09 Gasoline Upgrading

GasolineUpgrading:CatalyticReforming,Isomerization,&Alkylation
Chapters10&11
JohnJechura jjechura@mines.edu
Updated:August13,2015
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
GasolineFractionsNeedImprovement
GasolineUpgrading
Purpose
Increasethequalityoffeedstocksofthe
sameboilingrangeasgasoline
Products
Gasolineblendstocksofimprovedoctane
and/orvolatility
Characteristics
CatalyticReforming
Convertsnaphthenes toaromatics
Produceshydrogen
Isomerization
Rearrangesstraightchainsto
branchedisomers
Verylittlechangeinboiling
points
Alkylation
Useolefinsproducedinother
processes(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
EIA,Jan.1,2015database,publishedJune2015
http://www.eia.gov/petroleum/refinerycapacity/
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
14
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
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
21
C4&C5/C6Isomerization
C4isomerization
ConvertnC4 toiC4
iC4 moredesirableasalkylationfeedstock
C5/C6Isomerization
Improvetheoctaneratingofstraightrungasoline
Nparaffinsisomerizedtobranchedisoparaffins
WillalsoconvertanynC4 toiC4
HighRVP(about17psi) limitsitsuseingasolinepool
22
23
Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize
24
HistoryofIsomerization
AviationgasolineforWorldWarII
Butaneisomerizationwasdevelopedtocreatetheneededisobutanefeedstock
Aluminumchloridecatalyst
Manyoftheseunitswereshutdownafterthewar
TetraEthylLeadPhaseOutin1970s
StraightRunGasoline(SRG)reliedonTELforoctaneimprovement
ResearchOctaneNumber(RON)ofonly70
SRGmostlyparaffinicpentanes&hexaneswithsomeheptanesandoctanes
Isomerizationcouldprovideneededoctaneboost
EquivalentIsoparaffinshavehigherRON
25
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
26
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
27
IsomerizationChemistry
Primaryreactionistoconvertnormalparaffinstoisomericparaffins
Olefinsmayisomerizeandshiftthepositionofthedoublebond
1butenecoluldshifttoamixtureofcis2butene&trans2butene
Cycloparaffins(naphthenes)mayisomerize&breaktheringforminganolefin
Cyclobutanetobutene
28
EffectsofProcessVariables
Lowtemperature,moderatehydrogenpartialpressure,lowspace
velocitypromotelongrunlengths
Isomerizationyieldscontrolledbychemicalequilibrium
Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&
increasethefinalproductoctane
Temperatureprimaryprocesscontrolvariable
Highertemperaturesincreaseprocessingseverity(includinghydrocracking)
Otherprocessvariables
Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocracking
reactions
Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongs
catalystlife
Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields
29
ProcessImprovements
Numberofcombinationsoffractionationandisomerization
RemovingisopentanefromfeedincreasestheproductsRONto84
Additionofadepentanizeronproductstreamrecycleofnpentanerecycleincreases
productsRONto86
SeparationusingmolecularsievesincreasestheproductsRONto89
UOPcombinesPenexwithMolex
Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation
TotalrecyclewithadeisohexanizerincreasestheproductsRONto89
Suitableforblendingintopremiumatnooctanepenalty
30
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
31
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
32
Alkylation&Polymerization
Processestomakegasolinecomponentsfrommaterialsthataretoolightto
otherwisebeingasoline
Alkylation
Formalongerchainhighlybranchedisoparaffinbyreactinganalkylgroup(almost
exclusivelyisobutane)withalightolefin(predominatelybutylene)
Produceshighoctanegasoline
Polymerization
Formationofveryshortchains
Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctane
number
33
34
Alkylation:combinesmallmoleculesforgasolinewithgoodproperties
35
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
36
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
37
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
38
C4Isomerization
UOPsButamerTM processisahighefficiency,
costeffectivemeanstomeetisobutane
demandsbyisomerizingnC4toiC4
Equilibriumlimited
LowtemperaturefavorsiC4
Highactivitychloridedaluminacatalystsused
HighselectivitytoiC4byseparating&
recyclingnC4toextinction
Oncethroughlowercapitalcost
OnceThroughNButaneConversion
NButaneRecycledtoExtinction
39
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
40
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
41
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
42
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
43
Isobutane/OlefinInjection&Mixing
Moreimportantinsulfuricacidsystems
Acidviscosityatoperatingtemperatures
Provideoptimalreactionconditionsfortheveryfastreaction
Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios
Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsionto
disperseolefinasrapidlyaspossible
Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefininthe
emulsion
Leadstolowerquality&higheracidconsumptionfromesterificationreactions
44
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
45
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
46
STRATCOContactorTM Reactor
SulfuricAcidAlkylation(DuPont)
STRATCOAlkylationTechnologyImprovements
KevinBockwinkel
2007NPRAAnnualMeeting
http://www2.dupont.com/Sustainable_Solutions/en_US/assets/downloads/stratco/STRATCO_AlkylationTechnologyImprovements.pdf
47
HFAlkylationSystem
Differencestosulfuricacidsystems
Feeddriersessentialtominimizecatalystconsumption
WaterformsanazeotropewithHFleadingtoacidloss
HFstripperrequiredondepropanizeroverheadtocleanuppropaneforLPG
HFregeneratoroperatingonaslipstreamfromacidsettler
Manyacidsolubleorganiccompoundsdecomposebutsomemustberejectedasacidsolubleoil
Spentacidrequiresspecialneutralization
ConvertHFtocalciumfluoride&burnablewaste
Overallacidlossshouldbelessthanonepoundperbarrelofacidproduced
ElaborateHFventing,neutralization&recoverysystem
ConsideredbythepublictobeathreatintermsoflargereleasesofHF
NewdesignsminimizetheinventoryofHFintheunitfarbelowearlierdesigns
Riskisminimized,noteliminated
48
UOP/PhillipsAlkylationProcess
http://www.uop.com/processingsolutions/refining/gasoline/#alkylation
PetroleumRefiningTechnology&Economics,5th ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
49
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
Acid Oils
0.55
467.93
Stream Totals
24.31
19.60
70.15
401.94
492.24
492.24
RVP [psi]
6.0
Specific Gravity
0.70
RON, clear
95.0
MON, clear
FBP [C]
93.5
FBP [F]
383
0.55
195
50
GasolineUpgradingProcessComparisons
Pros
Cons
Reforming
Highoctane
LowRVP
Byproducthydrogen
Higharomatics(benzene)
Isomerization
BetteroctanethanLSR
Toolightforreforming
Lowaromatics&olefins
Verylowsulfurlevels
Octanestillrelativelylow
HighRVP
Alkylation
Goodoctane
LowRVP
Requireslightends issueifno
FCCU
HFcommunityconcerns
51
SupplementalSlides
Installedcosts
Technologyproviders
Effectsofreformingprocessvariables
Otherisomerizationblockflowdiagrams
Othersulfuricacidalkylationblockflowdiagrams
52
ReformerInstalledCost
Includes
ISBLfacilitiestoproduce102RON
reformatefromsulfurfreeHSRnaphtha
Productdebutanizer
Allnecessarycontrollers&
instrumentation
AllISBLfacilities
Heatexchangetoacceptfeed&release
productsatambienttemperature
Excludes
Coolingwater,steam&powersupply
Feed&productstorage
Initialcatalystcharge
Royalty
Feedfractionationordesulfurization
CRCPress,2007
53
Isomerization InstalledCost
Includes
Dryingoffeed&hydrogenmakeup
Completepreheat,reaction,&H2
circulationfacilities
Productstabilization
Heatexchangetocoolproductsto
ambienttemperature
instrumentation
Paidroyalty
Excludes
Hydrogensource
Feeddesulfurization
Feed&productstorage
Initialcatalystcharge
CRCPress,2007
54
AlkylationInstalledCost
Includes
Facilitiestoproducealkylate fromfeed
withiC4&C3toC5olefins
instrumentation
AllISBLfacilities
Feedtreating(molecularsievetoremove
moisturefromfeed)
Excludes
Feed&productstorage
CRCPress,2007
55
CatalyticReformingTechnologies
Provider
Axens(1)
Axens(2)
UOP
Features
Catalystregeneratedinplaceatendofcycle.Operatesin
pressurerangeof170350psig.
AdvancedOctanizingprocess,usescontinuouscatalyst
regenerationallowingpressuresaslowas50psig.
CCRPlatformingprocess.Radialflowreactorsarrangedin
verticalstack.
56
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
57
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.
58
EffectsofReformingProcessVariables
Reaction
Pressure
Temperature
Isomerizationofnaphthenes
Indeterminate
Indeterminate
Dehydrocyclization ofparaffins tonaphthenes
Lowpressure
Hightemperature
Dehydrogenationofnaphthenes toaromatics
Lowpressure
Hightemperature
Isomerizationofnormalparaffins toisoparaffins
Slightdependence
Slightdependence
Hydrocracking
Highpressure
Hightemperature
59
IsomerizationWith&WithoutiC5Removal
60
IsomerizationOptions
UOPPenexTM HydrocarbonOnceThrough
Limitedbyequilibrium 8084RONC
Isomerization/DIH Recyclesunconvertedlowoctaneisomers
8789RONC
DIP/Isomerization/SuperDIH
9093RONC
http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization
61
SulfuricAcidAlkylation
62
TimeTankReactors
63

09 Gasoline Upgrading

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09 Gasoline Upgrading

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GasolineUpgrading:CatalyticReforming,Isomerization,&Alkylation

C5/C6Isomerization Feedstocks &Products

Nonchloridedaluminacatalyst regenerable &

isobutane &isopentane canbe

FriedelCraftsreaction Lewisacid(HForH2S04)promotescarbonium ionona

Propylene,butylene,&pentenes areolefinsused butylenepreferred

Isobutane concentration isobutane:olefin ratio

Excessisobutane required typical

Dehydrocyclization ofparaffins tonaphthenes

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