Gasoline Upgrading: Reforming, Isomerization, & Alkylationjjechura/Refining/09_Gasoline_Upgrading.pdf · Gasoline Upgrading Purpose ... Gas oil streams tend to hydrocrack & deposit

GasolineUpgrading:Reforming,Isomerization,&AlkylationChapters10&11

Updated:July5,2017Copyright2017JohnJechura([email protected]) 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

Updated:July5,2017Copyright2017JohnJechura([email protected])

GasolineUpgrading

Purpose Increasethequalityoffeedstocksofthesame

boilingrangeasgasoline

Characteristics CatalyticReforming

Convertsnaphthenes toaromatics Produceshydrogen

Isomerization Rearrangesstraightchainstobranchedisomers Verylittlechangeinboilingpoints

Alkylation Useolefinsproducedinotherprocesses(primarily

FCCU) Produceisooctane Liquidacidcatalyst

Products Gasolineblendstocksofimprovedoctane

and/orvolatility

4


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


DependencyofOctaneonChemicalStructure

6


Light Naphtha

CrudeOil Desalter


Vacuum Distillation

Gas Separation &

Stabilizer

Solvent Deasphal-

ting

Coking

Visbreaking


Hydro-cracking

NaphthaReforming

Isom-erization

Sat Gas Plant

Polymer-ization

Alkylation


Treating & Blending

Coke

Fuel Gas

LPG

Aviation Gasoline


Jet Fuels

Kerosene

Solvents

Heating Oils

Diesel

ResidualFuel Oils

Lubricant

Greases

Waxes

Asphalts

HeavyNaphtha

Kerosene

DistillateAGO

LVGO

HVGO

VacuumResiduum

CatDistillates


DAO

Isomerate

Gas

AlkylFeed

Alkylate


Gases

Butanes

LPG

Reformate

Naphtha

Fuel OilBottoms

Distillates


CatNaphtha

Cycle Oils


HeavyCokerGasOil

Light CokerGas Oil

SulfurPlant Sulfur

Naphtha

Fuel Oil

SolventDewaxing

Lube Oil

Waxes


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

8


U.S.RefineryImplementation

9

EIA,Jan.1,2017database,publishedJune2017http://www.eia.gov/petroleum/refinerycapacity/


CharacteristicsofPetroleumProducts

10

Reforming:driveoffhydrogenforbettergasolinepropertiesw/ochangingsize


Feedstocks &Products

Hydrotreated heavynaphthafeedstock Lightstraightrunnaphthatendstocracktobutanes&lighter Gasoilstreamstendtohydrocrack&depositcokeonthereformingcatalyst

Catalystisnoblemetal(e.g.platinum) verysensitivetosulfur&nitrogen Feedstockshydrotreated forsulfur&nitrogenremoval Controlofchloride&wateralsoimportant

Severity Highseverityusedtomaximizearomatics

SenttoBTXseparationforaromaticfeedstocks

Lowseverityusedforgasolineblendstocks

Producesthemajorityofthehydrogenusedforhydrotreating

11


ReformingChemistry

Usesasolidcatalysttoconvertnaphthenestothecorrespondingaromatics&isomerizeparaffinicstructurestoisomericforms Bothreactionsleadtoamarkedincreaseinoctanenumber Bothreactionsleadtovolumeshrinkage

CorrelationspermittheuseofaPONAanalysisofthefeedforpredictionofyieldandqualityoftheproduct OriginallyfeedqualitiesmeasuredintermsofWatson"K"Factor aroughindicationofamountofparaffins

Aromaticslargelyuntouchedbyreactions

12

IsomerizationCH3 CH3

CH2

CH3CH3

HydrocrackingCH2CH3 CH3

+ H2 +

CH3 CH3

+ 3 H2

Dehydrogenation

+ H2

Dehydrocyclization

CH3

CH3

CH3

CH3

+ H2


ReformerYieldExample

13


ReformerYieldTrends

14

Note:YaxisisC5+gasolineyield


CombinedProductionTrends

15


BoilingPointRangesforProducts

16

-

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


EffectsofProcessVariables

Primarycontrolforchangingconditionsorqualitiesisreactortemperature Normallyabout950oFatreactorinlet Mayberaisedfordecliningcatalystactivityortocompensateforlowerqualityfeedstock Higherreactortemperatureincreasesoctaneratingbutreducesyield&runlength

Designconsiderationsforimprovementinqualitywillincludepressure,recycleratio,reactorresidencetime,&catalystactivity Lowreactorpressureincreasesyield&octanebutincreasescokemake Increasedhydrogenpartialpressureduetohydrogenrecycle(hydrogentohydrocarbonratio)suppressescokeformation,hydrogenyield&octanegain,butpromoteshydrocracking Lowspacevelocityfavorsaromaticsformationbutalsopromotescrackingbyoperatingclosertoequilibriumconditions Higheractivitycatalystscostmorebutincreasesrunlengthsand/oryields

17


SpecificCatalyticReformingProcesses

Hydroforming Earlycyclicprocessusedtoproducetoluenefor

TNTduringWorldWarII Molybdenumoxideonaluminacatalyst Rapidcokingofthecatalyst,requiringacyclic

regenerationofreactorsabouteveryfourhours Timingmechanismusedforlawnsprinklersystems

usedtoswitchfromreformingtoregenerationservice

Reactorsystemincludedoneextra"swing"reactoro Facilitateperiodicremoval&regenerationof

areactor

UOPSemiRegenerativePlatforming Lowplatinum Regenerationonceayear Madenaphthaoctaneimprovementaccessible

toallrefiners

UOPContinuousRegenerationofReformingCatalyst Movingbedprocess

Continuouslyregeneratingaportionofamovingbedofcatalysttoremovecoke&sustainactivity

Operatingpressuresloweredto50psig

Threereactorsstackedoneontopoftheother Gravityflowofthecatalystfromtoptobottom Reactantspassradiallythroughthecatalysttothe

innerconduitandthentothenextbed Modeofregenerationisproprietary probably

employsairoroxygenburningofthecokefollowedbyreduction&acidification

18


High&LowPressureReforming

19

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


UOPsCCRPlatformingTM Process

20

http://www.uop.com/objects/CCR%20Platforming.pdf


Light Naphtha

CrudeOil Desalter


Vacuum Distillation

Gas Separation &

Stabilizer

Solvent Deasphal-

ting

Coking

Visbreaking


Hydro-cracking

NaphthaReforming

Isom-erization

Sat Gas Plant

Polymer-ization

Alkylation


Treating & Blending

Coke

Fuel Gas

LPG

Aviation Gasoline


Jet Fuels

Kerosene

Solvents

Heating Oils

Diesel

ResidualFuel Oils

Lubricant

Greases

Waxes

Asphalts

HeavyNaphtha

Kerosene

DistillateAGO

LVGO

HVGO

VacuumResiduum

CatDistillates


DAO

Isomerate

Gas

AlkylFeed

Alkylate


Gases

Butanes

LPG

Reformate

Naphtha

Fuel OilBottoms

Distillates


CatNaphtha

Cycle Oils


HeavyCokerGasOil

Light CokerGas Oil

SulfurPlant Sulfur

Naphtha

Fuel Oil

SolventDewaxing

Lube Oil

Waxes


C4&C5/C6Isomerization

C4 isomerization ConvertnC4 toiC4 iC4moredesirableasalkylationfeedstock

C5/C6 Isomerization Improvetheoctaneratingofstraightrungasoline

Nparaffins isomerizedtobranchedisoparaffins WillalsoconvertanynC4 toiC4

HighRVP(about17psi) limitsitsuseingasolinepool

22



23




24

Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize


HistoryofIsomerization

AviationgasolineforWorldWarII Butaneisomerizationwasdevelopedtocreatetheneededisobutane feedstock Aluminumchloridecatalyst Manyoftheseunitswereshutdownafterthewar

TetraEthylLeadPhaseOutin1970s StraightRunGasoline(SRG)reliedonTELforoctaneimprovement ResearchOctaneNumber(RON)ofonly70

SRGmostlyparaffinicpentanes&hexaneswithsomeheptanes andoctanes

Isomerizationcouldprovideneededoctaneboost EquivalentIsoparaffins havehigherRON

25


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

26


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

27


IsomerizationChemistry

Primaryreactionistoconvertnormalparaffins toisomericparaffins

Olefinsmayisomerizeandshiftthepositionofthedoublebond 1butenecouldshifttoamixtureofcis2butene&trans2butene

Cycloparaffins (naphthenes)mayisomerize&breaktheringforminganolefin Cyclobutane tobutene

28


EffectsofProcessVariables

Lowtemperature,moderatehydrogenpartialpressure,lowspacevelocitypromotelongrunlengths

Isomerizationyieldscontrolledbychemicalequilibrium Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&increasethefinalproductoctane

Temperatureprimaryprocesscontrolvariable Highertemperaturesincreaseprocessingseverity(includinghydrocracking)

Otherprocessvariables Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocrackingreactions Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongscatalystlife Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields

29


ProcessImprovements

Removingisopentane fromfeed&bypassreactor

Usemolecularsievestoremove&recyclenormalparaffins Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation

Sidedrawofnhexane,2methylpentane,3methylpentane&recycle Octaneapproaching92RON Suitableforblendingintopremiumatnooctanepenalty

30

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


IsomerizationOptions

UOPsParIsom process

Nonchloridedaluminacatalyst regenerable &toleranttosulfur&water

Typicalproductoctanes81 87dependingonflowconfiguration&feedstockqualities

Typically97wt%yieldoffreshfeed

GTCTechnologysIsomalk2process

Optimizedforhighconversionratewithcloseapproachtothermalequilibrium

Produceupto93RONwithfullrecycle

Operates120oC 180oC(250oF 350oF)

Over98%massyield

31

2011RefiningProcessesHandbookHydrocarbonProcessing,2011


Light Naphtha

CrudeOil Desalter


Vacuum Distillation

Gas Separation &

Stabilizer

Solvent Deasphal-

ting

Coking

Visbreaking


Hydro-cracking

NaphthaReforming

Isom-erization

Sat Gas Plant

Polymer-ization

Alkylation


Treating & Blending

Coke

Fuel Gas

LPG

Aviation Gasoline


Jet Fuels

Kerosene

Solvents

Heating Oils

Diesel

ResidualFuel Oils

Lubricant

Greases

Waxes

Asphalts

HeavyNaphtha

Kerosene

DistillateAGO

LVGO

HVGO

VacuumResiduum

CatDistillates


DAO

Isomerate

Gas

AlkylFeed

Alkylate


Gases

Butanes

LPG

Reformate

Naphtha

Fuel OilBottoms

Distillates


CatNaphtha

Cycle Oils


HeavyCokerGasOil

Light CokerGas Oil

SulfurPlant Sulfur

Naphtha

Fuel Oil

SolventDewaxing

Lube Oil

Waxes


Alkylation&Polymerization

Processestomakegasolinecomponentsfrommaterialsthataretoolighttootherwisebeingasoline

Alkylation Formalongerchainhighlybranchedisoparaffin byreactinganalkylgroup(almostexclusivelyisobutane)withalightolefin(predominatelybutylene) Produceshighoctanegasoline

Polymerization Formationofveryshortchains Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctanenumber

33



34




35

Alkylation:combinesmallmoleculesforgasolinewithgoodproperties


OlefinAlkylation&Polymerization

1920s&1930sothermethodsusedtoimprovegasolineoctane TetraEthylLeadinStraightRunGasoline Thermalreformingofnaphtha Thermalpolymerizationofolefinic lightendsto

hexenes,heptenes,&octenes

Inlate1930s&early1940s,alkylationofolefinswasdevelopedtoimprovetheoctaneofaviationgasoline VladimirIpatieffhaddiscoveredaluminum

chloridecatalysisin1932

FCCsignificantlyincreasedtheproductionoflightends HighconcentrationoftheC3,C4,&C5isomers,

botholefinic &paraffinic Ledtodevelopmentofbothcatalytic

polymerization&alkylation

FollowingendoftheKoreanconflict(1953)refinersinvestigateduseoftheircatalyticpolymerizationandalkylationcapacityforproductionofhigheroctanemotorfuels Chicken&egg increasingoctaneproduction

capacity&higherperformanceenginesinautomobilesledtotheoctaneraceinmid1950s

Bothpolymerization&alkylationwereadapted alkylationbecamethedominantprocess

Bythe1960s,polymerizationunitswerebeingphasedout&newplantsutilizedalkylationtechnology

36


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

37


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

38


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

39


C4Isomerization

UOPsButamerTM processisahighefficiency,costeffectivemeanstomeetisobutane demandsbyisomerizingnC4 toiC4

Equilibriumlimited LowtemperaturefavorsiC4 Highactivitychloridedaluminacatalystsused

HighselectivitytoiC4 byseparating&recyclingnC4 toextinction Oncethroughlowercapitalcost

40


ProcessChemistryExamples

Isobutylene&isobutane form2,2,4trimethylpentane(isooctane)

Propylene&isobutaneform2,2dimethylpentaneasprimaryproductwith2,3&2,4dimethylpentaneassecondaryproducts

41

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




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

42


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

43


Isobutane/OlefinInjection&Mixing

Moreimportantinsulfuricacidsystems Acidviscosityatoperatingtemperatures

Provideoptimalreactionconditionsfortheveryfastreaction Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsiontodisperseolefinasrapidlyaspossible

Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefinintheemulsion Leadstolowerquality&higheracidconsumptionfromesterificationreactions

44


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.

45

1UnitedSteelworkersUnionCallsforIndustrywidePhaseoutofHydrogenFluorideinOilRefineryAlkylationUnitshttp://www.usw.org/media_center/releases_advisories?id=0207August31,2009


Autorefrigerated ReactorSulfuricAcidAlkylation(EMRE)

46

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)

47

STRATCOAlkylationTechnologyImprovementsKevinBockwinkel2007NPRAAnnualMeetinghttp://www2.dupont.com/Sustainable_Solutions/en_US/assets/downloads/stratco/STRATCO_AlkylationTechnologyImprovements.pdf


HFAlkylationSystem

Differencestosulfuricacidsystems Feeddriersessentialtominimizecatalystconsumption

Waterformsanazeotrope withHFleadingtoacidloss

HFstripperrequiredondepropanizer overheadtocleanuppropaneforLPG HFregeneratoroperatingonaslipstreamfromacidsettler

Manyacidsolubleorganiccompoundsdecomposebutsomemustberejectedasacidsolubleoil

Spentacidrequiresspecialneutralization ConvertHFtocalciumfluoride&burnablewaste Overallacidlossshouldbelessthanonepoundperbarrelofacidproduced

ElaborateHFventing,neutralization&recoverysystem ConsideredbythepublictobeathreatintermsoflargereleasesofHF NewdesignsminimizetheinventoryofHFintheunitfarbelowearlierdesigns

Riskisminimized,noteliminated

48


UOP/PhillipsAlkylationProcess

49

http://www.uop.com/processingsolutions/refining/gasoline/#alkylationPetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007


PhillipsAlkylationProcessMassBalance

50

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


Summary


GasolineUpgradingProcessComparisons

Pros Cons

Reforming Highoctane LowRVP Byproducthydrogen

Higharomatics(benzene)

Isomerization BetteroctanethanLSR Toolightforreforming Lowaromatics&olefins Verylowsulfurlevels

Octanestillrelativelylow HighRVP

Alkylation Goodoctane LowRVP

Requireslightends issueifnoFCCU

HFcommunityconcerns

52


SupplementalSlides


ReformerInstalledCost

Includes ISBLfacilitiestoproduce102RONreformate

fromsulfurfreeHSRnaphtha Productdebutanizer Allnecessarycontrollers&instrumentation AllISBLfacilities Heatexchangetoacceptfeed&release

productsatambienttemperature

Excludes Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge Royalty Feedfractionationordesulfurization

54

PetroleumRefiningTechnology&Economics,5th ed.Gary,Handwerk,&KaiserCRCPress,2007


IsomerizationInstalledCost

Includes Dryingoffeed&hydrogenmakeup Completepreheat,reaction,&H2circulationfacilities Productstabilization Heatexchangetocoolproductstoambient

temperature Allnecessarycontrollers&instrumentation Paidroyalty

Excludes Hydrogensource Feeddesulfurization Coolingwater,steam&powersupply Feed&productstorage Initialcatalystcharge

55



AlkylationInstalledCost

Includes Facilitiestoproducealkylatefromfeed

withiC4&C3toC5olefins Allnecessarycontrollers&

instrumentation AllISBLfacilities Feedtreating(molecularsievetoremove

moisturefromfeed)

Excludes Coolingwater,steam&powersupply Feed&productstorage

56



CatalyticReformingTechnologies

57

Provider Features

Axens (1) Catalystregeneratedinplaceatendofcycle.Operatesinpressurerangeof170 350psig.

Axens (2) AdvancedOctanizing process,usescontinuouscatalystregenerationallowingpressuresaslowas50psig.

UOP CCRPlatformingprocess.Radialflowreactorsarrangedinverticalstack.


IsomerizationTechnologies

58

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.


AlkylationTechnologies

59

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


EffectsofReformingProcessVariables

Reaction Pressure Temperature

Isomerizationofnaphthenes Indeterminate Indeterminate

Dehydrocyclization ofparaffins tonaphthenes Lowpressure Hightemperature

Dehydrogenationofnaphthenes toaromatics Lowpressure Hightemperature

Isomerizationofnormalparaffins toisoparaffins Slightdependence Slightdependence

Hydrocracking Highpressure Hightemperature

60


IsomerizationWith&WithoutiC5Removal

61


IsomerizationOptions

62

http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization

UOPPenexTM HydrocarbonOnceThroughLimitedbyequilibrium 8084RONC

Isomerization/DIH Recyclesunconvertedlowoctaneisomers8789RONC

DIP/Isomerization/SuperDIH9093RONC


SulfuricAcidAlkylation

63



TimeTankReactors

64



HFAlkylationProcessEffluentManagement

65

HandbookofPetroleumRefiningProcesses,3rd ed.Meyers(ed.)Chapter1.4,UOPHFAlkylationTechnologyDetrick,Himes,Meister,&NowakMcGrawHill,2004

Documents

Gasoline Upgrading: Reforming, Isomerization, & Alkylationjjechura/Refining/09_Gasoline_Upgrading.pdf · Gasoline Upgrading Purpose ... Gas oil streams tend to hydrocrack & deposit