GasolineUpgrading:CatalyticReforming,Isomerization,&Alkylation

Chapters10&11

JohnJechura jjechura@mines.edu
Updated:July22,2014

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

GasolineUpgrading
Purpose
Increasethequalityoffeedstocksofthe
sameboilingrangeasgasoline

Products
Gasolineblendstocksofimprovedoctane
and/orvolatility

Characteristics
CatalyticReforming
Convertsnaphthenes toaromatics
Produceshydrogen

Isomerization
Rearrangesstraightchainstobranched
isomers
Verylittlechangeinboilingpoints

Alkylation
Useolefinsproducedinotherprocesses
(primarilyFCCU)
Produceisooctane
Liquidacidcatalyst

DependencyofOctaneonChemicalStructure
RON
Paraffins
nbutane
isobutane
npentane
ipentane
nhexane
C6monomethyls
2,2dimethylbutane
2,3dimethylbutane
nheptane
C7monomethyls
C7dimethyls
2,2,3trimethylbutane
noctane
C8monomethyls
C8dimethyls
C8trimethyls
nnonane
C9monomethyls
C9dimethyls
C9trimethyls
ndecane
C10monomethyls
C10dimethyls
C10trimethyls
nundecane
C11monomethyl
C11dimethyls
C11trimethyls
ndodecane
C12monomethyl
C12dimethyls
C12trimethyls

94
102
62
92
24.8
76
91.8
105.8
0
52
93.76
112.8
15
25
69
105
20
15
50
100
30
10
40
95
35
5
35
90
40
5
30
85

MON
89.6
97.6
62.6
90.3
26
73.9
93.4
94.3
0
52
90
101.32
20
32.3
74.5
98.8
20
22.3
60
93
30
10
40
87
35
5
35
82
40
5
30
80

RON
Naphthenes
cyclopentane
cyclohexane
mcyclopentane
C7naphthenes
C8naphthenes
C9naphthenes
Aromatics
benzene
toluene
C8aromatics
C9aromatics
C10aromatics
C11aromatics
C12aromatics
Olefins/CyclicOlefins
nbutenes
npentenes
ipentenes
cyclopentene
nhexenes
ihexenes
TotalC6cyclicolefins
totalC7d
totalC8d
Oxygenates
MTBE
TAME
EtOH

MON

100
82.5
91.3
82
55
35

84.9
77.2
80
77
50
30

102.7
118
112
110
109
105
102

105
103.5
105
101
98
94
90

98.7
90
103
93.3
90
100
95
90
90

82.1
77.2
82
69.7
80
83
80
78
77

115.2
115
108

97.2
98
92.9

DevelopmentofaDetailedGasolineCompositionBasedOctaneModel
PrasenjeetGhosh,KarltonJ.Hickey,andStephenB.Jaffe
Ind.Eng.Chem.Res. 2006,45,337345

DependencyofOctaneonChemicalStructure

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

NaphthaReforming
Almosteveryrefineryintheworldhasa
reformer

Purposetoenhancearomaticcontentof
naphtha

Feedstockstoaromaticscomplex
Improvetheoctaneratingforgasoline

Manydifferentcommercialcatalytic
reformingprocesses
Hydroforming
Platforming
Powerforming
Ultraforming
Thermofor catalyticreforming

Primaryreactions
Dehydrogenation
naphthenes aroma cs
Isomerization
normalparaffins branched
isoparaffins
Hydrogenasbyproduct
Ultimatelyusedinhydrotreating
Catalyticreforming2ndtoFCCin
commercialimportancetorefiners

Reformatedesirablecomponentfor
gasoline

Highoctanenumber,lowvaporpressure,
verylowsulfurlevels,&lowolefins
concentration
USregulationsonlevelsofbenzene,
aromatics,&olefins
Airqualityconcerns

U.S.RefineryImplementation
Top 10 Total Reforming Capacities

EIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/
9

CharacteristicsofPetroleumProducts

Reforming:driveoffhydrogenforbettergasolinepropertiesw/ochangingsize

10

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 to

Dehydrogenation

Bothreactionsleadtoamarkedincreaseinoctane
number

CH3

CH3

thecorrespondingaromatics&isomerize
paraffinicstructurestoisomericforms

Dehydrocyclization
CH3
CH3

Bothreactionsleadtovolumeshrinkage

CorrelationspermittheuseofaPONAanalysis

3 H2

H2

CH3
CH3

ofthefeedforpredictionofyieldandqualityof
theproduct

+ H2

Isomerization

Originallyfeedqualitiesmeasuredintermsof
Watson"K"Factor aroughindicationofamount
ofparaffins

CH3

CH3
CH3
CH2

CH3

Aromaticslargelyuntouchedbyreactions
Hydrocracking
CH3 CH2

CH3
+ H2

12

ReformerYieldExample

Example
13

CombinedProductionTrends

15

BoilingPointRangesforProducts
Kaes's Example Naptha Hydrotreating & Reforming Problem
9,999 bpd Sour Naptha Feed
8,314 bpd Reformate
2,500
84-reformate
77-Ovhd liquids
75-Offgas

2,000
Incremental Yield [bpd]

1-Sour.naphtha

1,500

1,000

500

100

200

300

400

500

600

BPT [F]

16

EffectsofProcessVariables
Primarycontrolforchangingconditionsorqualitiesisreactortemperature
Normallyabout950Fatreactorinlet
Mayberaisedfordecliningcatalystactivityortocompensateforlowerqualityfeedstock
Higherreactortemperatureincreasesoctaneratingbutreducesyieldandrunlength

Designconsiderationsforimprovementinqualitywillincludepressure,recycleratio,reactor
residencetime,&catalystactivity
Lowreactorpressure increasesyield&octanebutincreasescokemake
Increasedhydrogenpartialpressure duetohydrogenrecycle(hydrogentohydrocarbon
ratio)suppressescokeformation,hydrogenyield&octanegain,butpromotes
hydrocracking
Lowspacevelocity favorsaromaticsformationbutalsopromotescrackingbyoperating
closertoequilibriumconditions
Higheractivity catalystscostmorebutincreasesrunlengthsand/oryields

17

SpecificCatalyticReformingProcesses
Hydroforming
Earlycyclicprocessusedtoproducetoluenefor
TNTduringWorldWarII
Molybdenumoxideonaluminacatalyst
Rapidcokingofthecatalyst,requiringacyclic
regenerationofreactorsabouteveryfourhours
Timingmechanismusedforlawnsprinklersystems
usedtoswitchfromreformingtoregeneration
service
Reactorsystemincludedoneextra"swing"reactor
o

Facilitateperiodicremoval&regenerationof
areactor

UOPSemiRegenerativePlatforming
Lowplatinum
Regenerationonceayear
Madenaphthaoctaneimprovementaccessibleto
allrefiners

UOPContinuousRegenerationofReforming
Catalyst
Movingbedprocess
Continuouslyregeneratingaportionofamoving
bedofcatalysttoremovecoke&sustainactivity
Operatingpressuresloweredto50psig

Threereactorsstackedoneontopoftheother
Gravityflowofthecatalystfromtoptobottom
Reactantspassradiallythroughthecatalysttothe
innerconduitandthentothenextbed
Modeofregenerationisproprietary probably
employsairoroxygenburningofthecoke
followedbyreduction&acidification

18

UOPPlatforming

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

19

UOPsCCRPlatformingTM Process

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

20

ReformerInstalledCost
Includes
ISBLfacilitiestoproduce102RON
reformatefromsulfurfreeHSRnaphtha
Productdebutanizer
Allnecessarycontrollers&
instrumentation
AllISBLfacilities
Heatexchangetoacceptfeed&release
productsatambienttemperature

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

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
21

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

22

C4&C5/C6Isomerization
C4isomerization
ConvertnC4 toiC4
iC4 moredesirableasalkylationfeedstock

C5/C6Isomerization
Improvetheoctaneratingofstraightrungasoline
Nparaffinsisomerizedtobranchedisoparaffins
WillalsoconvertanynC4 toiC4

HighRVP(about17psi) limitsitsuseingasolinepool

23

U.S.RefineryImplementation
Top 10 iC5/iC6 Isomerization Capacities

EIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/
24

CharacteristicsofPetroleumProducts

Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize

25

HistoryofIsomerization
AviationgasolineforWorldWarII
Butaneisomerizationwasdevelopedtocreatetheneededisobutanefeedstock
Aluminumchloridecatalyst
Manyoftheseunitswereshutdownafterthewar

TetraEthylLeadPhaseOutin1970s
StraightRunGasoline(SRG)reliedonTELforoctaneimprovement
ResearchOctaneNumber(RON)ofonly70
SRGmostlyparaffinicpentanes&hexaneswithsomeheptanesandoctanes

Isomerizationcouldprovideneededoctaneboost
EquivalentIsoparaffinshavehigherRON

26

C5/C6IsomerizationProcesses
Vaporphaseprocess
Hydrogenusedtosuppress
dehydrogenation&coking
Highyields&highselectivitytohigh
octaneisomericforms
Providesmoderate(butimportant)
contributiontothegasolinepool

Catalysttypes
Chloridealuminacatalyst
Organicchloridedepositedonactive
metalsites
o

Pros
Reformingconditionsnotappropriatefor
theparaffiniccomponentsinSRG
Essentiallyzerobenzene,aromatics,&
olefins
Verylowsulfurlevels

Cons
Highvaporpressure
Moderateoctanelevels (R+M)/2only85

Hightemperaturetreatmentwith
carbontetrachloride

Chloridessensitivetomoisture dryingof
feed&hydrogenmakeupessential

Acidiczeolitewithnoblemetalcatalyst
Platinumcatalyst
Doesnotrequireactivationbyhydrogen
chloride

27

C5/C6Isomerization Feedstocks &Products

Lightestnaphthafeedstock(SRG)with
pentanes,hexanes,&smallamountsof
heptanes
Feedoftendebutanized
Debutanized StraightRun

Sulfur&nitrogenmustberemoved

Products
Isoparaffins &cycloparaffins
Smallamountsoflightgassesfrom
hydrocracking
Unconvertedfeedstock

sincecatalystsemployanacidsitefor
activity

Increasedseverityincreasesoctanebut

Merox

Yieldsdependonfeedstock

Claytreating
Hydrotreating

CommonforStraightRunGasoline&
Naphthatobehydrotreated asone
stream&thenseparated

alsoincreasesyieldoflightends
characteristics&productoctane
Poorqualityfeedsmightyield85%or
lessliquidproduct
Goodfeedsmightyield97%liquid
product

28

IsomerizationChemistry
Primaryreactionistoconvertnormalparaffinstoisomericparaffins
Olefinsmayisomerizeandshiftthepositionofthedoublebond
1butenecoluldshifttoamixtureofcis2butene&trans2butene

Cycloparaffins(naphthenes)mayisomerize&breaktheringforminganolefin
Cyclobutanetobutene

29

EffectsofProcessVariables
Lowtemperature,moderatehydrogenpartialpressure,lowspace
velocitypromotelongrunlengths

Isomerizationyieldscontrolledbychemicalequilibrium
Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&
increasethefinalproductoctane

Temperatureprimaryprocesscontrolvariable
Highertemperaturesincreaseprocessingseverity(includinghydrocracking)

Otherprocessvariables
Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocracking
reactions
Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongs
catalystlife
Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields

30

ProcessImprovements
Numberofcombinationsoffractionationandisomerization
RemovingisopentanefromfeedincreasestheproductsRONto84
Additionofadepentanizeronproductstreamrecycleofnpentanerecycleincreases
productsRONto86
SeparationusingmolecularsievesincreasestheproductsRONto89
UOPcombinesPenexwithMolex
Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation

TotalrecyclewithadeisohexanizerincreasestheproductsRONto89
Suitableforblendingintopremiumatnooctanepenalty

31

IsomerizationOptions

GTCTechnologysIsomalk2process

UOPsParIsom process

Optimizedforhighconversionratewithclose

Nonchloridedaluminacatalyst regenerable &

approachtothermalequilibrium

Produceupto93RONwithfullrecycle
Operates120oC 180oC(250oF 350oF)
Over98%massyield

toleranttosulfur&water

Typicalproductoctanes81 87dependingonflow
configuration&feedstockqualities

Typically97wt%yieldoffreshfeed
2011RefiningProcessesHandbook
HydrocarbonProcessing,2011
32

Isomerization InstalledCost
Includes
Dryingoffeed&hydrogenmakeup
Completepreheat,reaction,&H2
circulationfacilities
Productstabilization
Heatexchangetocoolproductsto
ambienttemperature
Allnecessarycontrollers&
instrumentation
Paidroyalty

Excludes
Hydrogensource
Feeddesulfurization
Coolingwater,steam&powersupply
Feed&productstorage
Initialcatalystcharge
PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
33

Gases
Polymerization

Sulfur
Plant

Gas

Butanes
Alkyl
Feed
Gas
Separation &
Stabilizer

Fuel Gas
LPG

Alkylation

Polymerization
Naphtha

Isomerization

Light Naphtha

Alkylate

Isomerate

Aviation
Gasoline
Automotive
Gasoline

Reformate
Naphtha
Hydrotreating

Heavy
Naphtha

Sulfur

LPG

Sat Gas
Plant

Naphtha
Reforming

Solvents

Naphtha

Atmospheric
Distillation

Crude
Oil

Jet Fuels

Kerosene

Kerosene

Desalter

Distillate

Hydrocracking

AGO

LVGO
Vacuum
Distillation

Gas Oil
Hydrotreating

Fluidized
Catalytic
Cracking

Cat
Naphtha

Solvents
Distillate
Hydrotreating

Cat
Distillates

Treating &
Blending

Heating Oils
Diesel

Fuel Oil

HVGO

Cycle Oils

Residual
Fuel Oils

DAO
Solvent
Deasphalting

Visbreaking

Vacuum
Residuum

Coker
Naphtha

Heavy
Coker
Gas
Oil

SDA
Bottoms

Asphalts

Naphtha

Distillates
Fuel Oil
Bottoms
Lube Oil

Lubricant
Greases

Solvent
Dewaxing

Waxes
Waxes
Coking

Light Coker
Gas Oil

Coke

34

Alkylation&Polymerization
Processestomakegasolinecomponentsfrommaterialsthataretoolightto
otherwisebeingasoline

Alkylation
Formalongerchainhighlybranchedisoparaffinbyreactinganalkylgroup(almost
exclusivelyisobutane)withalightolefin(predominatelybutylene)
Produceshighoctanegasoline

Polymerization
Formationofveryshortchains
Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctane
number

35

U.S.RefineryImplementation
Top 10 Alkylation Capacities

EIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/
36

CharacteristicsofPetroleumProducts

Alkylation:combinesmallmoleculesforgasolinewithgoodproperties

37

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

Inlate1930s&early1940s,alkylationofolefinswasdevelopedtoimprovetheoctaneofaviation
gasoline
VladimirIpatieffhaddiscoveredaluminumchloridecatalysisin1932

FCCsignificantlyincreasedtheproductionoflightends
HighconcentrationoftheC3,C4,&C5isomers,botholefinic &paraffinic
Ledtodevelopmentofbothcatalyticpolymerization&alkylation

FollowingendoftheKoreanconflict(1953)refinersinvestigateduseoftheircatalyticpolymerization
andalkylationcapacityforproductionofhigheroctanemotorfuels
Chicken&egg increasingoctaneproductioncapacity&higherperformanceenginesinautomobilesledto
theoctaneraceinmid1950s

Bothpolymerization&alkylationwereadapted alkylationbecamethedominantprocess
Bythe1960s,polymerizationunitswerebeingphasedout&newplantsutilizedalkylationtechnology

38

SulfuricAcidvs.HFAlkylation
SulfuricAcidAlkylation

HFAcidAlkylation

Developedbyconsortiumofmajorrefiners&

DevelopedbyPhillipsPetroleum&UOP

contractors
AngloIranianOil,HumbleOil&Refining,Shell
Development,StandardOilDevelopment,&the
TexasCompany

HFcouldbereadilyregeneratedinalkylation
plantfacilities
Noneedtotransportcatalystinlarge
quantitiesforregeneration

FirstunitatHumbleBaytownRefinery,1938
Manyalkylationplantswerebuiltatthesametime
asthecatalyticcrackingunits
OperatedduringWorldWarIIforaviation
gasolineproduction

Sulfuricacidalkylationrequiredaccesstoacid
regenerationonalargescale
Mostlocatedondeepwaterforbargetransport
ofspentacidtoregenerationatacidplants&
returnoffreshacid
EconomichandicapforinlandMidwestern
refineries

39

Feedstocks &Products
Olefinic streamfromthecatalytic

Alkylatedesirablecomponentforhigh

cracker

performanceautomotivefuels

Butyleneisthepreferredolefinsince
itproducesthehighestoctane
number&yields

Veryhighoctaneindex(R+M)/2of95

isobutane &isopentane canbe

reactedwiththeolefin
Isopentane notusuallyusedsinceitis
agoodgasolineblendstock

Highoctanenumber&lowvapor
pressure

Catalyticcrackerfeedcontains

Lowvaporpressure
Vaporpressureisadjustedforfinal
boilingpoint
IBPadjustedforadditionofnormal
butane

Lowsulfurlevels
Essentiallynoolefins,benzeneor
aromatics

significantsulfur
Treatingunitoftenprecedes
alkylationunit

40

C4Isomerization
UOPsButamerTM processisahighefficiency,
costeffectivemeanstomeetisobutane
demandsbyisomerizingnC4toiC4

Equilibriumlimited
LowtemperaturefavorsiC4
Highactivitychloridedaluminacatalystsused

HighselectivitytoiC4byseparating&
recyclingnC4toextinction
Oncethroughlowercapitalcost

OnceThroughNButaneConversion

NButaneRecycledtoExtinction
41

AlkylationProcessChemistry
Acidcatalyzedalkylationcombinesisoparaffins &olefinstoformalkylate,highly
branchedalkanes
Usuallyonlyisobutane isused
Isopentane canbeagoodgasolineblendstockforwintergasoline

FriedelCraftsreaction Lewisacid(HForH2S04)promotescarbonium ionona

tertiaryisoparaffin thatrapidlyreactswithanydoublebonditencounters
(propylene,butylenes,orpentylenes)

Thereactioncarriedoutintheliquidphasewithanacid/reactantemulsion
maintainedatmoderatetemperatures

Propylene,butylene,&pentenes areolefinsused butylenepreferred

Highoctaneisooctanealkylateproduced
Lowerreactantconsumption

Alkylationreactionshavecomplexmechanisms&mayproducemanydifferent
varieties

42

ProcessChemistryExamples
Isobutylene&isobutaneform2,2,4trimethylpentane(isooctane)
H3C

H3 C
C

CH2

H3C

CH3

+
CH3

H3 C

CH3

H3C

H3 C

CH3

CH
CH3

CH3
H3C

CH3
CH2

CH

CH3

CH3

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

43

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

Feedstocks
OlefinFeed

Isoparaffin Feed

Butylenepreferred

Excessisobutane required typical

Producesthehighestisooctanelevels
ResultingResearchOctaneNumbersof
9395(withisobutane)
RONandMONareaboutequalfor
alkylation

Amountsofbutyleneconsumedper
alkylateproducedisthelowest
Sidereactionsarelimited

Propyleneworse
Octanenumbersarelow(8992RON)
Propylene&acidconsumptionarehigh

Penteneresultsaremixed

volumeratioofisobutane:olefin inthe
feedis610
Limitedisobutane solubilityinacid
phase
Olefinsneedtobesurroundedby
isobutane exposedtoacid ifnot,
olefinswillpolymerizeinsteadof
alkylate

Newerplantshavemultiinjection&
vigorousmixingsystems
Effectofisobutane isexpressedinterms
ofconcentrationinthereactionzone
Isobutane:olefin ratiosmaintainedat
10,000to1

Sidereactionsfrequent
45

Isobutane/OlefinInjection&Mixing
Moreimportantinsulfuricacidsystems
Acidviscosityatoperatingtemperatures

Provideoptimalreactionconditionsfortheveryfastreaction
Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios
Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsionto
disperseolefinasrapidlyaspossible

Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefininthe
emulsion
Leadstolowerquality&higheracidconsumptionfromesterificationreactions

46

ProcessConsiderations
SulfuricAcid
HFAcid
Increasingtemperaturereducesoctanenumber
Reaction
SulfuricAcidsystemsrunat45Fchilled HFsystemsrunat95Fcoolingwater
Temperature water,refrigeration,orautorefrigeration sufficient
required
Considered"spent"about88%sulfuricacid Keepintherangeof80%to95%
AcidStrength

Waterlowersacidactivity3to5timesas
fastashydrocarbondiluents
Acidregenerationonalargescalemost
locatedondeepwaterforbargetransport
Regeneration
ofspentacidtoregenerationatacidplants
&returnoffreshacid
Other
Dominantprocessbutrequiresextensive
Consideration recuperationofthespentacid

HFreadilyregeneratedonsitenoneed
totransportcatalystinlargequantitiesfor
regenerationotherthansmallacidmakeup
Smallerbuturbancommunityconcernsto
hazardsofHFescape1.

1UnitedSteelworkersUnionCallsforIndustrywidePhaseoutofHydrogenFluorideinOilRefineryAlkylationUnits

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

47

Autorefrigerated ReactorSulfuricAcidAlkylation(EMRE)

SulfuricAcidAlkylationTechnology
Dr.Girish K.Chitnis,Mr.RonD.McGihon,Mr.Aneesh PrasadandMr.ChristopherM.Dean
GrowingImportanceofAlkylationSeptember2009
http://www.exxonmobil.com/Apps/RefiningTechnologies/Files/Conference_2009_sulfuricalkylation_Sept.pdf
48

STRATCOContactorTM Reactor
SulfuricAcidAlkylation(DuPont)

STRATCOAlkylationTechnologyImprovements
KevinBockwinkel
2007NPRAAnnualMeeting
http://www2.dupont.com/Sustainable_Solutions/en_US/assets/downloads/stratco/STRATCO_AlkylationTechnologyImprovements.pdf

49

HFAlkylationSystem
Differencestosulfuricacidsystems
Feeddriersessentialtominimizecatalystconsumption
WaterformsanazeotropewithHFleadingtoacidloss

HFstripperrequiredondepropanizeroverheadtocleanuppropaneforLPG
HFregeneratoroperatingonaslipstreamfromacidsettler
Manyacidsolubleorganiccompoundsdecomposebutsomemustberejectedasacidsolubleoil

Spentacidrequiresspecialneutralization
ConvertHFtocalciumfluoride&burnablewaste
Overallacidlossshouldbelessthanonepoundperbarrelofacidproduced

ElaborateHFventing,neutralization&recoverysystem
ConsideredbythepublictobeathreatintermsoflargereleasesofHF
NewdesignsminimizetheinventoryofHFintheunitfarbelowearlierdesigns
Riskisminimized,noteliminated

50

UOP/PhillipsAlkylationProcess

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

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007

51

PhillipsAlkylationProcess
Component

Olefin Feed

Saturated
Butanes

Propane Yield

Motor-Fuel

Motor-Fuel

Butane Yield

Alylate Yield

3.13

0.19

Ethane

0.49

Propylene

21.04

Propane

17.42

0.30

18.77

Isobutane

191.81

13.48

0.34

Butenes

169.10

n-Butane

63.17

10.11

63.35

9.93

Pentanes

4.90

0.42

3.67

1.65

0.49

Alkylate

390.17

Acid Oils
Total
Stream Totals

Acid Oils

0.55
467.93

24.31

19.60

70.15

401.94

492.24

0.55
492.24

RVP [psi]

6.0

Specific Gravity

0.70

RON, clear

95.0

MON, clear
FBP [C]

93.5

FBP [F]

383

195

52

AlkylationInstalledCost
Includes
Facilitiestoproducealkylate fromfeed
withiC4&C3toC5olefins
Allnecessarycontrollers&
instrumentation
AllISBLfacilities
Feedtreating(molecularsievetoremove
moisturefromfeed)

Excludes
Coolingwater,steam&powersupply
Feed&productstorage

PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007

53

GasolineUpgradingProcessComparisons
Pros
Reforming
Highoctane

Cons
Reforming
Higharomatics(benzene)

LowRVP
Byproducthydrogen

Isomerization

Isomerization

BetteroctanethanLSR

Octanestillrelativelylow

Toolightforreforming

HighRVP

Lowaromatics&olefins
Verylowsulfurlevels

Alkylation
Goodoctane
LowRVP

Alkylation
Requireslightends issueifno
FCCU
HFcommunityconcerns

54

SupplementalSlides
Phillips66capacities
Technologyproviders
Effectsofreformingprocessvariables
Otherisomerizationblockflowdiagrams
Othersulfuricacidalkylationblockflowdiagrams

55

Phillips66Statistics

U.S.informationfromEIA,Jan.1,2014database,publishedJune2014
http://www.eia.gov/petroleum/refinerycapacity/

56

CatalyticReformingTechnologies

Provider
Axens(1)
Axens(2)
UOP

Features
Catalystregeneratedinplaceatendofcycle.Operatesin
pressurerangeof170350psig.
AdvancedOctanizingprocess,usescontinuouscatalyst
regenerationallowingpressuresaslowas50psig.
CCRPlatformingprocess.Radialflowreactorsarrangedin
verticalstack.

57

IsomerizationTechnologies

Provider

UOP(1)

Features
EitheroncethroughorIpsorbIsomwithnormal
paraffinrecycletoextinction.
ISOMPLUSzeolitebasedcatalyst.
ParIsomprocessuseshighperformancenonchlorided
aluminacatalysts

UOP(2)

HOT(hydrogenoncethrough)Penexprocess
eliminatesneedofrecyclegascompressor.Fixedbed
usinghighactivitychloridepromotedcatalyst.

UOP(3)

HOT(hydrogenoncethrough)Butamerprocess
eliminatesneedofrecyclegascompressor.Twoseries
reactorsprovidehighonstreamefficiency.

Axens
CDTECH

58

AlkylationTechnologies
Provider
CDTECH(1)
CDTECH(2)
DuPont
LummusTechnology
RefiningHydrocarbon
TechnologiesLLC
ExxonMobilResearch&
Engineering
UOP(1)

UOP(2)

Features
CDAlkyllowtemperaturesulfuricacidalkylation.
CDAlkylPluslowtemperaturesulfuricacidalkylation
coupledwitholefinpretreatmentstep.
UsesSTRATCOEffluentRefrigerationAlkylationprocess
usingsulfuricacid
AlkylCleanprocessusingsolidacidcatalyst.
Demonstrationunitonly.
RHTAlkylationprocessusessulfuricacid.Eductormixing
device.
Sulfuricacidalkylationusingautorefrigeratedreactor.
ModifiedHFAlkylationtoreduceaerosolformation.
IndirectAlkylation(InAlk)usessolidcatalyst.Olefins
polymerize&highermolecularweightmaterial
hydrogenated.

59

EffectsofReformingProcessVariables
Reaction

Pressure

Temperature

Isomerizationofnaphthenes

Indeterminate

Indeterminate

Dehydrocyclizationofparaffins
tonaphthenes

Lowpressure

Hightemperature

Dehydrogenationof
naphthenestoaromatics

Lowpressure

Hightemperature

Isomerizationofnormal
paraffinstoisoparaffins

Slight
dependence

Slightdependence

Hydrocracking

Highpressure

Hightemperature

60

IsomerizationWith&WithoutiC5Removal

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

61

IsomerizationOptions

UOPPenexTM HydrocarbonOnceThrough
Limitedbyequilibrium 8084RONC

Isomerization/DIH Recyclesunconvertedlowoctaneisomers
8789RONC

DIP/Isomerization/SuperDIH
9093RONC
http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization
62

SulfuricAcidAlkylation

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

63

TimeTankReactors

RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000

64