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Gasoline
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JohnJechura [email protected]:July22,2014
GasolineUpgrading:CatalyticReforming,Isomerization,&AlkylationChapters10&11
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 Gasoline
Solvents
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
2
GasolineUpgrading Purpose
Increasethequalityoffeedstocksofthesameboilingrangeasgasoline
Characteristics CatalyticReforming
Convertsnaphthenes toaromatics
Produceshydrogen
Isomerization Rearrangesstraightchainstobranchedisomers
Verylittlechangeinboilingpoints
Alkylation Useolefinsproducedinotherprocesses(primarilyFCCU)
Produceisooctane
Liquidacidcatalyst
Products Gasolineblendstocksofimprovedoctaneand/orvolatility
4
DependencyofOctaneonChemicalStructure
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
5
DevelopmentofaDetailedGasolineCompositionBasedOctaneModelPrasenjeetGhosh,KarltonJ.Hickey,andStephenB.JaffeInd.Eng.Chem.Res. 2006,45,337345
DependencyofOctaneonChemicalStructure
6
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 Gasoline
Solvents
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
7
NaphthaReforming Almosteveryrefineryintheworldhasa
reformer Purposetoenhancearomaticcontentof
naphtha Feedstockstoaromaticscomplex Improvetheoctaneratingforgasoline
Manydifferentcommercialcatalyticreformingprocesses
Hydroforming Platforming Powerforming Ultraforming Thermofor catalyticreforming
Primaryreactions Dehydrogenation
naphthenesaromacs Isomerization
normalparaffins branchedisoparaffins
Hydrogenasbyproduct Ultimatelyusedinhydrotreating Catalyticreforming2ndtoFCCin
commercialimportancetorefiners
Reformatedesirablecomponentforgasoline
Highoctanenumber,lowvaporpressure,verylowsulfurlevels,&lowolefinsconcentration
USregulationsonlevelsofbenzene,aromatics,&olefins Airqualityconcerns
8
U.S.RefineryImplementation
9
Top 10 Total Reforming Capacities
EIA,Jan.1,2014database,publishedJune2014http://www.eia.gov/petroleum/refinerycapacity/
CharacteristicsofPetroleumProducts
10
Reforming:driveoffhydrogenforbettergasolinepropertiesw/ochangingsize
Feedstocks &Products
Hydrotreatedheavynaphthafeedstock Lightstraightrunnaphthatendstocracktobutanes&lighter Gasoilstreamstendtohydrocrack&depositcokeonthereforming
catalyst
Catalystisnoblemetal(e.g.platinum) verysensitivetosulfur&nitrogen
Feedstockshydrotreatedforsulfur&nitrogenremoval Controlofchloride&wateralsoimportant
Severity Highseverityusedtomaximizearomatics
SenttoBTXseparationforaromaticfeedstocks
Lowseverityusedforgasolineblendstocks Producesthemajorityofthehydrogenusedforhydrotreating
11
ReformingChemistry
Usesasolidcatalysttoconvertnaphthenes tothecorrespondingaromatics&isomerizeparaffinicstructurestoisomericforms
Bothreactionsleadtoamarkedincreaseinoctanenumber
Bothreactionsleadtovolumeshrinkage CorrelationspermittheuseofaPONAanalysisofthefeedforpredictionofyieldandqualityoftheproduct
OriginallyfeedqualitiesmeasuredintermsofWatson"K"Factor aroughindicationofamountofparaffins
Aromaticslargelyuntouchedbyreactions
12
Isomerization
CH3CH3
CH2
CH3CH3
HydrocrackingCH2CH3 CH3
+ H2 +
CH3 CH3
+ 3 H2
Dehydrogenation
+ H2
Dehydrocyclization
CH3
CH3
CH3
CH3
+ H2
ReformerYieldExample
13
Example
CombinedProductionTrends
15
BoilingPointRangesforProducts
16
Kaes's Example Naptha Hydrotreating & Reforming Problem
-
500
1,000
1,500
2,000
2,500
0 100 200 300 400 500 600
BPT [F]
I
n
c
r
e
m
e
n
t
a
l
Y
i
e
l
d
[
b
p
d
]
84-reformate77-Ovhd liquids75-Offgas1-Sour.naphtha
9,999 bpd Sour Naptha Feed8,314 bpd Reformate
EffectsofProcessVariables Primarycontrolforchangingconditionsorqualitiesisreactortemperature
Normallyabout950Fatreactorinlet Mayberaisedfordecliningcatalystactivityortocompensateforlowerqualityfeedstock Higherreactortemperatureincreasesoctaneratingbutreducesyieldandrunlength
Designconsiderationsforimprovementinqualitywillincludepressure,recycleratio,reactorresidencetime,&catalystactivity
Lowreactorpressure increasesyield&octanebutincreasescokemake Increasedhydrogenpartialpressure duetohydrogenrecycle(hydrogentohydrocarbonratio)suppressescokeformation,hydrogenyield&octanegain,butpromoteshydrocracking
Lowspacevelocity favorsaromaticsformationbutalsopromotescrackingbyoperatingclosertoequilibriumconditions
Higheractivity catalystscostmorebutincreasesrunlengthsand/oryields
17
SpecificCatalyticReformingProcesses
Hydroforming EarlycyclicprocessusedtoproducetolueneforTNTduringWorldWarII
Molybdenumoxideonaluminacatalyst Rapidcokingofthecatalyst,requiringacyclicregenerationofreactorsabouteveryfourhours
Timingmechanismusedforlawnsprinklersystemsusedtoswitchfromreformingtoregenerationservice
Reactorsystemincludedoneextra"swing"reactor
o Facilitateperiodicremoval®enerationofareactor
UOPSemiRegenerativePlatforming Lowplatinum Regenerationonceayear Madenaphthaoctaneimprovementaccessibletoallrefiners
UOPContinuousRegenerationofReformingCatalyst
Movingbedprocess Continuouslyregeneratingaportionofamoving
bedofcatalysttoremovecoke&sustainactivity
Operatingpressuresloweredto50psig
Threereactorsstackedoneontopoftheother Gravityflowofthecatalystfromtoptobottom
Reactantspassradiallythroughthecatalysttotheinnerconduitandthentothenextbed
Modeofregenerationisproprietary probablyemploysairoroxygenburningofthecokefollowedbyreduction&acidification
18
UOPPlatforming
19
RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
UOPsCCRPlatformingTM Process
20
http://www.uop.com/objects/CCR%20Platforming.pdf
ReformerInstalledCost
Includes ISBLfacilitiestoproduce102RON
reformatefromsulfurfreeHSRnaphtha
Productdebutanizer Allnecessarycontrollers&
instrumentation
AllISBLfacilities Heatexchangetoacceptfeed&release
productsatambienttemperature
Excludes Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge Royalty Feedfractionationordesulfurization
21
PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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 Gasoline
Solvents
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
22
C4&C5/C6Isomerization
C4isomerization ConvertnC4 toiC4 iC4 moredesirableasalkylationfeedstock
C5/C6Isomerization Improvetheoctaneratingofstraightrungasoline
Nparaffinsisomerizedtobranchedisoparaffins
WillalsoconvertanynC4 toiC4
HighRVP(about17psi) limitsitsuseingasolinepool
23
U.S.RefineryImplementation
24
Top 10 iC5/iC6 Isomerization Capacities
EIA,Jan.1,2014database,publishedJune2014http://www.eia.gov/petroleum/refinerycapacity/
CharacteristicsofPetroleumProducts
25
Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize
HistoryofIsomerization
AviationgasolineforWorldWarII Butaneisomerizationwasdevelopedtocreatetheneededisobutanefeedstock Aluminumchloridecatalyst Manyoftheseunitswereshutdownafterthewar
TetraEthylLeadPhaseOutin1970s StraightRunGasoline(SRG)reliedonTELforoctaneimprovement ResearchOctaneNumber(RON)ofonly70
SRGmostlyparaffinicpentanes&hexaneswithsomeheptanesandoctanes
Isomerizationcouldprovideneededoctaneboost EquivalentIsoparaffinshavehigherRON
26
C5/C6IsomerizationProcesses
Vaporphaseprocess Hydrogenusedtosuppressdehydrogenation&coking
Highyields&highselectivitytohighoctaneisomericforms
Providesmoderate(butimportant)contributiontothegasolinepool
Catalysttypes Chloridealuminacatalyst
Organicchloridedepositedonactivemetalsiteso Hightemperaturetreatmentwithcarbontetrachloride
Chloridessensitivetomoisture dryingoffeed&hydrogenmakeupessential
Acidiczeolitewithnoblemetalcatalyst Platinumcatalyst Doesnotrequireactivationbyhydrogenchloride
Pros ReformingconditionsnotappropriatefortheparaffiniccomponentsinSRG
Essentiallyzerobenzene,aromatics,&olefins
Verylowsulfurlevels Cons
Highvaporpressure Moderateoctanelevels (R+M)/2only85
27
C5/C6Isomerization Feedstocks &Products Lightestnaphthafeedstock(SRG)withpentanes,hexanes,&smallamountsofheptanes
Feedoftendebutanized Debutanized StraightRun
Sulfur&nitrogenmustberemovedsincecatalystsemployanacidsiteforactivity
Merox Claytreating Hydrotreating
CommonforStraightRunGasoline&Naphthatobehydrotreated asonestream&thenseparated
Products Isoparaffins &cycloparaffins Smallamountsoflightgassesfromhydrocracking
Unconvertedfeedstock Increasedseverityincreasesoctanebutalsoincreasesyieldoflightends
Yieldsdependonfeedstockcharacteristics&productoctane
Poorqualityfeedsmightyield85%orlessliquidproduct
Goodfeedsmightyield97%liquidproduct
28
IsomerizationChemistry
Primaryreactionistoconvertnormalparaffinstoisomericparaffins
Olefinsmayisomerizeandshiftthepositionofthedoublebond 1butenecoluldshifttoamixtureofcis2butene&trans2butene
Cycloparaffins(naphthenes)mayisomerize&breaktheringforminganolefin Cyclobutanetobutene
29
EffectsofProcessVariables Lowtemperature,moderatehydrogenpartialpressure,lowspacevelocitypromotelongrunlengths
Isomerizationyieldscontrolledbychemicalequilibrium Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&increasethefinalproductoctane
Temperatureprimaryprocesscontrolvariable Highertemperaturesincreaseprocessingseverity(includinghydrocracking)
Otherprocessvariables Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocrackingreactions
Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongscatalystlife
Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields
30
ProcessImprovements
Numberofcombinationsoffractionationandisomerization RemovingisopentanefromfeedincreasestheproductsRONto84 AdditionofadepentanizeronproductstreamrecycleofnpentanerecycleincreasesproductsRONto86
SeparationusingmolecularsievesincreasestheproductsRONto89 UOPcombinesPenexwithMolex
Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation
TotalrecyclewithadeisohexanizerincreasestheproductsRONto89 Suitableforblendingintopremiumatnooctanepenalty
31
IsomerizationOptions
GTCTechnologysIsomalk2process
Optimizedforhighconversionratewithcloseapproachtothermalequilibrium
Produceupto93RONwithfullrecycle
Operates120oC 180oC(250oF 350oF)
Over98%massyield
UOPsParIsom process
Nonchloridedaluminacatalyst regenerable &toleranttosulfur&water
Typicalproductoctanes81 87dependingonflowconfiguration&feedstockqualities
Typically97wt%yieldoffreshfeed
32
2011RefiningProcessesHandbookHydrocarbonProcessing,2011
Isomerization InstalledCost
Includes Dryingoffeed&hydrogenmakeup Completepreheat,reaction,&H2
circulationfacilities
Productstabilization Heatexchangetocoolproductsto
ambienttemperature
Allnecessarycontrollers&instrumentation
Paidroyalty Excludes
Hydrogensource Feeddesulfurization Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge
33
PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
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 Gasoline
Solvents
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
34
Alkylation&Polymerization
Processestomakegasolinecomponentsfrommaterialsthataretoolighttootherwisebeingasoline
Alkylation Formalongerchainhighlybranchedisoparaffinbyreactinganalkylgroup(almostexclusivelyisobutane)withalightolefin(predominatelybutylene)
Produceshighoctanegasoline Polymerization
Formationofveryshortchains Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctanenumber
35
U.S.RefineryImplementation
36
Top 10 Alkylation Capacities
EIA,Jan.1,2014database,publishedJune2014http://www.eia.gov/petroleum/refinerycapacity/
CharacteristicsofPetroleumProducts
37
Alkylation:combinesmallmoleculesforgasolinewithgoodproperties
OlefinAlkylation&Polymerization
1920s&1930sothermethodsusedtoimprovegasolineoctane TetraEthylLeadinStraightRunGasoline Thermalreformingofnaphtha Thermalpolymerizationofolefinic lightendstohexenes,heptenes,&octenes
Inlate1930s&early1940s,alkylationofolefinswasdevelopedtoimprovetheoctaneofaviationgasoline
VladimirIpatieffhaddiscoveredaluminumchloridecatalysisin1932 FCCsignificantlyincreasedtheproductionoflightends
HighconcentrationoftheC3,C4,&C5isomers,botholefinic ¶ffinic Ledtodevelopmentofbothcatalyticpolymerization&alkylation
FollowingendoftheKoreanconflict(1953)refinersinvestigateduseoftheircatalyticpolymerizationandalkylationcapacityforproductionofhigheroctanemotorfuels
Chicken&egg increasingoctaneproductioncapacity&higherperformanceenginesinautomobilesledtotheoctaneraceinmid1950s
Bothpolymerization&alkylationwereadapted alkylationbecamethedominantprocess
Bythe1960s,polymerizationunitswerebeingphasedout&newplantsutilizedalkylationtechnology
38
SulfuricAcidvs.HFAlkylationSulfuricAcidAlkylation
Developedbyconsortiumofmajorrefiners&contractors
AngloIranianOil,HumbleOil&Refining,ShellDevelopment,StandardOilDevelopment,&theTexasCompany
FirstunitatHumbleBaytownRefinery,1938 Manyalkylationplantswerebuiltatthesametimeasthecatalyticcrackingunits
OperatedduringWorldWarIIforaviationgasolineproduction
Sulfuricacidalkylationrequiredaccesstoacidregenerationonalargescale
Mostlocatedondeepwaterforbargetransportofspentacidtoregenerationatacidplants&returnoffreshacid
EconomichandicapforinlandMidwesternrefineries
HFAcidAlkylation
DevelopedbyPhillipsPetroleum&UOP
HFcouldbereadilyregeneratedinalkylationplantfacilities
Noneedtotransportcatalystinlargequantitiesforregeneration
39
Feedstocks &Products Olefinic streamfromthecatalytic
cracker
Butyleneisthepreferredolefinsinceitproducesthehighestoctanenumber&yields
isobutane &isopentane canbereactedwiththeolefin
Isopentane notusuallyusedsinceitisagoodgasolineblendstock
Highoctanenumber&lowvaporpressure
Catalyticcrackerfeedcontainssignificantsulfur
Treatingunitoftenprecedesalkylationunit
Alkylatedesirablecomponentforhighperformanceautomotivefuels
Veryhighoctaneindex(R+M)/2of95 Lowvaporpressure
Vaporpressureisadjustedforfinalboilingpoint
IBPadjustedforadditionofnormalbutane
Lowsulfurlevels Essentiallynoolefins,benzeneoraromatics
40
C4Isomerization UOPsButamerTM processisahighefficiency,
costeffectivemeanstomeetisobutanedemandsbyisomerizingnC4toiC4
Equilibriumlimited LowtemperaturefavorsiC4 Highactivitychloridedaluminacatalystsused
HighselectivitytoiC4byseparating&recyclingnC4toextinction
Oncethroughlowercapitalcost
41
NButaneRecycledtoExtinction
OnceThroughNButaneConversion
AlkylationProcessChemistry
Acidcatalyzedalkylationcombinesisoparaffins &olefinstoformalkylate,highlybranchedalkanes Usuallyonlyisobutane isused
Isopentane canbeagoodgasolineblendstockforwintergasoline
FriedelCraftsreaction Lewisacid(HForH2S04)promotescarbonium iononatertiaryisoparaffin thatrapidlyreactswithanydoublebonditencounters(propylene,butylenes,orpentylenes)
Thereactioncarriedoutintheliquidphasewithanacid/reactantemulsionmaintainedatmoderatetemperatures
Propylene,butylene,&pentenes areolefinsused butylenepreferred Highoctaneisooctanealkylateproduced Lowerreactantconsumption
Alkylationreactionshavecomplexmechanisms&mayproducemanydifferentvarieties
42
ProcessChemistryExamples
Isobutylene&isobutaneform2,2,4trimethylpentane(isooctane)
Propylene&isobutaneform2,2dimethylpentaneasprimaryproductwith2,3dimethylpentane&2,4dimethylpentaneassecondaryproducts
43
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+
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
44
FeedstocksOlefinFeed
Butylenepreferred Producesthehighestisooctanelevels
ResultingResearchOctaneNumbersof9395(withisobutane)
RONandMONareaboutequalforalkylation
Amountsofbutyleneconsumedperalkylateproducedisthelowest
Sidereactionsarelimited Propyleneworse
Octanenumbersarelow(8992RON) Propylene&acidconsumptionarehigh
Penteneresultsaremixed Sidereactionsfrequent
Isoparaffin Feed
Excessisobutane required typicalvolumeratioofisobutane:olefin inthefeedis610
Limitedisobutane solubilityinacidphase
Olefinsneedtobesurroundedbyisobutane exposedtoacid ifnot,olefinswillpolymerizeinsteadofalkylate
Newerplantshavemultiinjection&vigorousmixingsystems
Effectofisobutane isexpressedintermsofconcentrationinthereactionzone
Isobutane:olefin ratiosmaintainedat10,000to1
45
Isobutane/OlefinInjection&Mixing
Moreimportantinsulfuricacidsystems Acidviscosityatoperatingtemperatures
Provideoptimalreactionconditionsfortheveryfastreaction Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsiontodisperseolefinasrapidlyaspossible
Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefinintheemulsion
Leadstolowerquality&higheracidconsumptionfromesterificationreactions
46
ProcessConsiderations
47
SulfuricAcid HFAcid
SulfuricAcidsystemsrunat45Fchilledwater,refrigeration,orautorefrigerationrequired
HFsystemsrunat95Fcoolingwatersufficient
Considered"spent"about88%sulfuricacid Keepintherangeof80%to95%
Waterlowersacidactivity3to5timesasfastashydrocarbondiluents
Regeneration
Acidregenerationonalargescalemostlocatedondeepwaterforbargetransportofspentacidtoregenerationatacidplants&returnoffreshacid
HFreadilyregeneratedonsitenoneedtotransportcatalystinlargequantitiesforregenerationotherthansmallacidmakeup
OtherConsideration
Dominantprocessbutrequiresextensiverecuperationofthespentacid
SmallerbuturbancommunityconcernstohazardsofHFescape1.
ReactionTemperature
AcidStrength
Increasingtemperaturereducesoctanenumber
1UnitedSteelworkersUnionCallsforIndustrywidePhaseoutofHydrogenFluorideinOilRefineryAlkylationUnitshttp://www.usw.org/media_center/releases_advisories?id=0207August31,2009
Autorefrigerated ReactorSulfuricAcidAlkylation(EMRE)
48
SulfuricAcidAlkylationTechnologyDr.Girish K.Chitnis,Mr.RonD.McGihon,Mr.Aneesh PrasadandMr.ChristopherM.DeanGrowingImportanceofAlkylationSeptember2009http://www.exxonmobil.com/Apps/RefiningTechnologies/Files/Conference_2009_sulfuricalkylation_Sept.pdf
STRATCOContactorTM ReactorSulfuricAcidAlkylation(DuPont)
49
STRATCOAlkylationTechnologyImprovementsKevinBockwinkel2007NPRAAnnualMeetinghttp://www2.dupont.com/Sustainable_Solutions/en_US/assets/downloads/stratco/STRATCO_AlkylationTechnologyImprovements.pdf
HFAlkylationSystem
Differencestosulfuricacidsystems Feeddriersessentialtominimizecatalystconsumption
WaterformsanazeotropewithHFleadingtoacidloss
HFstripperrequiredondepropanizeroverheadtocleanuppropaneforLPG HFregeneratoroperatingonaslipstreamfromacidsettler
Manyacidsolubleorganiccompoundsdecomposebutsomemustberejectedasacidsolubleoil
Spentacidrequiresspecialneutralization ConvertHFtocalciumfluoride&burnablewaste
Overallacidlossshouldbelessthanonepoundperbarrelofacidproduced
ElaborateHFventing,neutralization&recoverysystem ConsideredbythepublictobeathreatintermsoflargereleasesofHF NewdesignsminimizetheinventoryofHFintheunitfarbelowearlierdesigns
Riskisminimized,noteliminated
50
UOP/PhillipsAlkylationProcess
51
http://www.uop.com/processingsolutions/refining/gasoline/#alkylationPetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
PhillipsAlkylationProcess
52
Component Olefin Feed Saturated Butanes Propane YieldMotor-Fuel
Butane YieldMotor-Fuel
Alylate Yield Acid 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
AlkylationInstalledCost
Includes Facilitiestoproducealkylate fromfeed
withiC4&C3toC5olefins
Allnecessarycontrollers&instrumentation
AllISBLfacilities Feedtreating(molecularsievetoremove
moisturefromfeed)
Excludes Coolingwater,steam&powersupply Feed&productstorage
53
PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007
GasolineUpgradingProcessComparisons
Pros Reforming
Highoctane
LowRVP
Byproducthydrogen
Isomerization BetteroctanethanLSR
Toolightforreforming
Lowaromatics&olefins
Verylowsulfurlevels
Alkylation Goodoctane
LowRVP
Cons Reforming
Higharomatics(benzene)
Isomerization Octanestillrelativelylow
HighRVP
Alkylation Requireslightends issueifnoFCCU
HFcommunityconcerns
54
SupplementalSlides
Phillips66capacities
Technologyproviders
Effectsofreformingprocessvariables
Otherisomerizationblockflowdiagrams
Othersulfuricacidalkylationblockflowdiagrams
55
Phillips66Statistics
56
U.S.informationfromEIA,Jan.1,2014database,publishedJune2014http://www.eia.gov/petroleum/refinerycapacity/
CatalyticReformingTechnologies
57
Provider Features
Axens(1)Catalystregeneratedinplaceatendofcycle.Operatesinpressurerangeof170350psig.
Axens(2)AdvancedOctanizingprocess,usescontinuouscatalystregenerationallowingpressuresaslowas50psig.
UOPCCRPlatformingprocess.Radialflowreactorsarrangedinverticalstack.
IsomerizationTechnologies
58
Provider Features
AxensEitheroncethroughorIpsorbIsomwithnormalparaffinrecycletoextinction.
CDTECH ISOMPLUSzeolitebasedcatalyst.
UOP(1)ParIsomprocessuseshighperformancenonchloridedaluminacatalysts
UOP(2)
HOT(hydrogenoncethrough)Penexprocesseliminatesneedofrecyclegascompressor.Fixedbedusinghighactivitychloridepromotedcatalyst.
UOP(3)
HOT(hydrogenoncethrough)Butamerprocesseliminatesneedofrecyclegascompressor.Twoseriesreactorsprovidehighonstreamefficiency.
AlkylationTechnologies
59
Provider FeaturesCDTECH(1) CDAlkyllowtemperaturesulfuricacidalkylation.
CDTECH(2)CDAlkylPluslowtemperaturesulfuricacidalkylationcoupledwitholefinpretreatmentstep.
DuPontUsesSTRATCOEffluentRefrigerationAlkylationprocessusingsulfuricacid
LummusTechnologyAlkylCleanprocessusingsolidacidcatalyst.Demonstrationunitonly.
RefiningHydrocarbonTechnologiesLLC
RHTAlkylationprocessusessulfuricacid.Eductormixingdevice.
ExxonMobilResearch&Engineering Sulfuricacidalkylationusingautorefrigeratedreactor.UOP(1) ModifiedHFAlkylationtoreduceaerosolformation.
UOP(2)
IndirectAlkylation(InAlk)usessolidcatalyst.Olefinspolymerize&highermolecularweightmaterialhydrogenated.
EffectsofReformingProcessVariables
60
Reaction Pressure Temperature
Isomerizationofnaphthenes Indeterminate Indeterminate
Dehydrocyclizationofparaffinstonaphthenes Lowpressure Hightemperature
Dehydrogenationofnaphthenestoaromatics Lowpressure Hightemperature
Isomerizationofnormalparaffinstoisoparaffins
Slightdependence Slightdependence
Hydrocracking Highpressure Hightemperature
IsomerizationWith&WithoutiC5Removal
61
RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
IsomerizationOptions
62
http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization
UOPPenexTM HydrocarbonOnceThroughLimitedbyequilibrium 8084RONC
Isomerization/DIH Recyclesunconvertedlowoctaneisomers8789RONC
DIP/Isomerization/SuperDIH9093RONC
SulfuricAcidAlkylation
63
RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
TimeTankReactors
64
RefiningOverview PetroleumProcesses&Products,byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000