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SulfuricAcidAlkylationTechnologyDr.Girish K.Chitnis,Mr.RonD.McGihon,Mr.Aneesh PrasadandMr.ChristopherM.DeanGrowingImportanceofAlkylationSeptember2009http://www.exxonmobil.com/Apps/RefiningTechnologies/Files/Conference_2009_sulfuricalkylation_Sept.pdf
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
STRATCOContactorTM ReactorSulfuricAcidAlkylation(DuPont)
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STRATCOAlkylationTechnologyImprovementsKevinBockwinkel2007NPRAAnnualMeetinghttp://www2.dupont.com/Sustainable_Solutions/en_US/assets/downloads/stratco/STRATCO_AlkylationTechnologyImprovements.pdf
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
HFAlkylationSystem
Differencestosulfuricacidsystems Feeddriersessentialtominimizecatalystconsumption
Waterformsanazeotrope withHFleadingtoacidloss
HFstripperrequiredondepropanizer overheadtocleanuppropaneforLPG HFregeneratoroperatingonaslipstreamfromacidsettler
Manyacidsolubleorganiccompoundsdecomposebutsomemustberejectedasacidsolubleoil
Spentacidrequiresspecialneutralization ConvertHFtocalciumfluoride&burnablewaste Overallacidlossshouldbelessthanonepoundperbarrelofacidproduced
ElaborateHFventing,neutralization&recoverysystem ConsideredbythepublictobeathreatintermsoflargereleasesofHF NewdesignsminimizetheinventoryofHFintheunitfarbelowearlierdesigns
Riskisminimized,noteliminated
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
UOP/PhillipsAlkylationProcess
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http://www.uop.com/processingsolutions/refining/gasoline/#alkylationPetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
PhillipsAlkylationProcessMassBalance
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Component Olefin FeedSaturated Butanes
Propane YieldMotor-Fuel
Butane YieldMotor-Fuel
Alylate YieldAcid Oils
Ethane 0.49 0.49Propylene 21.04Propane 17.42 0.30 18.77Isobutane 191.81 13.48 0.34 3.13 0.19Butenes 169.10n-Butane 63.17 10.11 63.35 9.93Pentanes 4.90 0.42 3.67 1.65Alkylate 390.17Acid Oils 0.55Total 467.93 24.31 19.60 70.15 401.94 0.55Stream Totals 492.24 492.24RVP [psi] 6.0Specific Gravity 0.70RON, clear 95.0MON, clear 93.5FBP [C] 195FBP [F] 383
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
Summary
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
GasolineUpgradingProcessComparisons
Pros Cons
Reforming Highoctane LowRVP Byproducthydrogen
Higharomatics(benzene)
Isomerization BetteroctanethanLSR Toolightforreforming Lowaromatics&olefins Verylowsulfurlevels
Octanestillrelativelylow HighRVP
Alkylation Goodoctane LowRVP
Requireslightends issueifnoFCCU
HFcommunityconcerns
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
SupplementalSlides
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
ReformerInstalledCost
Includes ISBLfacilitiestoproduce102RONreformate
fromsulfurfreeHSRnaphtha Productdebutanizer Allnecessarycontrollers&instrumentation AllISBLfacilities Heatexchangetoacceptfeed&release
productsatambienttemperature
Excludes Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge Royalty Feedfractionationordesulfurization
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PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationInstalledCost
Includes Dryingoffeed&hydrogenmakeup Completepreheat,reaction,&H2circulationfacilities Productstabilization Heatexchangetocoolproductstoambient
temperature Allnecessarycontrollers&instrumentation Paidroyalty
Excludes Hydrogensource Feeddesulfurization Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge
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PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
AlkylationInstalledCost
Includes Facilitiestoproducealkylatefromfeed
withiC4&C3toC5olefins Allnecessarycontrollers&
instrumentation AllISBLfacilities Feedtreating(molecularsievetoremove
moisturefromfeed)
Excludes Coolingwater,steam&powersupply Feed&productstorage
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PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
CatalyticReformingTechnologies
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Provider Features
Axens (1) Catalystregeneratedinplaceatendofcycle.Operatesinpressurerangeof170 350psig.
Axens (2) AdvancedOctanizing process,usescontinuouscatalystregenerationallowingpressuresaslowas50psig.
UOP CCRPlatformingprocess.Radialflowreactorsarrangedinverticalstack.
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationTechnologies
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Provider Features
Axens EitheroncethroughorIpsorb Isom withnormalparaffinrecycletoextinction.
CDTECH ISOMPLUSzeolitebasedcatalyst.
UOP(1) ParIsom processuseshighperformancenonchloridedaluminacatalysts
UOP(2) HOT(hydrogenoncethrough)Penex processeliminatesneedofrecyclegascompressor.Fixedbedusinghighactivitychloridepromotedcatalyst.
UOP(3) HOT(hydrogenoncethrough)Butamer processeliminatesneedofrecyclegascompressor.Twoseriesreactorsprovidehighonstreamefficiency.
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
AlkylationTechnologies
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Provider Features
CDTECH(1) CDAlkyl lowtemperaturesulfuricacidalkylation.
CDTECH(2) CDAlkylPlus lowtemperaturesulfuricacidalkylationcoupledwitholefinpretreatmentstep.
DuPont UsesSTRATCOEffluentRefrigerationAlkylationprocessusingsulfuricacid
Lummus Technology AlkylClean processusingsolidacidcatalyst.Demonstrationunitonly.
RefiningHydrocarbonTechnologiesLLC
RHTAlkylationprocessusessulfuricacid.Eductor mixingdevice.
ExxonMobilResearch&Engineering
Sulfuricacidalkylationusingautorefrigerated reactor.
UOP(1) ModifiedHFAlkylationtoreduceaerosolformation.
UOP(2) IndirectAlkylation(InAlk)usessolidcatalyst.Olefinspolymerize&highermolecularweightmaterialhydrogenated.
KBR KSAATSolidAcidAlkylationtechnology
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
EffectsofReformingProcessVariables
Reaction Pressure Temperature
Isomerizationofnaphthenes Indeterminate Indeterminate
Dehydrocyclization ofparaffins tonaphthenes Lowpressure Hightemperature
Dehydrogenationofnaphthenes toaromatics Lowpressure Hightemperature
Isomerizationofnormalparaffins toisoparaffins Slightdependence Slightdependence
Hydrocracking Highpressure Hightemperature
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationWith&WithoutiC5Removal
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
IsomerizationOptions
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http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization
UOPPenexTM HydrocarbonOnceThroughLimitedbyequilibrium 8084RONC
Isomerization/DIH Recyclesunconvertedlowoctaneisomers8789RONC
DIP/Isomerization/SuperDIH9093RONC
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
SulfuricAcidAlkylation
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RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
TimeTankReactors
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RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChE CDROM,2000
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Updated:July5,2017Copyright2017JohnJechura(jjechura@mines.edu)
HFAlkylationProcessEffluentManagement
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HandbookofPetroleumRefiningProcesses,3rd ed.Meyers(ed.)Chapter1.4,UOPHFAlkylationTechnologyDetrick,Himes,Meister,&NowakMcGrawHill,2004
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