IICPT

Inqi Journal of Chcmicel

.rd P.trolcum Enginccritrg
lraqiJournalof andPetroleum
Chemical
Vol.8No.3(September
Engineering
2007)43-48
ISSN:1997-4884 Univcnity ofBrgbdd
Coll€c of EDtinE iog

in lsomerization
Studyof CatalystsDeactivation Process
to ProduceHigh OctaneGasoline
Khalid A. Sukkar,HayamM. Abrlul-Raheemo Amel Th. Jubernand Jabir Sh.Jurnaly'
ChemicalEngineering - University
Department - Iraq
of Technolog,t
' * - * Iraq
Chemical DepartmentCollegeof EngineeringUniversity
Engineering of Al-Nahrain

Abstract
In this study the isomerizationof desulfuerized light lraqi petroleumnaphtha(Al-DuraRefinery)with boilingpoint
range of 37 to 124 oC , 80.5API specificgravity and 68.2 octanenumber has beenirwestigated.Two typesof
catolystswereprepared (P1/HXand Pt/SrX) by impregnationof 0.8 wt%oPt on l3X-zeolite. The catalyst activity and
selectivitytowardisomerization, and catalyt deactivationwereinvestigated.
Theisomerizationunit consisledof a vertical tubular stainlesssteelreactorof 2 cm internaldiameter,3 cm external
diameterand 68 cm height.Theoperatingpressurewas atmospheric runs. Theliquidflow of light-
for all experimental
naphtha was A.4 IJh, and the catalystweight was 50 gm, H/H.C ratio usedwas 4 for all experimentalruns. The
isomerizationprocess wasstudiedat dfurent tenperaturesof 250, 270, 275, 300,325, and 350oC , Itwasfound that,
the optimumisomerizationtemperatureis 270"C
Theisomerizationactivities snd selectivitiesos afunction of timeshowedhigh activity at the beginningof the reaction
ord were deactivatedrapidly. This indicatesthat the deactivationof PI/HX and Pt/SrX resultsfrom the blocking of pore
nouth by the depositedcarbon. Thefollowing deaeliv;ationdecreasingorder, PI/HX > Pt/SrX wasfound. On the other
,nnd, PI/HX cotalyst showshigher activity and selectivitythqn that of Pt/SrX.
It waseoncludedthat,only an cverageof 90 wt% of the carbonatomsfeed into thereactor(light naphtha)is detected
in theproductstreamduetoformation of cokedepositswhich leadsto cqtalystdeactivation.Theresultsclearlyshowed
thot hydrogenis necessary for the ltydrogenationof olefinsin order to preventoligonerizationreactionthat leadslo
cokeformation and catalystdeactivation.

andPVSrXcatalysts,deactivation.
Icywortls; catalyticisomerization,light-napgtha,PIJHX

lnboduction In general,a catalystmay lose its activity or its

selectivitydueto poisoning,fouling,sinteringand lossof
Due to a heightenedawarenessof the environrnental activespecies[], Oneof the mostchallengingtasksin
poblem worldwide,expectations of cleanand unleaded the designand operationof industrialcatalyticprocesses
gasoline and world demand for gasoline have been is the prevention,or at least the control, of catalyst
ircreasing.Catzl5'ticisomerizationis regardedoneof the deactivation. Loss of catalyst activity is often
mostimportantprocesses in oil refinerieswhich produce accompaniedby a loss in selectivity. This leads to
cleanand high octanegasoline.Isomerizationconveftsn- greater formation of undesired by-products such as
butane, n-pentaneand n-hexaneinto their respective carbonoxides,poor utilizationof raw rnaterials,wasteof
boparaffinsof substantiallyhigher octanenumber.The energy,and increasedpollution [3,4]. Thus, solving
oommonfeedstockefor isomerizationprocessis the light deactivationproblemsis of paramountimportancefor the
saight run naphtha,which consistsof the lighter fraction economicand ecologic performanceof the process
cs tc6Lt,2l. industry.Understanding deactivationmechanisms could

IJCPEVol.8No.3(September
2007) 43
 otin,

ultimately lead to the design of inherently stable diameter,3 cm externaldiameter

and 68 cm height
catalysts,with considerable benefits.Solvine
-ofdeactivation (reactor volume 214 cm3).The reactor was heated
problemsrequiresa detailedknowledge th. ,uny uniformlyusingan electricalfurnace.Thetemperarure at
causesandmechanisms involved[6,7,gJ. the reactorcenterof the catalystbed and at different
, On theotherhand,foulingformationis regarded oneof points in reactor and system were determinedby
the most importanttypes of catalystdeictivationin manufacturingan interface system, (Computerized
isomerizationprocess.Generally,the kinetics of a TemperatureMeasurementSystem) which has ten
catalystdeactivationis a functionof temperature, time, calibrated thermocouple sensors typeK (iron-constantan).
pressure and the concentrations of different Theinterfaceis programmed
andrun by a computer(p4).
substances [9, l0]. The reactoris fittsd with accuratemeansfor controlof
The principal differences between the various pressure,gas and liquid flow rates. The experiments
industrialprocesses of isomerizationrelateto thecatalyst were conductedat atmospheric pressure.
Feedmixtures
used;this will in turn affectthe feedpretreatment steps of hydrogenand hydrocarbonwere preheatedto reactor
and spent catalyst characterization.The two principal temperature beforeenteringthe bed.
typesof catalystidentifiedin the industry areiplatinum
on zeolite,which operatesat temperatures above2OOoC,
and platinum chloride on alumina, which operatesat
temperatures below200 oCIll, l2]. Themainadvantage
of zeolitesoverplatinumon chlorinated alumina.atalyJtt
is that they have a much betterresistance againstfeed
impuritiessuch as water, which obviatesthe need for
expensivedrying facilities.Moreover,in zeolitebased
processesit is unnecessaryto continuouslyadd
chlorinating agents, remove hydrogen chloride from
effluent steams and take precautionsagainstcorrosion.
Manyauthon haveinvestigated the catalystdeactivation
phenomenon over PVA|2O3catalystusingn-pentane,n-
hexane,and n-heptaneas a feedstockfor isomerization
reaction [ll, 13,l4].
In order to designand optimize catalysts,a detailed
undentanding of the reaction mechanism,kinetic,
deactivation and catalyst properties is of primary
interesl The combinationbetweencatalystperformance
and understandingof catalystdeactivation will enable
the designof a new catalystwith reduceddeactivation
and increased acrivity and selectivity for desired
products.Therefore,the presentwork aimsto:
- providea substantiated Fig.(1)Generalview of experimental apparatus
knowledgeof the isomerization
reaction based on bifunctional zeolite catalystsby
using light-naphthaas a feed and determiningthe
optimumproc€ssconditions. Materials
- test the performance,deactivationrates and catalyst
Two typesof catalystsnamedPt/HX and pt/SrX were
stabilityunderoptimumprocess conditions prepared.The preparationof the catalysts were carried
out by impregnationof extrudates(3 x 5) mm of sodium
ExperimentalWork typel3X zeolite,SilAl = 2.8 ( Linde Company)with 0.8
wt% platinum.
Catalytic unit Dried and desulfurized Iraqi light petroleumnaphtha
The experimentalstudy was carriedout to investigate delivered by Al-Dura Refinery-Baghdad was used as a
the catalysts activity, selectivity and catalysts feedstock.Hydrogengas was suppliedfrom Al-Mansour
deactivation rate by building an experimental rig plant (purity is 99.9 %). Various rypes of chemical
specifiedfor isomerizationreaction,as shown in Figure compounds wereused.Hexachloroplatonic acid H2ptCl6
(l) whichrepresents generalview of experirnental unit. (40%wt Pt), strontiumchloride,ammoniumchloridewere
Figure(2) showsa schematicdiagramof a fixed bed obtainedfrom FlukaAG.
flow-typeapparatus.The isomerizationunit consistsof a The properties and chemicalanalysisof light-naphtha
verticaltubular stainlesssteelreactorof 2 cm internal are tabulatedin Tables(l) and (2) respectively. On the
otherhand,accordingto G.C, analysisshownin Table

44 IJCPEVol.BNo.3(September
2007)
 Khalid A. Suk*ar et oI

bt
d 1-lI eteringburette
tr 3-Dosiug putry
I
3-Liquidflonmeter
U
d J- I iddelralt'e
tr 5- IIJ flon'meter
t 6-5AlloletularSiete
j- Onewa.vtalve
f
8-II iringsettisr
t
3
9-feedpreheatiug zone
I 10-Temperamre s)-stem
control
1I- Pressure sf$em
toutt'ol
12-Smiuless reattor
steel
13-II eatiug e
fiu'uac
1.1- Tbermocouples
15-Computerizetliuterfares.Ystem
16-P4conpilter
l?- Cooliug sl'srem
18-Gas ChronatograPhY

apparatus'
Fig. (2) Schematicdiagramof the experimental

(2), the main componentsof the light-naphthafeed are Table(2) Chemicalanalysisof light-Iraqipetroleum
naphtha
n-pentane and n-hexane (35.70 and - 40'8 volYo
reipectively) which indicates that, the catalytic ComDosition wl%o
35.70
isomerizationfor suchfeed may be a dominantprocess' n-Pentane
40.80
n-Hexane
Therefore,such processcan be used to improve the MethvlCvcloPentane l l l3
octanenumberwhen optimum operatingconditionsare Bertzene 1,40
applied. Cvclohexane 2.82
n-HeDtane 3.15
leum n-Octane 1.88
Table( I ) TheproPerliesof I t-l i
t.54
Property Data Toluene
t{ 604 0.665 1.22
80.5 Total 99.64
API
Distillation
I,B.P, 3? oc of 13X-Zeolite'
Modification
5 Vol.7odistilled 42'C
l0 Vol.o/odistilled 48"C In orderto modify the NaX zeolitespecification,NaX
20 Vol.%distilled 52'c zeolite were exchangedwith two type of cations
30 Vot.%distilled 560C
40 Vol.% distilled 60.oc (Ammonium and Strontium). The Na+ ions were
50 Vol.%distilled 550C ixchanged for NH4+ ions to obtain the HX by ion
60 Vol,%distilled 68"C exchangingthe original NaX zeolite with (3 N )
70 Vol.% distilled 760c
g20c u*rotiiurn chloride-solution [4]' Thus ?8'75gm of
80 Vol.%distilled
90 Vol.o/odistilled 86'C ammonium chloride in 500m1 distillate water was
95Yol.%distilled 920C contactedwith 50gmof NaX zeolitewith stirringfor I hr
124'C oC . Then,the exchangingprocesscontinuedfor 4
E.B.P. at 50 oC.'The exchange
96 Vol.%
TotaldistiUate daysat laboratorytemperatureof25
TotalrecoveryResidue 0.7 Yol.o/o
J.3 \ol.Yo reiult shows82 % of exchanging rateofNa* by Sr-'
["oss
68.2 On other hand,SrX form zeolite was preparedby ion
SulfurContent < 3 ppm(Desulfurized) exchangingthe original NaX zeolite with (3 N )
KinematicViscosity 5.4x10'' m'ls strontium chloride solution [5, 6]' Thus 80gn of
at 25oC

IJCPEVol.8No.3(SePtember
2007) 45
 Study of catalysts dea9lry!!!9n in isomerizationprocess Io produce high octane gasoline

strontium chloride in 500m1 distillate water were aromatizationand cracking selectiviqr are low, while
contactedwith 50gm of NaX zeolite with stirr.ingfor l hr isomerizationof light-naphthais relativelyhigh. So that,asrhe
at 50oC. Then, the exchangingprocesscontinuedfor 4 reaction temperature increases above 300 oC the
days at laboratory temperatureof 25 oC with 85% of hydrocrackingand aromatizationreactionsareaccelerated and
exchangingrate of Na* by Sr*. isomerizationactivity and selectivity startedby,decreasing.
Then, the exchangedsamples(HX and SrX) were Therefore, according to Figure (4) the optimum reaction
.l10 oC
filtered, washedand dried at for l0 hours.The temperaturefor isomerizationis at 270 oC for such type of
preparedsample was washedwith deionizedwater to be catalystsand feed composition.On the other hand,Figure(3)
free of chloride ions, and drying procedureswere indicatesthat, the PI/HX catalystshows higher selectiviry
repeatedtwice. The obtainedzeoliteswere calcinedin air toward isomen than that of Pr/SrX.This is amriburedto high
at 5000C for 6 hoursto obtainthe HX and SrX forms. surfaceareaand the eflect of cationfvne that forms the final
catalyst.
Preparation
of PVHXandPt/SrXcatalysts
Table (3) Characterization
dataofprepared catalysts.
The exchangedzeolires(HX and SrX) were loaded
with Pt at concentrations Characteri;atron Pt/HX Pt/SrX
of 0.8 wt % by impregnation
processriith aqueoussolutionof hexachloroplatonic Source Prepared Preparcd
acid
Platinumcontent($t%o) 0.8wt% 0.8wt%
H2PIC16 . The preparedsolutionwas added dropwiseto
t h e z e o l i r eu i i h m i x i n g f o r 4 h o u r sa t 2 5 ' C . T h e m i x t u r e Area(m'lg)
Surface 340 325
ChlorineContent(wt7o) 0.25 0 .r 8
was then left at room temperaturefor 24 hours, it was (si/Ai) 2.8 2.8
stined interme,liately during this time. The mixture was
then slo*lr eraporatedto drynessover a period of 8
Catalystdeactivationis definedas a phenomenonin which
hours ar rsmperarureof 75oC. The resultingcatalysts
the sffuctureand stateof the catalystchange,leadingto the
u'ere driec in air ar I l0'C for an additional 12 hours.
loss of active sites on the catalyst'ssuface thus causing a
Then. the sanples riere calcinedin air at 500oCfor l0
decreasein catalystperformance,Therefore,eachcatalystwas
hours lincreaslrg ro that temperaturewith a rate of
subjectedto an aging period.After a pretreatrnent at 350 "C in
0.5"C mir I ar: i'rnaili reducedat 350oCin flowing H2
flowing hydrogen the catalyst was submitted to l0 hr of
fcrr-l rtrurs ,1. 5,. Then. the samplesare referredto as
standard reaction conditions (T=270 oC and atmospheric
P t H X a n dP : S : X c a t a l \ , s t s .
pressure).The catalytic activity, expressed in terms of
percentage iso-butanes,
iso-pentanes and iso-hexanes yield, is
Procedure plonedas a functionof onsffeamtime as shown in Figure(4).
B e t o r et : e e r p e r i r n e n t st h, e c a t a l y s w
t a s d r i e da t l l 0 Both catalyss showedgood stability,however,the activity of
'C in ii:rc:e; Pt/HX fell rapidly and it was even lower after l0 hr than that
Jlsruicr one hour and then reducedat 350
"C in hl crLrser florv for three hours. The operating of Pt/SrX. The fast catalystdeactivationthat was notedafter
pressure',r:;e he,,j constantat I bar for all experimental few hours of reaction time can be attributed to a high
runs. Th: ii.:.riJ t-lo* of light-naphtha was 0.4 Llhr , hydrogenation-dehydrogenationcapacity of platinum
and rhe Brnrrr.rnr of catalyst was 50 gm. A accordingto the conclusionssubmittedby the work of Tomp
hrdrogerhrC:o;arbon molar ratio used was 4 for all et al. Il l] andJorgeet al. u2l. Also,Figure(4) indicates thar,
experimerui i-u:rs.The isomerization processcarriedout both catalystsloseapproximately35% of their initial activity.
a t a r a n i e r . f : 3 n F e i a t J r evsa r i e db e f w e e n 2 5 0 , 2 7 5 , 3 0 0 ,
Ji). ano _.-'(_'-L 80
The feec a:c :he effluent reactor were analyzed in a
gas chromatogiaph(Shimadzu GC-2014) FID using
capillar_rcoiumn ( S.G.E., length=25 mm, l.D.= 0.22 70
mm, film=0.iun: t and usingN2 as a carriergas. I

U)

Resultsand Discussion 60
N
Table (3) shous the rnain characterizes of prepared
catalysts (PtlHX and Pr Sr.\. Ir is clearrhat,Pr/HXcaralyst
fU
showsa total surfaceareagieaterthanthat of Pt'SrX.
200 22s 2s0 27s 300 325 350
The reactiontemperatureinfluencesisomerization acti!'iN
T e m p e r a t u r e( o C )
and selectivityof the catalvstto a higler ertenl Figure(3)
shows the effect of reaction temper"arure on isomerzation
selectivitytoward branchedisomershrdrocarbons. lt is noted (3) The influenceof reactiontemperature
Fi_s. on
that, at low reaction temperatures ll,<. 2-\0. l-5 oC the isomerization selectivity

46 I J C P EV o l . 8N o . 3( S e p t e r n b e
2 r0 0 7 )

l
 Khalid A. Sukko a aI

show fast catalystdeactivationcausedby depositionof

carbonaceous materials(coke)on the catalystsurfaceand
s 8 0 pores.The major productformedin the beginningof the
reactionwas iso-butane. Higher contentsof iso-hexane
'! were detectedin the course of the deactivationrun.
; 6 0 However,the presenceof hydrogenin the reactionzone
(Hydroisomerization)is essential to minimize coke
5 5 0
formation[2, 12,13].
N
Figure(6) showsaromatization selectivityas a function
4 4 0
of reactiontime. In this figure, Pt/SrX catalystshows
3 3 0 higher aromatizationselectivity than that of PI/HX
catalyst.This is attributedto high concentration of active
acid sitesin this type of catalysts, in which promoted
aromatizationreaction take. This conclusion is in
agreement with theworkof Donket al. [14].
of PVHXandPVSrXcatalysts
Fig.(a)Deactivation
Conclusions
90
x In this paper the isomerizationof light-naphthafor
producing of branchedisomershas been investigated.
Normal paraffin isomerizationin presenceof hydrogen
8€) 7 0 (hydroisomerization) is an equilibriumlimitedreaction,
E 6 0 in which branchedparaffin isomersare favoredby low
ternperatures, Therefore,it was concludedthat, in order
5 5 0 to prevent the undesiredreactions of cracking and
N
aromatization,the isomerization process should be
b 4 0 oC as an optimum operating
carried out at 270
A 3 0 temperature for both PI/HX andPt/SrXcatalysts.
6 l0 t2 It was concludedthat only an averageof 90% wt of
Time(hr) the carbonatomsfeedinto the reactor(light-naphtha) are
detectedin the product This
stream. loss (- 10%) is due
to formation of coke depositswhich lead to catalyst
selectivitywith agingtime
Fig.(5)Losesof catalysts
deactivation.On the otherhand,the resultscleartyshow
that hydrogen is necessaryfor the hydrogenationof
\c 25 olefins in order to preventoligomerizationreactionthat
leadsto cokeformationandcatalystdeactivation.
.: 20 In spite of the presenceof cske depositspoisoningof
t) the metalsites,cokedepositsalsoblock the acidsitesof a
.{)9 l s zeolite.The followingdeactivationdecreasing order of
O >
catalystsPt/HX PVSrXwas found.On the otherhand'
o l 0 PI/HX catalystshowedhigher activity and selectivity
N thanof PVSTX.

Acknowledgment
L ( )
The authors gratefully acknowledgethe financial
supportprovided for this work by Ministry of Higher
Education and Scientific Research/ Scientists and
selectivityasa functionof reaction
Fig.(6)Aromatization CreatorsDeparrment-Baghdad.
time

On the otherhandFigure(5) showsthe isomerization References

selectivity toward paraffin isomers.The isomerization J.C.,
l- Maloncy,M.L., Gora,L., Mcleary, E.E.,Jansen,
selectivitywas reducedfrom 85% to 55o/ofor PtlHX and MaschmeyeqT. "Hydroisomerisation of Hexane
catalystand from 74Yoto 46Ysfor Pt/SrXunder l0 hours within a ReactorComposedof a Tubular Silicalite
of reactiontime. Both catalystsusedin the presentwork

IJCPEVol.BNo.3(SePtember
2007) 47
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IJCPEVol.BNo.3(September
2007)