2014 Alkylation Chemistry Paper

SULFURICACIDALKYLATIONCHEMISTRY
Mechanisms,OperatingVariables,&OlefinInteractions
Presentedatthe
2014STRATCOAlkylationBestPracticesWorkshop
CoeurdAlene,Idaho,USA
PaperBy:
KenKranz,
ManagingR&DChemist
Copyright 2014. E. I. du Pont de Nemours and Company. All rights reserved. The DuPont Oval Logo, DuPont, The miracles of science and all products denoted with a
or are trademarks or registered trademarks of E. I. du Pont de Nemours and Company or its affiliates.
SulfuricAcidAlkylationChemistry
TableofContents
1.0DuPontAlkylationTechnologyCenter............................................................................................1
2.0AlkylationChemistry......................................................................................................................1
2.1ReactionMechanism.............................................................................................................................1
2.2SecondaryReactions..............................................................................................................................3
2.3CarbonNumberDistributionofAlkylate..............................................................................................4
3.0SulfuricAcidCatalyst......................................................................................................................5
3.1SulfuricAcid/HydrocarbonEmulsion..................................................................................................5
3.2AcidSolubleOils.....................................................................................................................................7
4.0OperatingVariables.......................................................................................................................8
4.1IsobutaneConcentration.......................................................................................................................8
4.1Temperature..........................................................................................................................................9
4.2SulfuricAcidStrengthandSpendingStrength...................................................................................11
4.3OlefinSpaceVelocity...........................................................................................................................11
4.4Mixing...................................................................................................................................................11
5.0OtherVariables............................................................................................................................12
5.1Diluents.................................................................................................................................................12
5.2WaterinSulfuricAcid..........................................................................................................................12
5.3FeedContaminants..............................................................................................................................12
6.0SpecialConsiderationandInteractionsofDifferentOlefins..........................................................13
6.1IsobutyleneandButylenes..................................................................................................................14
6.2PropyleneandButylenes.....................................................................................................................15
6.3PropyleneandStagedPropyleneFeed...............................................................................................16
7.0Amylenes.....................................................................................................................................18
7.1EffectofIsopentaneinC5OlefinFeed................................................................................................19
7.2ComparingC5AlkylationwithC4Alkylation........................................................................................20
7.3DesignConsiderations.........................................................................................................................21
8.0AlkylationofButyleneswithIsopentane......................................................................................22
9.0Summary......................................................................................................................................23
1.0 DuPontAlkylationTechnologyCenter
TheworkoftheDuPontAlkylationTechnologyCenterisdirectedatbothmeetingexistingcustomer
requirements and continuing the alkylation R&D required to support our customers needs for
competitivetechnologywellintothefuture.
We have operated a laboratory R&D facility for a number of decades. Within the past 30 years,
various alkylation research projects such as 2step alkylation, alkylation additives, series olefin
processing, and propylene and amylene alkylation have been conducted. Projects have also been
conductedincooperationwithoutsidecompanies,refineries,anduniversities.
A significant part of our experiments in alkylation use flexible benchscale pilot plants. These are
used to determine sulfuric acid catalyst consumption, octane, yield, and other alkylate properties
under a wide range of operating conditions and with different feedstocks. We have decades of
experiencewiththesepilotplantswhichareusedtohelpbuildpredictionmodels.Operationofthe
plantscanalsobeadjustedtomatchtheperformanceofolderrefineryunits.
Currentresearchprojectsincludefurtherexperimentstoexpandandimproveuponourprediction
modelsandtoimproveourknowledgeofthealkylationprocess.Wecontinuetoprovidesupportto
theprocessengineeringgrouponproposalsandprojects.
Wealsohaveactiveprojectstoimprovethedesignandperformanceofouralkylationequipment.
For example, new technology for the reaction zone, including equipment improvement and
redesign,isunderinvestigationwiththepotentialtosignificantlyimprovefuturealkylationsystems.
2.0 AlkylationChemistry
ThealkylationreactioncombineslightC3C5olefinswithisobutaneinthepresenceofastrongacid
catalyst.Althoughalkylationcantakeplaceathightemperaturewithoutcatalyst,theonlyprocesses
of commercial importance involve low to moderate temperatures using either sulfuric or
hydrofluoricacid.
Alkylationreactionsarecomplexandconsequentlytheproducthasawideboilingrange.Over200
different isoparaffin isomers may be produced by alkylation. With careful attention to operating
conditions,theproductwillfallintothegasolineboilingrangewithmotoroctanenumbersfrom88
95 and research octane numbers from 9098. For the purposes of this paper only sulfuric acid
catalyzedalkylationwillbeconsidered.
TheSTRATCOContactorreactor,alongwiththeDuPontSTRATCOEffluentRefrigeratedAlkylation
process, are designed to promote reactions that favor the production of gasoline boiling range
productsandminimizecompetingreactions.Someoftheseunfavorablereactionscanresultinpoor
productqualitywithrespecttooctaneandendpoint,orgreaterthannecessaryacidconsumption.
2.1 ReactionMechanism
It is accepted that alkylation of isobutane with C3 C5 olefins involves a series of consecutive

andsimultaneousreactionsoccurringthroughcarbocationintermediates.Ageneralizedreaction
schemeforbutenealkylationcanbesummarizedasfollows
1
Thefirststepistheadditionofaprotontotheolefintoformatbutylcation.
Olefin
AlkylSulfate
Cation
This reaction with sulfuric acid results in the production of alkyl sulfates. Occasionally alkyl
sulfatesarecalledesters.Propylenetendstoformmuchmorestablealkylsulfatesthaneither
C4orC5olefins.
Witheither1buteneor2butene,thesecbutylcationformedmayisomerizeviamethylshiftto
giveamorestabletbutylcation.
secbutylcation
tbutylcation
These initiation reactions are required to generate a high level of ions but become less
importantatsteadystate.Typically,thiscanbeobservedasahigherrateofacidconsumption
initiallywhenusingfreshacid.
ThetbutylcationisthenaddedtoanolefintogivethecorrespondingC8carbocation:
butyl cation
i-butene
2,2,4-TMP+
2-butene
2,2,3-TMP+
1-butene
2,2-DMH+
2
TheseC8carbocationsmayisomerizeviahydridetransferandmethylshiftstoformmorestable
cations
ThentheC8cationsundergorapidhydridetransferasisobutane,orotherspecies,regenerates
thetbutylcationtoperpetuatethechainsequence
Unfortunately,thesearenottheonlyreactionsoccurringduringalkylation.Thereareanumber
ofsecondaryreactionsthat,ingeneral,tendtoreducethequalityofthealkylate.
2.2 SecondaryReactions
Polymerization results from the addition of a second olefin to the C8 cation formed in the
primaryreaction.TheC12+cancontinuetoreactwithanolefintoformalargercation:
Aswiththepreviouslydescribedmechanisms,theheavycationsmayatsomepointundergoa
hydride transfer from isobutane to yield a C12 C16 isoparaffin and a
tbutylcation.TheseheavymoleculestendtolowertheoctaneandraisetheD86T90andend
pointofalkylatecontainingthem.
3
Also,itisthoughtthatsomeofthesecationstendtoremainasalkylsulfatesandwillberetained
intheacidphase,ultimatelybecomingtheacidsolubleoilsresponsibleforacidconsumption.
Disproportionation causes the disappearance of 2 molecules of alkylate to give a lower and a
highermolecularweightisoparaffinthantheinitialone.
Experimentaldataindicatesthatdisproportionationoccurstoisoparaffinsincontactwithacidin
theabsenceofolefins.Someisoparaffinsseemtobemorepronetothisthanothers.
Crackingcanoccurtolargerisoalkylcations,producingsmallercationsandolefins
Olefins and cations produced by cracking are then subject to any of the previously described
reactionsleadingtoanarrayofparaffinichydrocarbons.
A hydrogen transfer mechanism occurs when alkylating amylenes to produce isopentane and
trimethylpentanes. Both isoamylenes and normal amylenes undergo this hydrogen transfer
mechanism.Normalamylenesundergoanadditionalstepbyfirstreactingwithatbutylcation
to form a trimethylhexane cation. The trimethylhexane cation isomerizes to form other
trimethylhexane cations and fragments to produce isoamylenes and a tbutyl cation. By
hydrogen transfer, the isoamylenes are converted to isopentane and the tbutyl cation is
convertedtoisobutylene.Theisobutylenereactswithisobutanetoproducetrimethylpentanes.
nC5=+iC4+TMH+
TMH+iC5=+iC4+iC5+iC4=
iC4=+iC4TMP
Thehydrogentransferreactionresultsinanetincreasedconsumptionofisobutaneaswellas
increasedyieldandoctanealongwithanincreaseinisopentaneproduction.
2.3 CarbonNumberDistributionofAlkylate
The table below is an example of typical carbon number distributions of true alkylate produced
frompropylene,butylenes,andamylenes.Theoperatingconditionsunderwhichthesealkylates
wereproducedaresomewhattypicalandnotnecessarilyoptimal.
Note that amylenes produce a significant amount of isopentane from the hydrogen transfer
reaction.ThisalsoresultsinproductionofC8isomers.
4
2014STRA
ATCOAlkylattionBestPraccticesWorksh
hop
SulfuricAcidAlkylation
nChemistry
3.0 SulffuricAcidC
Catalyst
3.1 Su
ulfuricAcid/Hydrocarbon
nEmulsion
Th
hesulfuricaccidcatalystismosteffectiveathighstrrengths,main
nlybetween 97wt%to88
8wt%
H2SO4. Water and acid soluble
s
oils from
f
olefin polymerizatio
on dilute thee acid during the
allkylationproccess.Someaacidsolubleo
oilsaredesiraableastheyaactassurfactaantsandhelp
pwith
th
heformationoftheacid/h
hydrocarbone
emulsion.
Alkylationsulfuricisgeneraallyspentataaround90wt %H2SO4ino
ordertoavoidanacidrun
naway
re
eaction. Acid
d runaway occcurs when the
t acid strenngth becomees too low, in
n the range o
of 86
87
7wt%,slowin
ngthesecond
dreactionste
epbetweentthealkylsulfaatesandisob
butane.Spentacid
normallycontaainsbetween
n23wt%wate
er.
healkylationreactionrequ
uiresahighin
nterfacialsurrfaceareabettweentheaccidcatalystan
ndthe
Th
hyydrocarbon.Thelowestaacidconsump
ptionandbesstoctaneare achievedwhentheemulssionis
accidcontinuou
us.Thismeansthattheacidisthemaainphaseand
dhydrocarbonisdispersed
dinto
th
heacid.Thisisdemonstraatedinthepiccturebelow.
5
Copyright 20
014. E. I. du Pont de Nemours
N
and Company
y. All rights reserved. The DuPont Oval Loogo, DuPont, The m iracles of science a
and all products denote
ed with a
or
o are trademarks or
o registered trademarrks of E. I. du Pont de Nemours and Compa
any or its affiliates.
2014STRA
hop
nChemistry
Maintaining
M
a sufficient accid/HC ratio in the Contaactor reacto
or keeps thee emulsion ass acid
co
ontinuous.A
Aratiobetwee
en45%and6
65%(vol/vol))isrecommended.Ahigherratioofaacidin
th
heContactor
reactordim
minishesthe residencetim
meofthehyd
drocarbonallowinglesstim
meto
fu
ullyreact.If theacid/HC ratiofallsbelow40vol%,,theemulsionmayinvertttoahydrocaarbon
co
ontinuous type emulsion.. This type of emulsion settles quickkly, but prod
duces poor q
quality
allkylate and greatly
g
increaases acid consumption. The picturee below show
ws a hydrocaarbon
co
ontinuousem
mulsion.
6
Copyright 20
N
and Company
ed with a
or
o are trademarks or
2014STRA
hop
nChemistry
Care must be
e taken when
n analyzing the
t sulfuric aacid catalyst. Acid titrattions are best for
determiningaccidstrengthrratherthanaspecificgravvitymeasurem
ment.Theaccidsolubleoilscan
co
oatthepHelectrodeandcausetheressponsetodeccrease.With
hautotitratorss,theoilscan
ncoat
th
heelectrodessuchthattheinstrumenth
hasdifficulty determiningtheendpoint.
Th
he acid hydrocarbon emu
ulsion must be
b broken coompletely and the hydroccarbon comp
pletely
se
eparatedfrom
mtheacidforbestresultsswhentitrati ngtheacid. Theacidsam
mpleshouldaalways
becentrifuged
dforaperiod
doftimesuchas15minuutes.Failure todosocan
ncauselowaacidity
re
eadings.
Oils
3.2 AccidSolubleO
Th
hereareoftenseveralweightpercento
ofacidsolublleoilsinthesspentacidwithabout2 3wt%
water,
w
depend
ding on ope
erating condittions. The acid soluble oils are alsso called con
njunct
polymersorre
edoils.Theo
oilsdohaveaaslightlyredddishtintwhen
nfirstproducced.Theseoiilsare
oxxidizedbythe
eacidovertim
meanddarke
en.Thisoxidaationreaction
nalsoproduccesSO2andw
water.
Th
he acid soluble oils cann
not be separated by graavity settlingg or centrifuggation. Theey are
co
ompletelysollubleintheaacid.Thecom
mpositionofthheseacidsolubleoilsisap
pproximatelyyC2025
molecules,abo
m
out250350m
molecularwt.,haveadenssityof~0.9,aabrominenumberof~190
0,and
an
niodinenumberof~380.
Th
herearesusp
pectedC5ringgstructuresin
ntheoils.Exaamplesoftheeseringstructturesare:
7
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and Company
ed with a
or
o are trademarks or
4.0 OperatingVariables
Thereare7importantreactionvariablesthatcanimpacttheproductqualityandoperatingcostof
analkylationunit
IsobutaneConcentration
OlefinSpaceVelocity
AmountofDiluents
ReactionTemperature
AcidConcentration
MixingIntensity
OlefinFeed
FeedContaminants
Thefollowingdataarepresentedtoexamineonlytheeffectoftheprocessvariableinquestion.
All other variables were held constant. Acid consumption was calculated based on net alkylate
productionwithdryfeedscontainingnocontaminants.
In the following graphs, the staged propylene data is presented considering the boost in acid
concentrationthatfollowingacidstageswillrealizeifnopropyleneispresentintheirfeed.Acid
consumption is also presented as the rate of acid consumption at a particular point in time. It
doesnotnecessarilyreflecttheoverallacidconsumptionthatwouldresultduetochangesinthe
consumptionrateastheaciditychangesandtheoverallspendingrangeused.
4.1 IsobutaneConcentration
Inordertopromotethedesiredalkylationreactions,whicharethoseinvolvingisobutaneand
olefins,itisnecessarytomaintainahighconcentrationofisobutaneinthereactionzone.Low
isobutaneolefinratiosincreasethelikelihoodofolefinolefinpolymerizationthatwillresultin
lower octane. Polymerization reactions also have ahigher rate of production of acid soluble
oils,resultinginhigheracidconsumption.
TypicalmolarI/Oratiosinthecompositefeedtothereactionzonenormallyrangefrom5/1to
10/1.TheresultofchangingI/Oratiosisillustratedbelow.
Octane of alkylates made from C4= and C5= feeds respond well to changes in I/O ratio.
IncreasingI/Ohaslittleeffectontheoctaneofalkylateproducedfrompropylene.
8
Sulfuric acid consumption vs. I/O

m ixed butylenes
0.40
#/gal
0.35
0.30
0.25
0.20
5
7
8
m olar I/O
10
DuPont STRATCO
Clean Fuel Technologies
RON vs. I/O
RON
mixed butylenes
96.4
96.2
96.0
95.8
95.6
95.4
95.2
95.0
94.8
94.6
94.4
94.2
5
7
8
m olar I/O
10
DuPont STRATCO
Clean Fuel Technology
4.1 Temperature
Typically,H2SO4alkylationiscarriedoutintheneighborhoodof50F.
9
Sulfuric acid consumption vs. reaction temperature

m ixed butylenes
0.80
0.70
0.60
#/gal
0.50
0.40
0.30
0.20
0.10
0.00
40F
45F
50F
55F
tem p
60F
65F
70F
DuPont STRATCO
RON vs. reaction temperature

m ixed butylenes
96.5
96.0
RON
95.5
95.0
94.5
94.0
93.5
40F
45F
50F
55F
tem p
60F
65F
70F
DuPont STRATCO
Higherreactiontemperaturesdramaticallyfavorpolymerizationreactionsthatwilldilutethe
acid.Equipmentcorrosionwillalsoincreasewithhigherreactiontemperatures.Lowreaction
temperaturesslowthesettlingrateoftheacidfromthealkylate.
Allfeedtypesrespondnegativelytoincreasedtemperaturewithrespecttotheoctaneofthe
alkylate.C3=andC5=feedsseemtobesomewhatmoretolerant.
10
4.2 SulfuricAcidStrengthandSpendingStrength
As the concentration of the sulfuric acid catalyst is reduced, the rate of production of acid
soluble polymers increases. C4= and C5= feeds show moderate increases in acid consumption
over the normal spending range of 98.590 wt% H2SO4. Feeds that contain high amounts of
propylenehaveamuchhigherrateofincreaseinacidconsumptionoverthenormalspending
range.
High sulfuric acid concentration must be maintained in order to minimize polymerization and
red oil production. At concentrations below 85wt%, catalyst activity is substantially decreased
and polymerization enhanced to the point that it is difficult to maintain acid strength. This
conditionisknownasacidrunaway.
Butylene and amylene feeds produce their best alkylate in the range of 9491 wt% H2SO4.
Propyleneproducesbetteralkylateastheacidconcentrationisreduced.
Recentpilotstudieshavefoundthatbothbutylenesandamylenescanbespenttoaloweracid
concentration without entering into a runaway condition. While the economics of alkylating
both butylenes and amylenes will benefit from lowering the acid spending strength, the acid
consumption of amylenes has a greater response than that of butylenes. Also the expected
decreaseinoctaneofalkylatesproducedatloweracidconcentrationsislessforamylenesthan
butylenes.
4.3 OlefinSpaceVelocity
Olefinspacevelocityisdefinedasthevolumeofolefinchargedperhourdividedbytheaverage
volume of sulfuric acid in the Contactor reactor. Values most often range from 0.25/hr to
0.50/hralthoughtheycanbehigherorlower.Ingeneral,higherolefinspacevelocitiestendto
increasesulfuricacidconsumptionratesanddecreasealkylateoctane.Inaddition,athigholefin
space velocities the heat of reaction becomes difficult to remove and the Contactor reactor
temperatureincreases.Increasedreactiontemperaturesarealmostalwaysdetrimentaltoacid
consumptionandoctane.Therefore,veryhigholefinspacevelocitiescauseadoublehiton
acidconsumptionandoctaneandshouldbeavoidedifpossible.
4.4 Mixing
Mixing is an important parameter as the alkylation reaction depends on the emulsion of the
hydrocarbonintothesulfuricacid.Thisisanacidcontinuousemulsion.Itispresumedthatthe
reactionoccursattheinterfaceofacidandhydrocarbon.Thebettertheemulsion,thefinerthe
dropletsandthebetterthereaction.TheContactorreactorneedstobekeptingoodshapeto
providegoodmixing
The amount of acid in the Contactor reactor also needs to be monitored to be assured of a
goodemulsion.IfthevolumeofacidtohydrocarbonintheContactorreactorfallsbelow40%
acid,ahydrocarboncontinuousemulsionmayresultwhichcausesacidconsumptiontoincrease
and alkylate octane to decrease. Too high of an acid/HC ratio, over 65%, may reduce the
residencetimeofthehydrocarbonintheContactorreactorandcauseasimilareffectasahigh
olefinspacevelocity.
11
5.0 OtherVariables
Othervariablesaffectthealkylationprocesstovariousdegrees.Theseincludediluents,amountof
waterintheacid,andfeedcontaminants.
5.1 Diluents
Diluents are compounds that are not involved in the alkylation reaction. They simply take up
spaceandarecarriedthroughtheprocess.Themostcommondiluentsarepropane,nbutane,
and npentane. High amounts of diluents reduce the hydrocarbon residence time in the
Contactorreactor.Fromareactionkineticsstandpoint,diluentscanget inthewayofthe
alkylationreactions.
5.2 WaterinSulfuricAcid
The sulfuric acid catalyst is diluted with acid soluble hydrocarbons due to byproducts of
undesirable alkylation reactions. The acid is also diluted with water from the hydrocarbon
streams. Spent 90 wt% sulfuric often contains 35 wt% water with the remainder being acid
solubleoils.
Sulfuric acid with larger amounts of water generally produces a somewhat lower octane
alkylate.Thiseffectismostpronouncedatloweracidities.Thereisnomeasurableeffectonthe
sulfuricaciddilutionrateexceptthatwatersimplydilutestheacid.Whileitmayormaynotbe
economicaltousedryingsystemssuchasmolecularsieves,itisimportanttooperatethefeed
coalescertoremoveasmuchwateraspossible.
5.3 FeedContaminants
Inadditiontowater,variouscontaminantsarealsosometimespresentinthehydrocarbonfeed.
Thesecontaminantsconsumesulfuricacidbutdonotappeartoaffectthealkylateoctane.The
tablebelowshowssomecommoncontaminantsandtheirrespectiveconsumptionofacidona
poundperpoundbasis.
12
SulfuricAcidDilutionFactors
(99.2%90.0%spendingrange)
Contaminant
#Acid/#Contaminant*
Water
EthylMercaptan
EthylDisulfide
HydrogenSulfide
Acetone10.6
Methanol
Ethanol
tButylAlcohol
Diethanolamine
DimethylEther
DiethylEther
MTBE
ETBE
TAME
1,3Butadiene
3Methyl1,2Butadiene
2Methyl1,3Butadiene(isoprene)
1,3Pentadiene(piperylene)
1,4Pentadiene
Cyclopentadiene
Ethylene
Acetylene
1Butyne(EthylAcetylene)
1Pentyne
Cyclopentene
Acetonitrile
Formaldehyde
Acetaldehyde
9.8
15.7
11.8
29.3
26.1
19.4
9.8
24.0
12.5
10.5
17.4
15.0
12.8
8.3
12.6
11.4
12.4
8.1
18.5
28.2
11.1
12.9
17.4
35
12.5
16.8
10.0
The factors provided in Table 1 are approximate for an acid dilution range of 99.290.0 wt%
H2SO4. To apply these values to other acid strengths, the formula below can be used to
calculateacidconsumption:
AcidConsumption=

(ValueFromTable1)(SpentAcidWt%)
(9.8)(FreshAcidWt%SpentAcidWt%)
6.0 SpecialConsiderationandInteractionsofDifferentOlefins
Historically,refinershavealkylatedprimarilybutyleneswithisobutane.Somequantityofpropylene
mayhavebeenincludedwiththesebutylenefeedsaseconomicsdictated. Recently,refinershave
been including amylenes in the feedstock to help meet vapor pressure requirements and/or to
reducetheolefincontentofthegasolinepool.
13
Under typical butylene alkylation conditions, propylene and amylenes produce alkylate that has a
muchloweroctanevaluethanbutylenealkylate.Also,propyleneandamylenesconsumethesulfuric
acidcatalystatamuchhigherratethandobutylenes.Asexpected,whenacombinedC3/C4/C5olefin
feed is alkylated with isobutane, there is a corresponding drop in alkylate octane and increase in
sulfuric acid consumption. However, by taking advantage of some special properties of propylene
and amylenes, any penalty can be kept to a minimum. Significant benefits can be obtained by
segregatingtheolefins,thenalkylatingeacholefingroupattheirpreferredreactionconditions.
Aspreviouslydiscussed,propyleneformsstablepropylsulfatealkylsulfatesthatcanbereactedin
otheracidstagesifpropyleneisnotpresentinthefeed.Ifthereisasignificantamountofpropylene
in the feed, it may be desirable to segregate the propylene to the first or second acid stages,
dependingontheamountofpropyleneandthenumberofacidstages.Thereactionconditionscan
then be adjusted for the acid stages with propylene to maximize the octane and minimize the
sulfuricacidconsumption..
Indecidingonhowandwhentosegregatetheolefins,interactionsbetweentheolefinsneedtobe
considered.Theinteractionsaffectsulfuricacidcatalystconsumptionandalkylateoctane.
6.1 IsobutyleneandButylenes
There is a long history of the alkylation of butenes with sulfuric acid catalyst. However,most
commercialexperienceislimitedtobutenefeedsthatcontainaround28wt%isobutyleneasa
percentageofbutenesandfeedsthathavebeenprocessedthroughanMTBEunitthatcontain
less than 5 wt% isobutylene. The alkylate produced from an MTBE raffinate typically has a
higheroctanethanalkylateproducedfromfeedscontaining28wt%isobutylene.Thetrendin
octane versus isobutylene content has widely been extrapolated to project the octane of
alkylateproducedfromisobutylenealone.Pilotstudiesindicatethat,inpart,thedegradationin
octane with increasing isobutylene is due to interactions between the isobutylene and n
butenes.Asshowninthegraphbelow,athighconcentrationsofisobutylene,therateofoctane
degradationisslowed.
Average Octane (R+M)/2
Octane of Butylene Alkylate vs. Isobutylene

Content
96.0
95.0
Observed
94.0
93.0
Commercial Experience
Extrapolated
92.0
91.0
0%
20%
40%
60%
80%
100%
Wt% Isobutylene in Total Butene
14
Thisinformationisimportantfornewalkylationunitsbeingconsideredforemerginggasolinemarkets.
Ofteninthesemarkets,thereareinsufficientsourcesofisobutaneavailabletoalkylatetheentire
buteneolefinstream.Instead,thebutenefeedstreamcanbefractionatedtorecoverthecontained
isobutaneandaportionoftheolefins.Isobutaneandolefinsrecoveredinthisfashionwillberichin
isobutylenebecauseofthehighervolatilityofisobutylenecomparedtonbutenes.Alkylateproduced
fromthisfeedusingsulfuricacidcatalystmayhavealoweroctanethanalkylateproducedfromthe
entirestream.
Average Octane (R+M)/2
Octane of Butene Alkylate vs. Isobutylene Content

96.0
95.5
95.0
94.5
94.0
93.5
0%
10%
20%
30%
40%
50%
60%
70%
80%
90%
Wt% Isobutylene in Total Butene
Atpreferredconditions,a100%isobutylenefeedcanproducealkylatewithan(R+M)/2octane
of94.5andupto96RON.
6.2 PropyleneandButylenes
Alkylate produced from alkylating propylene has a rather low octane value of around 90
(R+M)/2 due to the dimethylpentanes that are produced. On the other hand, these C7
isoparaffins give lower ASTM D86 end point temperatures compared to alkylate from
butylenes.
The interaction that occurs when propylene and butylenes are alkylated together also affects
the alkylate octane. While small amounts of propylene may not have a large effect on acid
consumption, the alkylate product octane decreases to a greater extent than a linear trend
wouldsuggest.Evenwhenpropylenecomprisesonly20%oftheolefinsinapropylene/butylene
feed, the alkylate octane can be over an octane number lower than a linear trend would
suggest.
15
EffectofIncreasingPropyleneonOctane
94.5
94.0
Octane (R+M)/2
93.5
93.0
Theoretical
92.5
92.0
91.5
91.0
Actual Octane
90.5
90.0
0
20
40
60
80
100
Vol% Propylene in a C3=/Mix C4=Feed
Changes in the alkylate composition show an increase in the C10+ isoparaffins which suggest
interaction between the stable propyl sulfates and other olefins. It could be possible for a
propyl sulfate to react with another C3C5 olefin to form a C6C8 cation. These cations can
undergo a hydrogen transfer to become C6C8 isoparaffins or combine with isobutane to
becomeC10C12orheaviercations.Theselargercationscouldalsoundergohydrogentransfer
tobecomeheaviesorfragmentintovariousisoparaffins.Testshaveshownadecreaseofpropyl
sulfatespresentintheacidwhenbutylenesoramylenesareaddedtothefeed.
Because the interaction of propylene and butylenes produces a greater amount of heavier
isoparaffins, this produces a dramatic effect on the distillation properties of the alkylate. A
propylene/butylene feed produces an alkylate with a higher T90 than compared to feeds with
propyleneorbutylenesalone.TominimizeT90,itisbesttoalkylatepropyleneandbutylenesas
separatelyaspossible.
6.3 PropyleneandStagedPropyleneFeed
Thefirststepreactionofpropylenewiththeacidtendstoformmorestablealkylsulfatesthan
eitherC4orC5olefins.Theseacidsolublesulfatesarestableenoughthattheywillcarryontothe
next acid stage. In the past, DuPont has presented data relating to propylene alkylation
consideringonlythepropylenestage,calculatingacidconsumptiononthatrateofconsumption
ofthepropylenestageonly.
Inthelab,wehavefoundthatwhentheacidfromapropylenestageissentontoanotherstage
where isobutane and nonpropylene olefins are present, these propyl sulfates will react,
effectivelyboostingtheacidconcentrationofthatacidstage.Thisdramaticallyreducessulfuric
acidconsumption.
16
The graph below shows how acidity is recovered when the propylene feed is stopped and
isobutaneonlyisfedtothereactor.
Propylene acidity "pop-up"
stop olefin feed & switch to isobutane
97%
96%
95%
WT% H2SO4
94%
93%
92%
91%
90%
89%
88%
87%
0h
1h
2h
3h
Hours
4h
5h
ThepropylsulfatedilutedacidshowsamarkedincreaseinH2SO4concentration.Insomecases,
theacidinthepropylenestagelostasmuchas9wt%andrecoveredover7wt%,afterwashing
theacidwithisobutane
As the sulfuric acid strength gets lower, it is easier to have a buildup of propyl sulfates. It is
preferabletoalkylatehighpropylenefeedswithhighstrengthacidthatisnormallypresentin
the first one or two acid stages in an alkylation unit. Keeping propylene out of the last acid
stage can dramatically reduce acid consumption. The following graph shows the difference
betweenalkylatingan80/20propylene/butylenefeedinallacidstagesvs.beingfollowedbyall
butylenesin afinalacidstage. Thedifferencebetween thetwo linesisdue tothe buildupof
propylsulfatesdilutingthesulfuricacidcatalyst.
17
80/20 C3=/C4= Acid Consumption Rate vs. Acid Strength
# H2SO4/Gal Acid Consumption Rate
C3= Not
Staged
C3=
Staged
0
96
95
94
93
wt% H2SO4
92
91
90
The buildup of propyl sulfates are greatly affected by reaction temperature. Low reaction
temperaturesdonotdrivethereactionofpropylsulfatesandisobutane.Previousinformation
statedthatpropyleneneedstobealkylatedathigherreactiontemperatures.Iftheacidfrom
thehighpropylenestageisfedtoanotherstagethatdoesnotcontainpropyleneinthefeed,the
propyl sulfates will be recovered and higher reaction temperatures are not necessary. When
propyleneisstaged,lowerreactiontemperaturesarepreferable.
7.0 Amylenes
Refinersarealkylatingmoreamylenestohelpreducethevaporpressureandolefincontentofthe
gasolinepool.Optimumreaction conditionsforamylenesaresimilartothoseforbutylenes,but
because the acid consumption for amylenes is greater than for butylenes, actual savings from
optimizingreactionconditionsisgreaterforamylenes.
FollowingisanaverageFCCmixedamylenefeedanalysis.
18
AverageMixedAmyleneFeedAnalysis
Component
AverageWt%
BoilingPointF/C
3Methyl1Butene
1.4
68/20
Isopentane
44.8
82/28
1Pentene
4.7
86/30
2Methyl1Butene
8.3
88/31
2Methyl1,3Butadiene
0.20
93/34
nPentane
6.9
97/36
trans2Pentene
10.6
97/36
cis2Pentene
5.7
99/37
2Methyl2Butene
14.3
100/38
1Pentyne
0.09
104/40
3Methyl1,2Butadiene
0.13
1,3Pentadiene(trans&cis)
0.41
108/42
Cyclopentadiene
0.12
109/43
Cyclopentene
1.7
111/44
Cyclopentane
0.7
120/49
Thecompositionanddistributionoftheamylenesdirectlyaffecttheacidconsumptionandoctane
of the alkylate produced. Cyclopentene is an undesirable C5 olefin resulting in higher acid
consumptionandloweroctane.Ifpossible,mostcyclopenteneshouldbeleftintheFCCgasoline
andnotfedintothealkylationunit.
7.1 EffectofIsopentaneinC5OlefinFeed
Isopentane is present in the amylene feed stream in significant amounts. In a mixed amylene
feed, the ratio of isopentane to amylenes is about one. Pilot studies have shown that, like
isobutane,isopentaneisreactiveandwillalkylatewithpropylene,butylenesandamylenes.The
amount of isopentane present in an olefin feed stream has a direct effect on the amount of
isopentaneproduced,thesulfuricacidconsumption,andthequalityofthealkylate.
Becauseisopentaneisareactant,increasingtheamountofisopentaneinthefeedwilldecrease
the net amount of isopentane produced. Increasing amounts of isopentane also reduce the
amountofisobutaneconsumed.
19
If enough isopentane is present, there will be a net consumption of isopentane. The graph
below shows the consumption of isobutane and isopentane when alkylating amylenes as
isopentaneissubstitutedforisobutane.
Isobutane/Isopentane Blends with Amylenes

consumption of isobutane and isopentane
Consumption of isobutane or isopentane (vol/vol

olefin)
2.50
isopentane consumption
2.00
1.50
isobutane consumption
1.00
production occurs
below the line
0.50
0.00
0%
20%
40%
60%
80%
100%
-0.50
Vol% Isopentane in total iC4/iC5
Unfortunately,sincemoreC10+isoparaffinsareproduced,theoctaneofthealkylateislowerand
theASTMD86distillationtemperaturesarehigher.Aninterestingphenomenonseenathigher
levelsofisopentane,whereitisconsumed,isthatthemotoroctanenumberbecomesgreater
thantheresearchoctanenumber.
Among the economic decisions on whether to alkylate propylene and/or amylenes is the
alkylate yield of the olefins. Past references to the yield of amylenes have shown rather low
numbersinthe1.551.60bblalkylateperbblolefinrange.Experiencewithouralkylationpilot
plant and commercial data indicate that the yield for amylenes can be significantly higher.
Depending,ontheamountofisopentaneinthereactionzoneandoperatingconditions,typical
yields for mixed amylenes can vary from about 1.76 2.04 bbl alkylate/bbl olefin. For some
refiners, this range of amylene alkylate yield can impact the economics enough to make
alkylationofamylenesattractive.
7.2 ComparingC5AlkylationwithC4Alkylation
The alkylate produced from C5 olefins has a much higher motor octane than the C5 olefins
themselvesalthoughtheresearchoctaneofthealkylateissomewhatlower.Theoveralleffect
on octane is positive. The larger effect is on sensitivity. Alkylating C5 olefins reduces the
sensitivityofthegasolineblend.ThesameistrueforalkylatingC4olefins.
TypicalpropertiesofC5alkylateareshowninthefollowingtable.Theacidconsumptionislower
than previously reported. These revised values are on a cyclopentene and contaminant free
20
basis.SelectivelyhydrogenatingandsweeteningtheC5olefinstreamisessentialtoachievethe
acidconsumptionshown.
True alkylate octane in the table refers to the net reaction product rather than the alkylate
product.WithC3andC4alkylation,thereisnormallyonlyasmalldifferencebetweenthetrue
alkylateandalkylateproductoctane,especiallyatlowRVP.Incontrast,withC5alkylation,the
difference can be large. The difference is the result of pentanes in the olefin feed that carry
throughtothealkylateproduct.
C4alkylate
C5alkylate
TrueAlkylateRON
9498
8791
TrueAlkylateMON
9295
8689
TrueAlkylateVol.Yield
1.701.78
1.681.95(vol.pervol.olefin)
ReactionIsobutane
1.101.16
0.961.20(vol.pervol.olefin)
AcidConsumption*
0.30.6
0.40.8(lb./galnetalky)
(*dependentoncontaminants)
7.3 DesignConsiderations
Both C4 and C5 alkylate properties become optimum at intermediate sulfuric acid strengths.
However, the optimum intermediate strength for C5 alkylation is lower than that for C4
alkylation.
Adding C5 alkylation capacity to an existing alkylation unit allows for staging acid from the
existing unit to the new C5 unit. Thus the existing unit can run at higher acid strengths and
producehigherqualityalkylatewhiletheC5alkylatecanruntheaciddowntoalowerstrength.
ThisarrangementrequireslessincrementalacidthanrunningC5inparallelandusingfreshacid.
21
8.0 AlkylationofButyleneswithIsopentane
Isopentane with mix C4=

acid consum ption (lb/gal net)
0.80
Acid Con (#/gal)
0.70
0.60
0.50
0.40
0.30
0.20
0.10
0.00
0
20
40
60
80
percent iC5/total isoparaffins

DuPont STRATCO
Isopentane with mix C4=
True alky octane predicted
predicted true octane vs. %iC5

96.0
95.0
94.0
93.0
92.0
91.0
90.0
89.0
88.0
RON
M ON
20
40
60
80
percent iC5/total isoparaffins

DuPont STRATCO
22
2014STRA
hop
nChemistry
9.0 Sum
mmary
In alkkylating lightt olefins witth isobutane in the pre sence of sulfuric acid, tthere are seeveral
mechanisms that collectively describe the
e results see n both in th
he laboratoryy and comm
mercial
produ
uction.
Alkylaation takes place
p
in an acid continu
uous liquid eemulsion pro
oduced by m
mixing appropriate
amou
untsofhydroccarbonswithsulfuricacid.
Inthe
ecommercialalkylationprrocessthere arefivereacttionvariablesstoconsider.Ifthesevariables
areke
eptnearoptim
mum,ahigho
octanealkylatecanbeprooducedwithm
minimalacidcatalystdiluttion.
Greatt acid savingss can be reaalized by segregating proopylene and reacting it in
n the highestt acid
strenggthreactor.A
Anysignifican
ntamountofpropyleneshhouldnotbeaalkylatedatlo
owacidstren
ngth.
Isopentane reacts like isobutane. The pressence of relaatively large amounts of isopentane in the
amyle
enefeedstreaamaffectsaccidconsumptiionandoctanne.
Interaactionsoccurbetweendiffferentolefinss.Theseinte ractionsneed
dtobeconsid
deredifsignificant
amou
untsofpropyleneandamyylenesareinttheolefinfee d.
It is possible
p
to saafely spend sulfuric
s
acid to a lower cconcentration
n when alkylaating butylen
nes or
amyle
enes,witham
mylenesbeinggpreferredattloweracidcooncentrations.
23
Copyright 20
N
and Company
ed with a
or
o are trademarks or

2014 Alkylation Chemistry Paper

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2014 Alkylation Chemistry Paper

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SULFURICACIDALKYLATIONCHEMISTRY

It is accepted that alkylation of isobutane with C3 C5 olefins involves a series of consecutive

Sulfuric acid consumption vs. I/O

RON vs. I/O

Sulfuric acid consumption vs. reaction temperature

RON vs. reaction temperature

Average Octane (R+M)/2

Octane of Butylene Alkylate vs. Isobutylene

Wt% Isobutylene in Total Butene

Average Octane (R+M)/2

Octane of Butene Alkylate vs. Isobutylene Content

Wt% Isobutylene in Total Butene

Vol% Propylene in a C3=/Mix C4=Feed

# H2SO4/Gal Acid Consumption Rate

Isobutane/Isopentane Blends with Amylenes

Consumption of isobutane or isopentane (vol/vol

Isopentane with mix C4=

percent iC5/total isoparaffins

Isopentane with mix C4=

True alky octane predicted

predicted true octane vs. %iC5

percent iC5/total isoparaffins

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