GasolineUpgrading:CatalyticReforming,

Isomerization,&Alkylation
Chapters10&11
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
2
PurposeofGasolineFinishingProcesses
Feedstockssameboilingrangeas
gasolineorslightlylower
Startwithlowoctanegasoline
blendstocks
CatalyticReforming
Convertsnaphthenes to
aromatics
Produceshydrogen
Isomerization
Rearrangesstraightchainsto
branchedisomers
Verylittlechangeinboilingpoints
Increasemolecularsize
Alkylation
Useolefinsproducedinother
processes(primarilyFCCU)
3
DependencyofOctaneonChemicalStructure
RON MON RON MON
Paraffins Naphthenes
nbutane 94 89.6 cyclopentane 100 84.9
isobutane 102 97.6 cyclohexane 82.5 77.2
npentane 62 62.6 mcyclopentane 91.3 80
ipentane 92 90.3 C7naphthenes 82 77
nhexane 24.8 26 C8naphthenes 55 50
C6monomethyls 76 73.9 C9naphthenes 35 30
2,2dimethylbutane 91.8 93.4
2,3dimethylbutane 105.8 94.3 Aromatics
nheptane 0 0 benzene 102.7 105
C7monomethyls 52 52 toluene 118 103.5
C7dimethyls 93.76 90 C8aromatics 112 105
2,2,3trimethylbutane 112.8 101.32 C9aromatics 110 101
noctane 15 20 C10aromatics 109 98
C8monomethyls 25 32.3 C11aromatics 105 94
C8dimethyls 69 74.5 C12aromatics 102 90
C8trimethyls 105 98.8
nnonane 20 20 Olefins/CyclicOlefins
C9monomethyls 15 22.3 nbutenes 98.7 82.1
C9dimethyls 50 60 npentenes 90 77.2
C9trimethyls 100 93 ipentenes 103 82
ndecane 30 30 cyclopentene 93.3 69.7
C10monomethyls 10 10 nhexenes 90 80
C10dimethyls 40 40 ihexenes 100 83
C10trimethyls 95 87 TotalC6cyclicolefins 95 80
nundecane 35 35 totalC7d 90 78
C11monomethyl 5 5 totalC8d 90 77
C11dimethyls 35 35
C11trimethyls 90 82 Oxygenates
ndodecane 40 40 MTBE 115.2 97.2
C12monomethyl 5 5 TAME 115 98
C12dimethyls 30 30 EtOH 108 92.9
C12trimethyls 85 80
4
DevelopmentofaDetailedGasolineCompositionBasedOctaneModel
PrasenjeetGhosh,KarltonJ.Hickey,andStephenB.Jaffe
Ind.Eng.Chem.Res. 2006,45,337345
60
40
20
0
20
40
60
80
100
120
140
0 50 100 150 200 250 300 350 400 450 500
BoilingPoint[F]
R
e
s
e
a
r
c
h

O
c
t
a
n
e

N
u
m
b
e
r
Aromatics
Naphthenes
Olefins&CyclicOlefins
Isoparaffins
NormalParaffins
U.S.RefineryImplementation
5
Top 20 Atmospheric Distillation Capacity
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
6
NaphthaReforming
Almosteveryrefineryintheworldhasareformer
Purposetoenhancearomaticcontentofnaphtha
Feedstockstoaromaticscomplex
Improvetheoctaneratingforgasoline
Manydifferentcommercialcatalyticreformingprocesses
Hydroforming
Platforming
Powerforming
Ultraforming
Thermoforcatalyticreforming
Primaryreactions
Dehydrogenation naphthenesaromacs
Isomerization normalparansbranchedisoparans
Hydrogenasbyproduct
Ultimatelyusedinhydrotreating
Catalyticreforming2ndtoFCCincommercialimportancetorefiners
Reformatedesirablecomponentforgasoline
Highoctanenumber,lowvaporpressure,verylowsulfurlevels,&lowolefinsconcentration
USregulationsonlevelsofbenzene,aromatics,&olefins
Airqualityconcerns
7
CharacteristicsofPetroleumProducts
8
Reforming:driveoffhydrogenforbettergasolinepropertiesw/ochangingsize
CatalyticReformingTechnologies
9
Provider Features
Axens(1)
Catalystregeneratedinplaceatendofcycle.Operatesin
pressurerangeof170350psig.
Axens(2)
AdvancedOctanizingprocess,usescontinuouscatalyst
regenerationallowingpressuresaslowas50psig.
UOP
CCRPlatformingprocess.Radialflowreactorsarrangedin
verticalstack.
Feedstocks&Products
Hydrotreatedheavynaphthafeedstock
Lightstraightrunnaphthatendstocracktobutanes&lighter
Gasoilstreamstendtohydrocrack&depositcokeonthereforming
catalyst
Catalystisnoblemetal(e.g.platinum) verysensitivetosulfur&
nitrogen
Feedstockshydrotreatedforsulfur&nitrogenremoval
Controlofchloride&wateralsoimportant
Severity
Highseverityusedtomaximizearomatics
SenttoBTXseparationforaromaticfeedstocks
Lowseverityusedforgasolineblendstocks
Producesthemajorityofthehydrogenusedforhydrotreating
10
ReformingChemistry
Usesasolidcatalysttoconvertnaphthenestothecorrespondingaromatics&
isomerizeparaffinicstructurestoisomericforms
Bothreactionsleadtoamarkedincreaseinoctanenumber
Bothreactionsleadtovolumeshrinkage
CorrelationspermittheuseofaPONAanalysisofthefeedforpredictionofyield
andqualityoftheproduct
OriginallyfeedqualitiesmeasuredintermsofWatson"K"Factor aroughindicationof
amountofparaffins
Aromaticslargelyuntouchedbyreactions
11
ReformingChemistry
12
CH
3
CH
3
+ 3 H2
Dehydrogenation
+ H2
Dehydrocyclization
CH
3
CH
3
CH
3
CH
3
+ H2
Isomerization
CH
3
CH
3
CH
2
CH
3
CH
3
Hydrocracking
CH
2
CH
3
CH
3
+ H2 +
UseofYieldCharts
Vol% Wt% Density
H2S H2Correction
Hydrogen Fig10.7
C1+C2 Fig10.6
C3 Ratio Fig10.6 Pure
C4s
IC4
Fig10.5
41.5% Ratio Pure
NC4 58.5% Ratio Pure
C5+Gasoline Fig10.4 Ratio
Total 100%
13
Notes:
YaxisofFig10.4isC5+gasolineyield
TypicallyusetheWatsonKFactoroffeedinFig10.4.
ReformerYieldExample
14
Example
Sul fur Waterdensi ty@60F= 8.33718 l b/gal
FeedInformation: AveBPT Speci fi c API Watson Content 350.162 l b/bbl
F Gravi ty Gravi ty KFactor wt% H2Mol Wt= 2.02
297.4 0.7724 51.7 11.80 0.100 Sul furMol Wt= 32.064
scfpermol = 379.5
TargetRON: 99.0
ProductDistribution:
Fraction bbl/day lb/hr lb/day vol% wt% API SpGr lb/bbl mol/hr scf/hr mol/day
Feed 40,000 450,763 10,818,310 51.7 0.7724 270.5
H2S 479 11,500 14 5,335 337
H2 15,228 365,477 7,539 2,860,840 180,929
C1+C2 12,153 291,678 2.70
C3 2,154 15,933 382,386 3.53 147.6 0.5070 177.5
Isobutane(IC4) 1,148 9,425 226,206 2.87 119.9 0.5629 197.1
nbutane(NC4) 1,618 13,784 330,821 4.04 110.8 0.5840 204.5
C5+ 31,831 383,760 9,210,243 79.58 39.7 0.8263 289.4
Total 36,750 450,763 10,818,310
UncorrectedYields
Sul fur 451 10,818 14 337
H2(uncorrected) 15,257 366,158 3.38 7,553 2,866,174 181,266
C4(Total ) 6.91
YieldsonOilFeed StandardDensities
ProductYieldsfromReformer
GasolineYieldvs.ReformateOctane
15
Notes:
YaxisisC5+gasoline
yield
Typicallyusethe
WatsonKFactorof
feedinFig10.4.
LightEndsProduction
16
Notes:
TypicalC4Split:
iC4=41.5%,nC4=58.5%
CombinedProductionTrends
17
Combination Yields from Figures 10.4 to 10.7
0
1
2
3
4
5
6
7
8
9
10
89 90 91 92 93 94 95 96 97 98 99 100 101
Reformate RON Clear
%

L
i
g
h
t

E
n
d
s

Y
i
e
l
d
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
V
o
l
%

G
a
s
o
l
i
n
e

Y
i
e
l
d
Feedstock Watson K Factor is 11.8
Gasoline
Vol% C4s
Wt% C3
Wt% C1+C2
Wt% H2
BoilingPointRangesforProducts
18
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-reformate
77-Ovhd liquids
75-Offgas
1-Sour.naphtha
9,999 bpd Sour Naptha Feed
8,314 bpd Reformate
EffectsofProcessVariables
Primarycontrolforchangingconditionsorqualitiesisreactortemperature
Normallyabout950Fatreactorinlet
Mayberaisedfordecliningcatalystactivityortocompensateforlowerqualityfeedstock
Higherreactortemperatureincreasesoctaneratingbutreducesyieldandrunlength
Designconsiderationsforimprovementinqualitywillincludepressure,recycle
ratio,reactorresidencetime,&catalystactivity
Lowreactorpressure increasesyield&octanebutincreasescokemake
Increasedhydrogenpartialpressure duetohydrogenrecycle(hydrogentohydrocarbon
ratio)suppressescokeformation,hydrogenyield&octanegain,butpromotes
hydrocracking
Lowspacevelocity favorsaromaticsformationbutalsopromotescrackingbyoperating
closertoequilibriumconditions
Higheractivity catalystscostmorebutincreasesrunlengthsand/oryields
19
EffectsofProcessVariables
20
Reaction Pressure Temperature
Isomerizationofnaphthenes Indeterminate Indeterminate
Dehydrocyclizationofparaffins
tonaphthenes
Lowpressure Hightemperature
Dehydrogenationof
naphthenestoaromatics
Lowpressure Hightemperature
Isomerizationofnormal
paraffinstoisoparaffins
Slight
dependence
Slightdependence
Hydrocracking Highpressure Hightemperature
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
21
UOPPlatforming
22
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
UOPsCCRPlatforming
TM
Process
23
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
24
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
25
C4&C5/C6Isomerization
C4isomerization
ConvertnC
4
toiC
4
iC
4
moredesirableasalkylationfeedstock
C5/C6Isomerization
Improvetheoctaneratingofstraightrungasoline
Nparaffinsisomerizedtobranchedisoparaffins
WillalsoconvertanynC
4
toiC
4
HighRVP(about17psi) limitsitsuseingasolinepool
26
CharacteristicsofPetroleumProducts
27
Isomerization:rearrangemoleculesforbettergasolinepropertiesw/ochangingsize
IsomerizationTechnologies
28
Provider Features
Axens
EitheroncethroughorIpsorbIsomwithnormal
paraffinrecycletoextinction.
CDTECH ISOMPLUSzeolitebasedcatalyst.
UOP(1)
ParIsomprocessuseshighperformancenonchlorided
aluminacatalysts
UOP(2)
HOT(hydrogenoncethrough)Penexprocess
eliminatesneedofrecyclegascompressor.Fixedbed
usinghighactivitychloridepromotedcatalyst.
UOP(3)
HOT(hydrogenoncethrough)Butamerprocess
eliminatesneedofrecyclegascompressor.Twoseries
reactorsprovidehighonstreamefficiency.
HistoryofIsomerization
AviationgasolineforWorldWarII
Butaneisomerizationwasdevelopedtocreatetheneededisobutanefeedstock
Aluminumchloridecatalyst
Manyoftheseunitswereshutdownafterthewar
TetraEthylLeadPhaseOutin1970s
StraightRunGasoline(SRG)reliedonTELforoctaneimprovement
ResearchOctaneNumber(RON)ofonly70
SRGmostlyparaffinicpentanes&hexaneswithsomeheptanesandoctanes
Isomerizationcouldprovideneededoctaneboost
EquivalentIsoparaffinshavehigherRON
29
C5/C6IsomerizationProcesses
Vaporphaseprocess
Hydrogenusedtosuppressdehydrogenation&coking
Highyields&highselectivitytohighoctaneisomericforms
Providesmoderate(butimportant)contributiontothegasolinepool
Catalysttypes
Chloridealuminacatalyst
Organicchloridedepositedonactivemetalsites
o Hightemperaturetreatmentwithcarbontetrachloride
Chloridessensitivetomoisture dryingoffeed&hydrogenmakeupessential
Acidiczeolitewithnoblemetalcatalyst
Platinumcatalyst
Doesnotrequireactivationbyhydrogenchloride
30
C5/C6IsomerizationProcesses
Pros
ReformingconditionsnotappropriatefortheparaffiniccomponentsinSRG
Essentiallyzerobenzene,aromatics,&olefins
Verylowsulfurlevels
Cons
Highvaporpressure
Moderateoctanelevels (R+M)/2only85
31
C5/C6Isomerization Feedstocks &Products
Lightestnaphthafeedstock(SRG)with
pentanes,hexanes,&smallamountsof
heptanes
Feedoftendebutanized
Debutanized StraightRun
Sulfur&nitrogenmustberemovedsince
catalystsemployanacidsiteforactivity
Merox
Claytreating
Hydrotreating
CommonforStraightRunGasoline&
Naphthatobehydrotreated asone
stream&thenseparated
Products
Isoparaffins &cycloparaffins
Smallamountsoflightgassesfrom
hydrocracking
Unconvertedfeedstock
Increasedseverityincreasesoctanebut
alsoincreasesyieldoflightends
Yieldsdependonfeedstock
characteristics&productoctane
Poorqualityfeedsmightyield85%or
lessliquidproduct
Goodfeedsmightyield97%liquid
product
32
IsomerizationChemistry
Primaryreactionistoconvertnormalparaffinstoisomericparaffins
Olefinsmayisomerizeandshiftthepositionofthedoublebond
1butenecoluldshifttoamixtureofcis2butene&trans2butene
Cycloparaffins(naphthenes)mayisomerize&breaktheringforminganolefin
Cyclobutanetobutene
33
EffectsofProcessVariables
Lowtemperature,moderatehydrogenpartialpressure,lowspace
velocitypromotelongrunlengths
Isomerizationyieldscontrolledbychemicalequilibrium
Removingisoparaffins fromfeedstockcanshiftthereactorequilibrium&
increasethefinalproductoctane
Temperatureprimaryprocesscontrolvariable
Highertemperaturesincreaseprocessingseverity(includinghydrocracking)
Otherprocessvariables
Higherpressuresincreasecatalystlifebutincreasesundesirablehydrocracking
reactions
Increasedhydrogenpartialpressurepromoteshydrocrackingbutprolongs
catalystlife
Spacevelocitybalancedagainstcapitalcost,temperature,runlength&yields
Contaminantsreducecatalystlife
34
ProcessImprovements
Numberofcombinationsoffractionationandisomerization
RemovingisopentanefromfeedincreasestheproductsRONto84
Additionofadepentanizeronproductstreamrecycleofnpentanerecycleincreases
productsRONto86
SeparationusingmolecularsievesincreasestheproductsRONto89
UOPcombinesPenexwithMolex
Separationcarriedoutentirelyinvaporphase norefluxutilitiesbutcyclicoperation
TotalrecyclewithadeisohexanizerincreasestheproductsRONto89
Suitableforblendingintopremiumatnooctanepenalty
35
IsomerizationOptions
36
http://www.uop.com/processingsolutions/refining/gasoline/#naphthaisomerization
UOPPenex
TM
HydrocarbonOnceThrough
Limitedbyequilibrium 8084RONC
Isomerization/DIH Recyclesunconvertedlowoctaneiosemrs
8789RONC
DIP/Isomeriaztion/SuperDIH
9093RONC
Isomerization InstalledCost
Includes
Dryingoffeed&hydrogenmakeup
Completepreheat,reaction,&H2
circulationfacilities
Productstabilization
Heatexchangetocoolproductsto
ambienttemperature
Allnecessarycontrollers&
instrumentation
Paidroyalty
Excludes
Hydrogensource
Feeddesulfurization
Coolingwater,steam&powersupply
Feed&productstorage
Initialcatalystcharge
37
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
Light Naphtha
Crude
Oil
Desalter
Atmospheric
Distillation
Vacuum
Distillation
Gas
Separation &
Stabilizer
Solvent
Deasphal-
ting
Coking
Visbreaking
Fluidized
Catalytic
Cracking
Hydro-
cracking
Naphtha
Reforming
Isom-
erization
Sat Gas
Plant
Polymer-
ization
Alkylation
Naphtha
Hydro-
treating
Treating &
Blending
Coke
Fuel Gas
LPG
Aviation
Gasoline
Automotive
Gasoline
Solvents
J et Fuels
Kerosene
Solvents
Heating Oils
Diesel
Residual
Fuel Oils
Lubricant
Greases
Waxes
Asphalts
Heavy
Naphtha
Kerosene
Distillate
AGO
LVGO
HVGO
Vacuum
Residuum
Cat
Distillates
Gas Oil
Hydro-
treating
DAO
Isomerate
Gas
Alkyl
Feed
Alkylate
Polymerization
Naphtha
Gases
Butanes
LPG
Reformate
Naphtha
Fuel Oil
Bottoms
Distillates
Distillate
Hydro-
treating
Cat
Naphtha
Cycle Oils
SDA
Bottoms
Coker
Naphtha
Heavy
Coker
Gas
Oil
Light Coker
Gas Oil
Sulfur
Plant
Sulfur
Naphtha
Fuel Oil
Solvent
Dewaxing
Lube Oil
Waxes
38
Alkylation&Polymerization
Processestomakegasolinecomponentsfrommaterialsthataretoolightto
otherwisebeingasoline
Alkylation
Formalongerchainhighlybranchedisoparaffinbyreactinganalkylgroup(almost
exclusivelyisobutane)withalightolefin(predominatelybutylene)
Produceshighoctanegasoline
Polymerization
Formationofveryshortchains
Productisnearlyallolefinic highresearchoctanebutmoderatemotoroctane
number
39
CharacteristicsofPetroleumProducts
40
Alkylation:combinesmallmoleculesforgasolinewithgoodproperties
AlkylationTechnologies
41
Provider Features
CDTECH(1) CDAlkyllowtemperaturesulfuricacidalkylation.
CDTECH(2)
CDAlkylPluslowtemperaturesulfuricacidalkylation
coupledwitholefinpretreatmentstep.
DuPont
UsesSTRATCOEffluentRefrigerationAlkylationprocess
usingsulfuricacid
LummusTechnology
AlkylCleanprocessusingsolidacidcatalyst.
Demonstrationunitonly.
RefiningHydrocarbon
TechnologiesLLC
RHTAlkylationprocessusessulfuricacid.Eductormixing
device.
ExxonMobilResearch&
Engineering Sulfuricacidalkylationusingautorefrigeratedreactor.
UOP(1) ModifiedHFAlkylationtoreduceaerosolformation.
UOP(2)
IndirectAlkylation(InAlk)usessolidcatalyst.Olefins
polymerize&highermolecularweightmaterial
hydrogenated.
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)refinersinvestigateduseoftheircatalyticpolymerizationand
alkylationcapacityforproductionofhigheroctanemotorfuels
Chicken&egg increasingoctaneproductioncapacity&higherperformanceenginesinautomobilesledto
theoctaneraceinmid1950s
Bothpolymerization&alkylationwereadapted alkylationbecamethedominantprocess
Bythe1960s,polymerizationunitswerebeingphasedout&newplantsutilizedalkylationtechnology
42
SulfuricAcidvs.HFAlkylation
SulfuricAcidAlkylation
Developedbyconsortiumofmajorrefiners&
contractors
AngloIranianOil,HumbleOil&Refining,Shell
Development,StandardOilDevelopment,&the
TexasCompany
FirstunitatHumbleBaytownRefinery,1938
Manyalkylationplantswerebuiltatthesametime
asthecatalyticcrackingunits
OperatedduringWorldWarIIforaviation
gasolineproduction
Sulfuricacidalkylationrequiredaccesstoacid
regenerationonalargescale
Mostlocatedondeepwaterforbargetransport
ofspentacidtoregenerationatacidplants&
returnoffreshacid
Economichandicapforinlandmidwestern
refineries
HFAcidAlkylation
DevelopedbyPhillipsPetroleum&UOP
HFcouldbereadilyregeneratedinalkylation
plantfacilities
Noneedtotransportcatalystinlarge
quantitiesforregeneration
43
Feedstocks &Products
Olefinicstreamfromthecatalyticcracker
Butyleneisthepreferredolefinsinceit
producesthehighestoctanenumber&
yields
isobutane&isopentanecanbereacted
withtheolefin
Isopentanenotusuallyusedsinceitisa
goodgasolineblendstock
Highoctanenumber&lowvapor
pressure
Catalyticcrackerfeedcontainssignificant
sulfur
Treatingunitoftenprecedesalkylation
unit
Alkylatedesirablecomponentforhigh
performanceautomotivefuels
Veryhighoctaneindex(R+M)/2of95
Lowvaporpressure
Vaporpressureisadjustedforfinal
boilingpoint
IBPadjustedforadditionofnormal
butane
Lowsulfurlevels
Essentiallynoolefins,benzeneor
aromatics
44
C4Isomerization
UOPsButamer
TM
processisahighefficiency,
costeffectivemeanstomeetisobutane
demandsbyisomerizingnC4toiC4
Equilibriumlimited
LowtemperaturefavorsiC4
Highactivitychloridedaluminacatalystsused
HighselectivitytoiC4byseparating&recycling
nC4toextinction
Oncethroughlowercapitalcost
45
NButaneRecycledtoExtinction
OnceThroughNButaneConversion
ProcessChemistry
Acidcatalyzedalkylationcombinesisoparaffins&olefinstoformalkylate,highly
branchedalkanes
Usuallyonlyisobutaneisused
Isopentaneisagoodgasolineblendstock
FriedelCraftsreaction Lewisacid(HForH
2
S0
4
)promotescarboniumionona
tertiaryisoparaffinthatrapidlyreactswithanydoublebonditencounters
(propylene,butylenes,orpentylenes)
Thereactioncarriedoutintheliquidphasewithanacid/reactantemulsion
maintainedatmoderatetemperatures
Propylene,butylene,&pentenesareolefinsused butylenepreferred
Highoctaneisooctanealkylateproduced
Lowerreactantconsumption
Alkylationreactionshavecomplexmechanisms&mayproducemanydifferent
varieties
46
ProcessChemistryExamples
Isobutylene&isobutaneform2,2,4trimethylpentane(isooctane)
Propylene&isobutaneform2,2dimethylpentaneasprimaryproductwith2,3
dimethylpentane&2,4dimethylpentaneassecondaryproducts
47
C CH
2
C H
3
C H
3
+
H
+
C
+
CH
3
C H
3
C H
3
C
+
CH
3
CH
3
C H
3
CH
CH
3
CH
3
C H
3
+
H
+
C
CH
3
CH
3
C H
3
CH CH
3
CH
3
CH
2
+
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
48
TypeofOlefin
Butylenepreferred
Producesthehighestisooctanelevels
ResultingResearchOctaneNumbersof9395(withisobutane)
RONandMONareaboutequalforalkylation
Amountsofbutyleneconsumedperalkylateproducedisthelowest
Sidereactionsarelimited
Propyleneworse
Octanenumbersarelow(8992RON)
Propylene&acidconsumptionarehigh
Penteneresultsaremixed
Sidereactionsfrequent
49
Isobutaneconcentration
Excessisobutanerequired normalvolumeratioofisobutanetoolefininthe
feedis610
Limitedisobutanesolubilityinacidphase
Olefinsneedtobesurroundedbyisobutaneexposedtoacid ifnot,olefinswill
polymerizeinsteadofalkylate
Newerplantshavemultiinjection&vigorousmixingsystems
Effectofisobutaneisexpressedintermsofconcentrationinthereactionzone
Isobutanetoolefinratiosmaintainedat10,000to1
50
Isobutane/OlefinInjection&Mixing
Moreimportantinsulfuricacidsystems
Acidviscosityatoperatingtemperatures
Provideoptimalreactionconditionsfortheveryfastreaction
Injectolefinfeedstockinincrementalfashiontoincreaseisobutane/olefinratios
Newerplantsdesignedformultiinjectionlocationsintoanagitatedemulsionto
disperseolefinasrapidlyaspossible
Systemswithsinglepointinjectioncaneasilyhaveanoverloadofolefininthe
emulsion
Leadstolowerquality&higheracidconsumptionfromesterificationreactions
51
ReactionConditions
Reactiontemperature
Mostnoticeablevariableinbothreaction
systems
Increasingtemperaturereducesoctane
number
HFsystemsrunat95F
Coolingwatersufficient
Sulfuricacidsystemsrunat45F
Refrigerationmayberequired
Oftenemployautorefrigerationofthe
reactantmasstoprovidecoolantfor
thereactors
Acidstrength
HFacidstrengthisnotanimportant
variableintherangeof80%to95%
Sulfuricacidstrengthissomewhata
functionofthediluent
Waterlowersacidactivity3to5times
asfastashydrocarbondiluents
Acidisconsidered"spent"ataround
88%sulfuricacid
52
Sulfuricvs.HFAcidAlkylation
Sulfuricacidalkylationisdominantprocess
Sulfuricacidplantsrequireextensiverecuperationofthespentacid
generallydoneoffsite
Largercoastalrefinerstendtohavesulfuricacidalkylationplantswithbarge
orshorthaultransportationtoacidregenerationfacilities
HFplantsgenerallysmaller&catalystregenerationisdoneinplantwith
asmallacidmakeup
UrbancommunityconcernstohazardsofHFescape
UnitedSteelworkersUnionCallsforIndustrywidePhaseoutofHydrogen
FluorideinOilRefineryAlkylationUnits
http://www.usw.org/media_center/releases_advisories?id=0207
August31,2009
53
SulfuricAcidAlkylation
54
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
TimeTankReactors
55
RefiningOverview PetroleumProcesses&Products,
byFreemanSelf,EdEkholm,&KeithBowers,AIChECDROM,2000
Autorefrigerated ReactorSulfuricAcidAlkylation
(EMRE)
56
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
STRATCOContactor
TM
Reactor
SulfuricAcidAlkylation(DuPont)
57
STRATCOAlkylationTechnologyImprovements
KevinBockwinkel
2007NPRAAnnualMeeting
http://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
58
UOP/PhillipsAlkylationProcess
59
http://www.uop.com/processingsolutions/refining/gasoline/#alkylation
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
PhillipsAlkylationProcess
60
Component Olefin Feed
Saturated
Butanes
Propane Yield
Motor-Fuel
Butane Yield
Motor-Fuel
Alylate Yield
Acid Oils
Ethane 0.49 0.49
Propylene 21.04
Propane 17.42 0.30 18.77
Isobutane 191.81 13.48 0.34 3.13 0.19
Butenes 169.10
n-Butane 63.17 10.11 63.35 9.93
Pentanes 4.90 0.42 3.67 1.65
Alkylate 390.17
Acid Oils 0.55
Total 467.93 24.31 19.60 70.15 401.94 0.55
Stream Totals 492.24 492.24
RVP [psi] 6.0
Specific Gravity 0.70
RON, clear 95.0
MON, clear 93.5
FBP [C] 195
FBP [F] 383
AlkylationInstalledCost
Includes
Facilitiestoproducealkylate fromfeed
withiC4&C3toC5olefins
Allnecessarycontrollers&
instrumentation
AllISBLfacilities
Feedtreating(molecularsievetoremove
moisturefromfeed)
Excludes
Coolingwater,steam&powersupply
Feed&productstorage
61
PetroleumRefiningTechnology&Economics,5
th
ed.
Gary,Handwerk,&Kaiser
CRCPress,2007
GasolineUpgradingProcessComparisons
Pros
Reforming
Highoctane
LowRVP
Byproducthydrogen
Isomerization
BetteroctanethanLSR
Toolightforreforming
Lowaromatics&olefins
Verylowsulfurlevels
Alkylation
Goodoctane
LowRVP
Cons
Reforming
Higharomatics(benzene)
Isomerization
Octanestillrelativelylow
HighRVP
Alkylation
Requireslightends issueifno
FCCU
HFcommunityconcerns
62