09 Gasoline Upgrading

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


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

Automotive Gasoline

Solvents

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

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&regenerationofareactor

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


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

Automotive Gasoline

Solvents

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

22

C4&C5/C6Isomerization

C4isomerization ConvertnC4 toiC4 iC4 moredesirableasalkylationfeedstock

C5/C6Isomerization Improvetheoctaneratingofstraightrungasoline

Nparaffinsisomerizedtobranchedisoparaffins

WillalsoconvertanynC4 toiC4

HighRVP(about17psi) limitsitsuseingasolinepool

23


24

Top 10 iC5/iC6 Isomerization Capacities



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


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

Automotive Gasoline

Solvents

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

34

Alkylation&Polymerization

Processestomakegasolinecomponentsfrommaterialsthataretoolighttootherwisebeingasoline

Alkylation Formalongerchainhighlybranchedisoparaffinbyreactinganalkylgroup(almostexclusivelyisobutane)withalightolefin(predominatelybutylene)

Produceshighoctanegasoline Polymerization

Formationofveryshortchains Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctanenumber

35


36

Top 10 Alkylation Capacities



37

Alkylation:combinesmallmoleculesforgasolinewithgoodproperties

OlefinAlkylation&Polymerization

1920s&1930sothermethodsusedtoimprovegasolineoctane TetraEthylLeadinStraightRunGasoline Thermalreformingofnaphtha Thermalpolymerizationofolefinic lightendstohexenes,heptenes,&octenes

Inlate1930s&early1940s,alkylationofolefinswasdevelopedtoimprovetheoctaneofaviationgasoline

VladimirIpatieffhaddiscoveredaluminumchloridecatalysisin1932 FCCsignificantlyincreasedtheproductionoflightends

HighconcentrationoftheC3,C4,&C5isomers,botholefinic &paraffinic 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


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


IsomerizationOptions

62

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

UOPPenexTM HydrocarbonOnceThroughLimitedbyequilibrium 8084RONC

Isomerization/DIH Recyclesunconvertedlowoctaneisomers8789RONC

DIP/Isomerization/SuperDIH9093RONC

SulfuricAcidAlkylation

63


TimeTankReactors

64


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09 Gasoline Upgrading