Jo urnal of Sci entific & Industri al Resea rc h

Vo l. 62 , Octobe r 2003 , pp 963-978

Catalytic Naphtha Reforming: Revisiting its Importance in the Modern Refinery*

Uday T Turaga ':l and R amnarayanan Ramanath an b
"Bartl esv ille Techn o logy Ce nt e r, ConocoPh illips, Bartl esv ill e, O K 74004, USA
Th e paper rev iews catalytic naphth a re fo rming, a process th at has co mpl e ted 50 y o f ex iste nce and ha s improved th e
quality o f human life g loball y. Al so examines in det ail are the hi stori cal backgro und o f rci'o rmin g, reac tio n c he mi stry.
reacti o n the rmodynamics, process detail s, process variab les, co mme rcial processes, and future o utl ook. Rece nt e nvironment al
regulation s have co mpl etely re-d rawn the obj ecti ves o f refo rmin g and have even qu es tion ed its releva nce. Atte mpt s are also
made to ex pl ain , in brief, the new c hallenges faced by reformi ng.

Keywords: Catalyt ic nap hth a refo rming, Re fin ery, Napht ha re fo rming, Reforming

Introduction
The Charles Stark Draper Prize, ofte n referred to
as the Nobe l Prize for the e ngineering profess ion , has
been awarded eight- times s ince its inception in 1988:
for the development of the integrated circuit, the
turbojet engine, the FORTRAN computer langu age,
the communication sate llite, fibre optics, the creation
of the internet, medical dru g de live ry , and catalytic
naphtha refo rming. In awardin g Vl adimir Hae nse l the
Charles Stark Drape r Prize in 1997, the National
Acade my of Engineering gave deserved recogniti o n
to catal ytic reformin g - a revo luti o nary pe trol eum
refinin g process that in an e nviro nme ntall y be ni g n
way created c lea n and abundant trans portation fuel
(Figure I ), e nabl ed the mode rn pl asti cs indu stry, and
improved standards of livin g g loballi . Figure I
shows the quantum jump in o il consumption ,
ex plained in part because of re formin g, whil e Figure 2
shows the distributi o n of the cataly sts bus iness
amongst variou s sectors and processes in c ludin g
reforming. Haense l2 inve nted Platformin g ; th e first
commercial reforming process li censed by UOP,
thereby g iving birth to catalytic re formin g.
Th e catalyti c reformin g process converts
petrol eum naphtha to hi gh-octane gaso lin e poo l
' Dedicated to th e me mo ry o f Vl adimir Haensel
ICo rresponding auth or
Phone: (91 8) 66 1-0 I 13, Fax: (9 18) 662- 1 I 15
E-mai l: Ud ay. T .Tura rga @co noco phillips.com
hDe partment of C hemi stry, Th e Pennsylvania State Uni vers it y,
Uni versity Park, PA 16802 , USA

co mpo nents. T hese hi g h-octa ne gaso lin e poo l

co mpo ne nts are mainl y bran c hed and aromat ic
hydrocarbo ns, w hi c h are less prone to ignite
pre mature ly in inte rnal co mbu stion e ng in es and thu s
reduce " kn ockin g" substantiall y. The naphtha fraction
of c rude o il , predominantl y co nta in s a lkan es and
cycloalkanes, which in a catal yti c refo rme r are
"se lective ly re formed" to aromati cs. Hydrogen an
important byprodu ct o f the process . find s nume rou s
application s within th e re finin g indu stry parti cularly
for the prod uct io n of c lean fu e ls. Th e presence of
refo rmin g in a re finin g co n fig urati on of the 1980s is
de pi c ted in Fi gure 3.
Hydroformin g, th e process jointly developed by
the Standard Oil Compan y (now Exxo n Researc h and
Engineerin g C o mpan y), th e Standard Oil Co mpany of
Indiana (now American Oil Co mpany), and the MW
Ke llogg
Company
in vo lved
the
cata lyti c
de hydrogenati o n of me th ylcyc lo hexane (prese nt in
petrol eum naphtha) to to lu e ne: th e concept w hi c h
eventuall y led to th e deve lopme nt of cata lyti c
re formin g . Th e first co mme rc ia l unit of H ydrofonnin g
went on stream in 1940 at th e Pa n Ame ri can Refinin g
Company in T ex as C ity, Tex as using a fix ed-bed
molybde na-a lumina c ataly st a nd was carri ed out at an
external hydrogen pressure of about 15 atmos to avoid
rapid deac ti vati o n of th e ca ta lys t.
The second W o rld War played a significant rol e
in cata lyz in g th e tec hn o log ica l growth of the
petrol eum indu stry and ca ta lyti c reformin g was no
exce ption . Th e need fo r hi gh-oc tane gasoline ror the

964

J SCI IND RES VOL 62 OCTOBER 2003

Consumption
Cons~ption

1990

1.2 , - - ------------------------------------------------------

E'h'rifi~ti0(Y
0.8

Platfom1ing

0 .0

Alkylation

Continuous

0.4

Batch
ni>tma';00
Distillation

0.2

o ~~-.----=F====~~~-----~--~~--~----~--~
1880
1900
1920
1840
1860
1940
1960
1980
2000
2020

Figu re I - Oil refining birth through 2000'"

Environment
HDT+ Hye
25

40

~
Refining

40

Fi gure 2a -

FCC

r-I

Ch,;;OO"

Applications 01 calalysi s,6

allied forces was substantial but th e need for

trinitrotoluene (TNT) obtai ned from tolue ne was
greater. In those days, TNT was an importa nt, and
perhaps the on ly exp los ive whose increasing demand
resulted in six more unit s of the Hydroforming
process'. UOP deve loped and licensed the fixed -bed
Platforming process using Pt on halided alu mina
catalyst4 ,5. It was with P latform ing and its vastly
superior Pt catalyst that the entire business, sc ience
and technology of catalyti c reforming achieved iconic
status in the refining industry. Almost 50 y later,
P! atformjng as a commercial process of UOP, in

40

\
Fi gurc 2b -

Other 5

Alkylation
25
REF +
(SOM t5

Applicali ()!1s Orcatalysis in relining'('

particu lar, and ca talytic reforming , in general, are

preferred processes in commerc ial use the worldover
for producing hi gh-octane gaso lin e, hydrogen , and
aromati cs as petroche mi cal feedstock s.

Chemistry of Catalytic Reforming

The important reactions (Figure 4 ) wh ich OCellI'
during ca talytic reformin g are: (a) Dehydrogenation
of naphthenes (cyclohexanes in particular), to
aromatics , (b) Dehydroisomeri za ti on of alky lcyc lopentanes to aroma ti cs, (c) Dehydrocyclizatio n of
alkanes to aromatics, (d) Iso me rization of n-alkanes to

965

TURAGA et a l.: CAT ALYTI C NAPHTHA REFORM ING

Refinery fu el
KefineryGas

LPG

II

Naptha

UG

Hz
Crude
Distillation

--+I

-.

Isomerization l C5+J

t t

fractio nation

Refonning

-,..

Gasoli
letfuel

Hz

LPG

HDS

.--

Alkylation

Di esel

Heat! ngOil

f CC
Vacuum
Distillation

- - . Heavy Fuel 0 il
Coke

I Visbreaking
Refinery Fuel
Refinery Fuel
Figure 3 -

(s)

(b)

o ------..-0
(;
-0
- - -- -

(d)

PI s it!;!'

~,-----------~-------------------~~

0 + 3H,

(e) C- C-C-C-C-C-C

+ H,

Hydroca rbon feed

----. RI h +

(<ldsorbcd)

< 4 - - Poisons (c(lke . . -

3H,

fast

adsorbed)

---+

Initial poisons + H2
(coke adsorbed)

slow

Poisons (gas lind surface

transport )

+ 4H ,

C
I
C- C-C-C-C-C

C-C- C-C-C-C-C _

Systematic of a relinery ci rca 19801.1(,

{oj C-C-C-C-C-C-C -~_ C-C-C-C

Initial poi sons

'--""'New unsaturat es
slow crac kin ~

-::;==:::!:

I)ol ymcri zed po isons .. R2

slowc!>1

~~------------------,------------------~

+ C-C-C
Acid s ites (rate controll ing)

Figure 4a -

Catalyt ic reform in g reac ti o ns'

branc hed a lkanes, and (e) C racking o r fragme ntati on

react io ns (hyd rocrack ing or hydrogeno lys is) yie ldin g
products of carbon num ber lower th an that of the
6
reactants .
The dehydrogenati on of cyc lohexanes (a). the
dehydroisome rization of a lkyicyc lopentanes (b) , and
the dehydrocyc li zation of n-alkanes (c), to produce
aromati cs are stro ngly e ndothermi c reacti o ns and are
facilitated by highe r temperatures and lower hyd rogen

Fi gure 4b -

Pos tul ateu mec hani sm for rerorm in g~

parti a l pressures . Th e constra int of catalyst

deac ti vatio n from coke depos iti o n, however, does not
all ow operat io n of reformin g units at high
te mpe ratures and low hyd rogen parti a l press ures
7
dictated by the rm ody nami cs Para ffin iso meri zati on
to a lke nes (d) a nd hyd rocrack in g and hydrogenolysis
(e) a re exo th e rmi c reac ti ons wi th the latter be ing
hydrogen co nsumin g . Tabl es I and 2 :-.ummari ze the

J SCI I. D RES VOL 62 OCTOBER 2003

966

thermodynamic and kinetic aspects of the reactions

taking place in a commercial reformer.

Mechanistic and Kin etic Featu res

Re forming ca talysts are typica lly metals
supported o n an ox ide carrier and possess two
d iffe rent types of ca ta lyti c activities : an ability to
hydrogenate and de hydrogenate hydroca rbon s and the
ability to catal yze hyd rocarbon rea rra ngeme nts . Th e
fo rmer is a pure ly me ta l-cata lyzed reaction and does
not require acid sites, while the latter is ca talyzed by
R
ac id s ites o n the support ,9 . Dehydroi so me rization and
iso me ri zat io n requ ire metal sites for alkane or
cyc loa lk ane de hydrogenati on to a lke nes throug h a
carbocatio n-like species fo llowed by rearran gement
on acid s ites to form the isome ric branched a lke ne and
finally yie lding the isome ric branched alkan e through
hydrogenati o n on metal sites . The tran s po rtation of
th e inte rmediates between the se active sites occurs
throu g h th e gas phase 10 . From the precedin g mode l,
we obse rve that the rates for these reac tions are
limited by the catalytic activity o f the acidic sites.
There fore , co ntinued inc rease in the meta l content in
reforming ca tal ys ts leads to no appreciable increase in
catalytic activity and , in fac t, covers up the acid s ites

9
and red uces the overall re f ormlllg rate.

Reforming Catalysts
Catal ys is has played a c riti cal rol e III the
e vo luti o n o f re finin g tec hnology (Figure I) a nd

catalytic re formin g is no exce ption " . T he dec isive

para mete r, which established UOP's Platformin g
process as the most prefe rred technology for catalytic
re forming was th e discove ry of th e Pt on alumina
2
(Pt/AI 2 0 , ) catal yst by Hae nse l
Chevron' co mme rci a li zed th e Pt-R e/A I2 0 1
bime talli c ca tal ys t di scovered at th e ir researc h cente r,
c hang in g th e co urse o f ca tal yti c refo rmin g and th e
1
sc ie nce of re fo rmin g ca tal ys is conc lusi ve ly. Exxo n l 2.1.
de ve lo ped a nd com me rc iali zed the Pt-lri AI 20 :; seri es
of bimetallic re formin g catal ys ts. Both these catal ysts
were mu c h mo re active than th e traditional Pt catalyst,
with the Pt-Jr/AI 20 , deve loped by Exxo n di splay in g
substantiall y g reate r ac ti vity. The bimetalli c cata lys ts
all but co mpl ete ly re placed the Pt/AI 2 0 ; catal yst in
the 1970s and ea rl y 1980s. Impro ved act iviti es o f
th ese bimetalli c catal ysts e nabl ed re formin g units to
run for lon ger durations be twee n regene rati o ns , o r for
a g ive n le ngth of time, allowed lowe r pressures fo r
hi g he r re fo rmate yie ld s.
Platilllllll on A llIl1lina

Th e amount of Pt dispe rsed o n alumina in

com me rc ial refo rmin g ca tal ys ts is 0 .3-0. 6 wt pe r ce nt.
C hl o rine is also present in th e amounts o f 0.3-1.0 wt
pe r cent. T hese cata lysts a re prepared by
impregnation of alumina with c hl o roplatinic ac id
followed by calcination in air be twee n 825-875 K.
S urface area of th e a lumina usuall y used is 150-300
2
m /g. The press ure drop and diffu s io n limitati o ns

Table 1- Thermod ynami c data for lypical rcformin g reacli on ~ x

Reaclio n
Cyclohexane H benzene + 3H:!

6 H"
kl l mol of hydrocarhon

6 x 10 "

220.7

0. 086

Melh ylcyclopenlane H cyclohexane

II-hexane H benzene + 4H:!

0.78 x 10

l1-hexane H2-lllelh ylpenlane

II-hexane H I-hexenc + H:!
Table 2 -

Kpat 500C. P in allll

- IS.X
5

265.(

1.1

-5.9

0. 037

129.6

Rale behav ior and heal effecls or impmlanl rci'ormin g reac li olls x

ReaCl ion lype

Relalive rale

Effecl of increase in lOlal pre~s un;

Heal effect

Hydrocrac kin g

Sl owest

Increases ra le

Qu ile exolhermi c

Dehydrocyc lizat ion

Sl ow

Small dec rease in rale

End ol hermi c

Iso meri zali un of paraffi ns

Rapid

Decreases rale

Mil dlyexo lherm ic

Rapid

Decreases ra le

Mildl yexo lhermi c

Para ffi n de hydroge natio n

Qu ile ra pi d

Decreases

Naphthene deh ydrogenalion

Very rapid

Decreases conversi on

Na phlhene

i~omer i zati on

c o n ve r~ i o n

End olhermi c
Very endolherm ic

TURAGA et al.: CATALYTIC NAPHTHA REFORMI NG

determine the shape of the reforming catalysts and the

preferred shapes are usually pe llets. or extruda.tes.
Di spersion of the metal on the alumma support IS . a
critica l parameter for reforming, as for any catalytiC
process, and is defined as the ratio of the amount of
ex posed me ta l on the surface to th e tota l amount of
metal in the catalyst. Chemisorption studies have
shown that freshly prepared Pt/ AI 20 , reformin g
cata lysts are c harac terized by ex tre mely high Pt
di spersion. Hydrogen c he misorption , extended X-ray
absorption fine structure (EXAFS) and anomalous
X-ray scattering studies have a lso confirmed high Pt
dispersion which ex ists in an amorphous state,
ac hi eves mi croc rysta llinity on reduction with
hydrogen. Other studies, e.g., 195 Pt NMR, ha ve a lso
reached si mi lar conclusions'.

Acidic Properties of the Alumina

Catalytic reformin g as a process stimulated
tre mendou s interest in the role of the support in the
science of catalysis and led to so me very seminal
studies . 14 Alumina, known to be amphoteric, has a lo t
of hydroxyl groups on its surface which are the prime
source for Br(llnsted (p rotonic) acidity and respon sibl e
for hydroca rbon rearrangement reaction s. The
presence of c hlorine (fluorine, in the early 1950s) in
reforming catalysts is thou ght to impart acidity in
a lumina by interactin g with the surface hydroxyl
groups,
although
fundamental
studi es
and
understandino- on thi s particular aspect of reformin g
b
.
6
catal ysts are still not comprehensive .

Platinum-Rh enium Catalysts

These a lumina supported bimetalli c catal ysts
genera lly contain an amount of rhe nium comparable
to the amount of Pt (ofte n 0.3 wt per cent each) . These
cata ly sts are prepared differently from other
bimetallic catalysts and organometallic precursors as
dirhenium decacarbony l, Re2(CO)1O are used to
impregnate Pt supported on a lumin a. Fundamental
studies invo lving characterization tech niqu es as
chemisorpti on , EXAFS and X-ray absorpti o n have
shown that rhenium exists in the reduced form and is
ex treme ly sensi tive to poi sonin g by sulphur and less
sensitive to coke deact ivation co mpared to Pt. It is
believed that Pt and rhenium are extensively
coordinated to each other in bimeta llic clusters, whil e
their individual coordination to oxygen in the a lumina
framework is small. These stud ies indicate that the
composition and concentrati on of these clusters vary
WI'de I y 15 .

967

Platinum-Iridium Catalysts
Platinum-iridium
bimetallic
clusters
are
prepared by impregnatin g the alumina support with an
aqueous solution of c hl orop latini c and chloroiridic
ac id s 15. After the impregnated suppo rt is dried and
ca lcined at mild co nditi o ns. it is ex posed to flowing
hydrogen to reduce Pt and lr. The catal yst contai ns
co mparabl e amounts of Pt and Ir with a total metal
content of 0.5-1.0 wt per ce nt. The me tal dispers ion is
c lose to one, implyin g that almost all Pt and Ir atoms
in th e catalyst are on the surface. Inte raction between
Pt and Ir has been studi ed ex te ns ive ly but co nclu sive
results on the type of inte ract io n, if at aiL are still
e lu sive' . Iridium unde rgoes ox idative agglomeration
to form clusters of Ir02 at hi g h te mpe ratures and so
Pt-Ir bimetallic cata lysts are calcined at te mperatures
mu c h lower th an those used fo r Pt o n a lumina
cataly sts and log icall y th e regenerati o n procedures for
these catalysts are diffe re nt.

Platinum-Tin Catalysts
These cata lysts were introdu ced in catalytic
refo rming units by UOP with th e ir Continuous
Catalytic Reformin g (CC R) process. The co mbined Pt
and Sn content of th ese cata lys ts is less than 0 .8 wt
per ce nt. These catal ysts are prepared us ing chlorided
precursors and are red uced above 673 K. The Pt-Sn
catalysts are th e focus of inte nse research because of
two issues: th e ox idati o n numbe rs of Sn after
exposure of th e catalysts to hydrogen and th e extent to
l5
which bimeta llic e ntiti es of Pt a nd Sn are present .
UOP introdu ced these with the Contin uous Cata lytic
Re former (CCR ) becau se of th e tend e ncy of PtSn/AI 20 , to deactivate rapidl y.

PlatinumlKL Zeolite Caw lvsts

All comme rcial cata lys ts are limited by low
se lecti vity o f the aroma ti za tion of Cr, and C 7 alkanes
re lative to that of hi g he r carbon numbe r alkan es in
the naphtha bo ilin g range. The yie ld o f th ese
cata lysts fo r co nvert in g C(, a lkan es to benze ne is
typically only about 10 pe r ce nt as against 60 per
cent for me th ylcyc lo pent a ne and 90 pe r cent for
l6
cyclo hexane . It has been suggested that thi s may be
du e to th e ac idic chlorided alumina support. A
ca tal yst in which KL zeol ite is used as a su pport for
platinum has a s ig nifi ca nt advantage over
co nve ntion a l refNmin g ca tal ysts. The KL zeolite has
narrow (0.71 nm ) un idirec tiona l chan ne ls and is not
acid ic. The Pt in th e c hann els had di spe rs ion a lmost

968

J SCI IND RES VOL 62 OCTOBER 20m

'
equa I to one 17- 19 . TIle p Iattnum
cata Iyzes aromatizati o n of C 6 and C 7 alkanes with hi g h selectivity.
Since the KL zeolite is not acidic, competing
reac ti o ns of isomeri zation and hydrocrackin g are
strongl y suppressed and thus the aromatization of
a lkan es proceeds unhinde red . T his catalyst , howe ver,
suffers fro m e xtre me sensitivity to sulphur
pOi so nlll g .

Deacti va tion. and Regeneration

Most catalysts, whethe r operated co mme rc ially
or in a laboratory , eventually deacti vate . Deac tivat ion
is very important in commercial operation because it
influ e nces the choice of the operational conditions
and fixes the cycle length between regene ration and
the total I ife of the catalyst. Among th e processes of
petroleum refinin g and the petroc he mical indu stries ,
catal yti c reformin g of naphtha has one of the more
co mpli cated deactivation phe nomena because the
cata lyst presents nearly all the kn ow n causes of
deacti vatio n.
Th e process ing of hydrocarbon s is ge nerall y
acco mpani ed by the formation of carbonaceou s
de pos its on the catal ys t surface . The phe nomenon is
refe rred to as coking and depe nds on catalyst
co mposi tion , operational conditions , and feed
co mpos ition . Coke is formed on acid catalysts
(cracking or isomerization of hydrocarbon s), metalli c
catalysts ( methane stea m re formin g, hydrogenation ,
o r de hydroge nation), and bifunctional me tal-acid
catal ys ts (naphtha reforming, paraffin isome ri zation ,
o r hyd roc rac king) . In the case of naphth a re formin g,
coke formation is the most rapid cause of
deactivation . Refo rming cataly sts a lso deactivat e
because of poi soning by sulphur and nitrogen
compounds, sinterin g (decrease of meta lli c area),
decrease o f chloride concen tration , and heavy metal
depositi on.
Bifunctional catalysts coke from accumulation
of carbon containing s pec ies on the meta l and the
suppo rt H On metalli c sites, two mode ls ex pl a in coke
fo rmati o n. The first mode l invo lves a ser ies of
fragmentat io n a nd
success ive de hyd rogenati o n
reaction s forming carbon atoms, which may co mbin e
to form more g raphiti c and toxic coke depos its. T he
second mec ha ni s m suggests th at th e ro utes o f coke
depos iti on are based on po lyme rizat io n reacti o ns with
the formation of different types of carbonaceous
deposits o n th e me ta l surface . Co ke formation o n acid
sites is assu med to ari se from po lymeri zat io n of

de hydroge nated inte rmediates

me tallic fun cti o n (Figure 4b).

gene rated

by

the

Coke depos iti o n occurs throu ghout commercial

operation on bo th the acid and meta l s ites with the
rate of depos ition be in g hi g he r at the beg innin g. It is
believed that the initial rapid co ke formation occurs
mainly on th e metal fun cti o n. Refo rmin g typi ca ll y
contain 0.3 wt pe r cent Pt whi c h is e nough to result in
enou gh steady-state ac tivity to produ ce all the olefins
that ca n be iso me ri zed o r cyc li zed o n th e ac id
fun c ti o n. Th e initial fa st co king of th e me tal s ites until
a pse ud o steady state o f th e me tal funct ion is reac hed
is call ed a lin eo ut pe ri od . At lo nge r time operations.
the acid function is more deac ti vated by th e s low coke
depos ition .
Co mme rc ia l
naphth a
refo rm ing
catal ys ts
typi ca ll y co ntrol the main react ion :.; name ly th e
iso me ri zati o n and de hyd rocyc li zati o n of C 6 -C 9
paraffins , throu g h th e acid fun c tionality . However, if
th e meta lli c co mpo ne nt is less ac ti ve or th e wo rkin g
pressure is very low, th e me tal may become th e
co ntro llin g fun c ti o n of th e main refo rmi ng reac ti o ns.
Th e le ngth of th e run is also important. If th e run
takes place onl y during th e lin eou t peri d , it could be
co ncluded th at th e me ta l fun ct io n contro ls th e cata lyst
deact ivati on . Thu s, res ults obtained und e r certa in
co nditions cann ot be ex trapo lated to other conditi o ns.
The hea rt o f the naphtha reforming process is
the catalyst and mos t of the process improve me nts
have re lated to catal ys t life and sta bility. Catalyst
regene rati on in c ludes severa l steps such as
e liminati o n of co ke
by co ntrolled
burnin g,
oxyc hl o rinati o ll to re vive th e meta l and ac id
functionalities, redu cti o n with hyd rogen, and , finally
activation by sulphating. With res pec t to ca tal yst
rege ne rati o n, th e re are two mode ls to inte rpret th e
cok e-burnin g phenome no n: ( i) A ho mogeneo us
mode l, when c he mi ca l reaction is the co ntro llin g steps
of th e process. In thi s case the gaseo us reactants
diffu se throu g h the so lid phase reac ting in a ll the
parti c le vo lume a nd ( ii ) A s hrinking core mode l th at
proposes th e ex iste nce of a no n-reac ting nuc le us
w hose s ize dec reases wit h time surrou nd ed by a
cOlllp le te ly burnt s he ll.
T o increase th e stab ilit y of refo rming catal ysts,
some resea rc hers ha ve eva lu ateJ dea lulllinatecl ZSM12, zeo lite ~ , and thei r co mpo sites wit h yAhO, fo r th e
refo rmin g of industrial naphth a. Th ey found that
dea lumin ated ZSM- 12 de mo nstrates unique time-on-

TURAGA

el

969

al.: CATALYTIC NAPHTHA REFORMING

hi ghe r aromati c conversi on, hi gh reformate yie ld s,

more e fficient catalyst regene ration , longe r cata lyst
life and surface stability, and lower pressures and less
hydrogen recyc le.

stream stability for the reaction investigated. Thi s

behavior is a combined result of the acidity and pore
stmcture of the zeolite which do not favour coke
formation. Zeo lites with channel intersections s lightl y
larger than the zeolite aperture do not favor coke
formation . The results demon strated that the
composite cataly sts produce more gaso line-range
hydrocarbon s and show much better time-on-strea m
be haviour than conventi onal yAI 2 0 , catalysts.

Commercially, refo rme rs are typi ca ll y operated

to produ ce a produc t o f co nstant Researc h Octane
Numbe r (RON). Operating co nditi ons of a reformer
a re usuall y described in te rms of severity. As catalyst
deac tivati on in c reases, seve rit y IS in creased to
compensate for loss of cata lyst activity thereby
maintaining product RON . Co mmerc ial reformers are
des igned to process both virg in and c racked naphthas
at 5-30 atmos and 700-800 K. Press ure is achieved by
the partia l pressure of hydrogen, which is 50-80 pe r
cent of the total press ure. Hydroge n pressure
dec reases catalyst deac ti vation and excess ive
aromatization . A hi gh RO re formate yield requires
lower pressures and more stable ca tal ys ts. Indu stri al
catalytic reforme rs invo lve three section s: feedstock
pre treatment, reaction sec ti on, and product separati on
and stabili zer units.

The Reforming Process

Catalyti c reforming has evolved rapidly during
the past five decades to e me rge as one of the most
advanced processes available to the refining industry
with several commercial licensors (Table 3). The
differences c haracterizin g these processes are:
(i) Nature of the catalysts used , (ii ) Catalyst
regeneration procedures, and (iii ) Equipment
conformation and process configuration. Catalytic
reforming processes are modified depending upon
process and product configurations which include

Table 3 - Li sl of reforming li censors"

Supplier

Catalyst description

Ac tivc metal

Acreon catalyst company

AR 403. AR 405: aromati cs producti on

Pt + promoter

Procatalyze

CR20 I: continu ous regeneration

Pt/S n

E20 I-E I000: gaso line/aromati cs r rod uction

Pt or Pt/Re

RG seri es: low to hi gh pressure app li cati ons

1"1. Pt/Rc. Ptl Re+ promoter

Pt/lI' + promoter
Criterion catalysts company

PH F 4,5: gasoline or BTX

p~odu c tion

Proprci lary

PRH F seri es: gasoline or BTX prod uctio n

Kx 120-190 seri es for gasoli ne and I3TX
Indian Petrochemical Corporation
Limited

IRC 100 I, 1002 : aromatics and gaso linc app li cntions

PI. Pt/Rc

Instituto Mexieana del Petroteo

MP-RNA-I , 2: gasoline/BTX

Pt/ Rc

IMP-R A-4: for cont inuous proccsses

Pt/Sn

R-30 series: continuous regenerati on

Prop reil:lry

R-SO seri es: hi gh severity semi -rcgeneration

Pt/R e

R-60 scrics: hi gher stabi lity

Pt/Re

R-72 seri es: hi gher severity semi-regcncration

Prop rcit ary

R -132, 134 seri es: continuous regcncration

Proprcitnry

UOP

Kataleuna Gm bH

8815/03 , 05 : mono metalli cs [all scries

88 19/B:

bime ~ all ie

1'0 1'

gasolinclBTX I

PI
Pt/ Rc

8823: bimetallI C

Pt/Re

8842: continuou s rege ncr:lIi Oil

Pt/Sn

970

J SCI IND RES VOL 62 OCTOBER 20m

Feedstock Pretreatment
The prime obj ec ti ve of feedstock pretreatment is
remova l of pe rmanent catalyst poisons such as
arseni c, lead, and coppe r and to reduce te mporary
cata lys t poi sons suc h as, sulphur, oxygen, and
nitrogen to lower levels (Tabl e 4). Naphtha
hydrotreatment in vo lves vapor-ph ase reaction with
hyd rogen ove r a sul phur-res istant cata lyst suc h as,
Co-Mo/A I20 1 fo ll owed by cooling, ph ase se parat ion,
and effici e nt stripping of a ll H1S and NH, ou t of
treated naphth a . Wate r is al so removed as its presence
leads to acidi c mod ification of a lumin a. C hl orine, at a
predete rmined level in th e cata lyst, is necessary to
influe nce and gene rate des ired a lumin a ac idity but
c hl o rine in the feed leads to se lec ti vity shifts in th e
catalyst , a nd frequ en tl y, excess ive hyd rocrack in g.
C hl o rine is thu s washed away from the feed UStng
wate r o r a lco ho l.

Th e Reforming Reacto r
The reacti on section o f a conventi ona l re forme r
consists of multi-bed reactors in seri es with pre- and
re-heaters between the reactors. Des ired product RON
requires at leas t three or four reactors. The feed stock ,
naph th a, is mi xed with hydrogen (usuall y recyc led
Table 4 -

Nap htha Pretreatment Indieators24

S S; 10 ppm or 5 ppm at hig h

severity
H20

S;

4 ppm

N S;

ppm

Pb ... As ... Cu < 20 ppb

from the process itse l f) and heated to the des ired

te mperature be fore it e nte rs the first reac tor.
Temperature profiles a re an import;}l1t co ns iderat io n
in reac tor des ig n (T ab le 5) . The ove rall reformin g
reac tions a re e nd oth e rmi c and isothe rma l operati o n,
a lthoug h desirabl e, is impract ica l o n a co mme rc ia l
sca le. T o overco me thi s difficulty, the reac tors are
separated into seve ral ad iabat ic zones ope ratin g at
7SSK w ith hea te rs in be twee n stages to supp ly
necessary hea t of reac ti o n, th e re by ho ld in g the ove rall
se ri es o f reac to rs at a co nstant te mpe rature .
Reacto r sys te ms are se lected depending o n
refo rmin g unit co nfi gurati o ns. Initi a ll y, ax ial
downfl ow reac to r sys te ms were used as th ey were
c hea pe r but the hu ge pressure drops c reated by th e m
led to the usage o f radial dow n fl ow reac to rs in fixedbed syste ms . Presentl y, man y re fo rming units use a
co mbin ati o n of both types of reacto rs . Th e reac ti on
te mpe rature in the first reacto r dec reases rap idl y d ue
to the de hydrogenati o n o/" cyc loakanes to a ro matics,
wh ich co nsumes heat. T he efflu ent fro m th e first
reac to r is th e n heated and fed to th e seco nd reacto r
w he re
it
un de rgoes
de hyd ro isomeri zati o n of
cyc lope nta nes at a s lowe r rate th a n in th e first reac to r.
Th e seco nd reacto r o pe rates w ith a te mperature drop
of 29S-30SK. Th e las t stage reac to r in vo lves
wh ic h
is
hyd roc rac kin g
and
hydroge no lys is,
exothe rmi c leadin g to s li g ht te mpe rature c hanges. T he
first reactor is th e small es t in s ize fol lowed by the
second , whil e the third a nd fo urth a re ve ry large
reac to rs refl ectin g th e time take n by the react io ns

Table 5 - Typi cal operating co nditi ons for a three- reactor system"'
Rea ctor I

Reactor 2

Re,lCtor 1

Inl et temperature. K

775

775

775

Exit temperature, K

706

844

76')

Temperature drop. K

69

31

Ii

Octane number

65.5

79.5

SlO.O

Octane- number increase

27.0

14.0

10. 5

Dehydrogenat ion,
Dehydro iso meri zati on

Dehydrogenat ion.
Dehydroi so meri za tion ,

J-I ydrocracking .

J-Iydmcrack ing,
Dehyclrocyclizati on

Dehyu n. cyc liza ti on

Principal reactions

LHSV , If I per reactor

5.5

2.4

1.7

Per cent of total catalyst

charge

15

35

50

971

TURAGA el af.: CATALYTIC NAPHTHA REFORMING

beds are regene rated at low pressure of about 8 at mos

with air as the source of oxyge n. The catalyst
inve ntory can be rege nerated 5-10- times before its
activity falls below the eco nom ic minimum, when it is
replaced . As ca talyti c activity decreases , aromatic
yield and hydrogen purity also drops because of
increased hydrocrackin g.

taking place in each of these reactors. The catalyst

loaded in the first reactor is only 10-20 per cent of the
total catalyst c harge. Temperature profile (/'.,.7) along
the reactors is another important parameter and is
indicative of the type of reactions occurring in each
reactor.

Product Separation and Stabilization

The advent of bi- and multi-metallic catalysts

allowed the operation of semi-regenerative units at
14-17 atmos for the same cyc le le ngths compared to
hi ghe r pressures of ~o atmos using PI. Se miregene rati ve re formers are generally built with three
to four catalyst beds in se ries (Figure 5). The fourth
reactor is usua ll y added to so me units to all ow an
increase in eit he r severity or throu ghput whil e
maintaining th e same cycle lengt h. Catalyst amount
increases with th e cycle le ngth . The product RON
achievable through thi s is usually 85- 100, depending
on optimized feedstock quality, gasoline qualities and
quantities , a nd operating conditions required to
achieve a specified cyc le le ngth. Most li censors have
se mi-regene rative design op ti ons (Tabl e ~).

Effluents from the reactors are cooled and

separated into gaseous and liquid products . The
gaseous products consist of 60-90 mol per cent
hydrogen and the rest CIA hydrocarbons. The liquid
product, known as the reformate, consists of C).IO
hydrocarbon s with aromatics in the range of 60-70 wt
per cent. The crude reformate is purified in a
stabilizer where volatile and light hydrocarbons are
removed, using a single-column operation under
sufficient pressure to permit condensation of reflux
from the overhead vapor. Part or most of the
overheads are removed as vapor.

Process Class!fication
Catalytic reforming processes are classified,
based on th e mode and frequency of catalyst
regeneration, into three types: (a) Semi-regenerative,
(b) Cyclic (Fully regenerative) , and (c) Continuous
Regenerative (Moving bed) process. There are more
than 800 commercial (Table 6) installations of the
catalytic reforming processes worldwide with a total
22 24
capacity of 9.5 million barrels/d . .

Cyclic (Fully Regenerative) Prucess

The !:yclic process, typ ica ll y uses a train of five

to s ix fixed cata lys t beds, s imilar to the se miregene rative process, with one additional swing
reactor, which is a spare reactor used to substitute any
of the regular reactors in th e train while th e regular
rector is being rege nerated (Figure 6). This enables
only one reactor to be taken off-s tream while the
whole process and re formate y ie ld s continue
unaffected. Catalyst rege ne ration takes place at longer
intervals as compa red to th e sem i-regenerat ive
process. The cyc li c refo rme r ope rates at low pressure,
wide-ran ge boilin g feed and low hydrogen to
hydroca rbon ratio.

Semi-regenerative Process

The semi-regenerative catalytic reforming

process is characterized by continuous operation over
long periods with decreas ing catalyst activity and
increasing reformin g severity to maintain conversion
to a specific RON . The semi-regenerative process is
the conventional reforming process, which operates
continuously for more then I y. Eventually the
reformers are shut down periodically and the catalyst
Table 6 -

The cycl ic process produces re formate of RON

100-\ 04 but also leads to ex te nsi ve cok in g due to low

Regional distribution of catalytic reformers by process design in I<)<)3 ~.j

Region

Per cent of Reformers

\

Semi-regenerative

Cyclic

Continllolls

United States

57

13

14

16

Europe

66

II

17

Japan

70

10

15

a Other includes non-regenerative and moving bed systems

J SCI IND RES VOL 62 OCTOBER 2003

972

Light ends to
Recovery

Reactors

Heater

Stabilizer

Reformate

Figure 5 -

Semi-regenerative reformers"

Fresh Feed

Recycle Gas Compressor

Flash Drum
Product H2
Product to Stabili zer

Du
Reactor
Heater

Figure 6 - Cyclic regenerati ve reformers"

TURAGA

el

973

al.: CATALYTIC NAPHTHA REFORMING

pressure and high-octane severity . Using lowe r

pressures enables production of a higher C 5+
reformate yield and hydrogen . The process suffe rs
from the drawbacks that the reactor sizes shou ld all be
the same to enable switching and also that the reactors
alternate between a reducing atmosphere during
normal operation and an oxidizing atmosphere during
regeneration .

changes in unit operatin g conditi o ns are carri ed out by

changes in ope ratin g parameters (Tabl e 7 and 8). The
variables , which affect performance of the catal yst
and c han ge the y ie ld and quality of reformate are
feed stock prope rti es, reacti on te mperature, space
hydrogen-tovelocity, reac ti on pressure, a nd
hydrocarbon mo le ratio .

Continuous Regenerative (Moving Bed) Process

Boiling range of th e feed is an important

parameter whi c h ca n be contro ll ed and th e max imum
ASTM end point o f 478K is spec ifi ed for reformer
reac tor c harge. Thi s is because hyd rocarbo ns boiling
above 478K are known to form polycyclic aromatics
and thus coke. As a rul e, a c han ge in te mperature by
13K in feed ASTM e nd point costs about 35 per cent
of catalyst life between ASTM e nd po int ranges of
463-491 K for the feed. Straight run naphth as are the
25
major feedstocks for reforme rs .

UOP in the late I 960s made another advance in

the technology of catalytic reforming by introduc ing
the Continuous Cata lytic Reformer (CCR) which
produces hi gh octane reformate and high-purity
hydrogen on a continuous basis, using small amounts
of a highly active catalyst. The process has the best of
the cyclic reforming process while at the same time
avo iding its drawbacks. In thi s process, small
quantities of catalyst are continuously withdrawn
from an operating rector, tran sported to a regeneration
unit, rege ne rated and then returned to the reactor
system. The most common des ign involves stacking
of all reactors on top of one another with the last
reactor set bes ide the stacked reactors. The reactor
syste m has a common catalyst bed that moves as a
co lumn of particles from the top to bottom of the
reactor. Operating pressures are in the range of 3.5- 17
atmos to produce a reformate of RON 95-108
(Figure 7).

Operating Parameters
Catalytic reformers are designed for flexibility
in operation and product configuration for which

Feedstock Properties

Feedstocks with appreciable conten t of

un saturated hydrocarbons ari sin g from thermally
cracked , cata lyt ica lly cracked, coke r and pyrolysis
naphth a mu st all be hydrotrea ted before reforming to
prevent undu e hydroge n co nsumpti o n and excess ive
catal ys t deacti vation . In add iti o n to havi ng sulphur
and nitrogen. th ese stocks also co ntain substantial
olefins and diolefins , which are undes irab le in
reforme r feed for several reaso ns. The most important
side r eaction in a refo rme r is hydrogenati on of o lefins
causing excess ive hydroge n consumption . In addi ti on,
thi s undes ired side reac ti on markedly reduces the
reformate RON . More importantl y, o lefins te nd to
polyme ri ze and form coke on cata lyst surfaces.
REFORMATE

FEED [Naptha]

Parrafins : 24 wi %

Parrafins : 63 wt %

Oxygenates: 1 wt %

Nitrogenates: 23 wt %
Aromatics: 14 wt %

...

Distill Range: 85 - 160 C

CCR REFORMER
P = 4 -7 Bar

Aromatics: 75 wt %
Distill Range: 60 - 170 0 C

T=495-515 C
Typical RON: 45

C I-C4 : 8 wt %
Reformate : 88 wt %
Figure 7 -

Mass balance for co ntinu ous catalyti c reformin g"

974

J SCI IND RES VOL 62 OCTOBER 2003

Table 7 - Yield-octane relationship, reforming C(, 633K naphtha, constant teJllperature2~

Pressure (atmos)

Co+ yield (vol. , per cent)

Octane C 5+ (R+O)"

90

92

83

99

14

87

92

14

80

99

17

82

92

17

76

99

34

88

92

" Research octane number in the absence of tetraeth yl lead .

Table 8 -

Increase

Influence of feed properti es and product distribution 2~

H2

H2

Cs+

Delta

Reactor

purity a

yield

yield

temp.

temp.

Feed property
API

Paraffin s

Naphthenes

Aromatics

Initi al boiling point

Final boiling point

0(-)

()

()

()

Process variable
Separator pressure
Separator temperature
Reactor pressure
Reformate RON C
a +, Increase; -, Decrease; 0, No effect

Reaction Temperature

Refo rmers are generally des igned as a series of

reactors , which lead to c hanges in catalyst bed
te mpe ratures as feed flow s through them. It is thus
common practice to measure either the WeightedA verage reac tor Inl et Te mpe rature (WA IT) or the
Weighted-A verage Bed T e mperature (W ABT). WAIT
is the sum of th e inlet temperature to each reactor
multiplied by the wei g ht pe r cent of total catalyst in
eac h reactor. Similarly, WABT is the sum of the
ave rage of the inl et and out let temperatures of each
reactor multipli ed by the weight per cent of the
catalyst in the reac tor. In day-to-day operations, it is
a lways eas ie r to operate WAIT than W ABT.

Reaction te mpe ratures are ch osen to balance

inc reased catal yst activity (max imu m in th e range
733-798K) with inc reased deactivati on rate (occurrin g
in the te mpe rature ran ge 755-773K). Low-pressure
processes a re operated at s li g htl y hi g he r te mpe ratures
to opt imi ze co nve rsio n\ to hi g h-RON products .
Catalytic refo rmin g res ult s in in c reased reformate
RON with reacto r te mperature and as a rul e for th e
RON ran ge of 90-95, WAIT s hou ld increase by 226
For a RON ran ge of 95-100,
3K1RON increase
WAIT inc rease should co rres pond to 3-4K1RON
increase. Eac h feedstock , howeve r, ha s its own
tempe rature-oc tan e re lati o nship and there is no widely
accepted corre lati o n to accou nt fo r all feedstock-

TURAGA e/ af.: CATALYTIC NAPHTHA REFORMING

temperature relationships. Also, increased RON

reformates have a reduction in yield by about 13
volume per cent of the reformer charge.
Space Velocity

Space ve locity is an important reforming process

variable and is a measure of the contact time between
the reactants and the catalyst. Thi s is ex pressed as
e ither the Liquid Hourly Space Velocity (volume per
hour of reactor charge per volume of catalyst, LHSV)
or the Weight Hourly Space Veloc ity (weight per
hour of reactor charge per weight of catalyst, WHSV).
Modern commercial reformers usually operate in an
LHSV range of 1-2/h . At lower LHSV values, contact
time increases, leading to undes ired side reactions and
increased hydrocracking, reducing reformate yield.
This choi ce, however, represents a compromise
between reducing undes ired hydrocracking and
increase in des ired de hydrocyclizati on. Aromatizati on
and isomeri zation , however, are not affected by
changes in space velocity as the se reaction s are very
fast and approach equilibrium values even at lower
contact times .

975

Hydrogen-to-Hydrocarbon Ratio

Hydrogen is essential in refo rming to avoid

unwanted side reaction s and reduce catalyst
deactivation . Hi gh hydrogen-to-hydroc arbon ratios
require hi gh hydrogen recycle rates and increased
energy cos ts. Operating at redu ced hydrogen-tohydroca rbon rati os leads to sav in gs in terms of energy
cos ts and hence th e va lu e c hose n is lower bound by
the des ired amount o f hydrocrac kin g and the
maxImum
acceptable
deactivation .
Reformers
desi gned 111 th e 1950s used a hydrogen-tohydrocarbon rati o of 8-10 and a hydrogen partial
pressure of 19-35 atmos while modern reformers
operate in hydrogen-to-hydroca rbon ratio range of 2-5
and a parti al hydrogen pressure o f 5-1 I atmos, a
change due to hi ghl y active catalysts.

Recent Developments

Generally, for a reformate of 90-100 RON ,

doubling LHSV requires an increase of 15-20K in
reactor inlet temperature. Higher paraffinic naphthas
require a 20-30K increase in rector inlet temperature
as space velocity doubl es. Naphthas, which are low in
paraffins, require only 8-12K increase in reactor inl et
27
temperature as space ve locity doubl es .

Catalytic refo rmin g, in add iti on to fulfillin g its

original obj ecti ve of produ c in g hi gh octane gasoline
has also been used for va ri ous appl ication s, including
producti on of aromatics , liquefied petro leum gas
(LPG), hydrogen, and upgrad in g o lefini c feedstocks
and raffinates. Almost 75 di ffe rent refo rmin g catalysts
are ava il able currentl y for specific goa ls, using
spec ifi c feed stocks. C<ltalytic reforming is presentl y
used for three broad purposes: octane boosting,
feedstoc k
aromatics
production
and
o lefinic
upgradin g. Recent de velopments have focus ed on
imparting fl ex ibility to re forming units to process
variabl e feedstocks us in g new ca talys ts .

Reaction Pressure

OClan.e Boosting

Over the past five decades, reformer unit

pressures have dropped substanti all y. Reformers of
th e 1950s used a pressure range of 19-35 atmos while
modern reformers operate between 5-1 I atmos. Each
of the three or four reformer reac tors has different
pressures and an average reactor pressure is preferred.
Decreased pressures lead to increased aro matics and
hydrogen yie lds but also in crease co king and cata lys t
deactivati on. It has been demonstrated that at 100
RON , there is an increase in the per cent yie ld of
reformate from 79.7 to 83.5 by a reduc ti on in pressure
from 21 to 8 atmos . In oth er words , at the 100 RON
leve l, liquid yie ld increases or decreases by about 2
vo l per cent of c hargel 8 atmos change in pressure. At
the 90 RON leve l, the yie ld difference is abou t I
liquid vol per cent of charge/8 atmos chan ge in
2R 29
pressure . . Similar qu antitative corre lation s have not
yet been reported for hydrogen yie ld .

Thi s is a post-reforming process which cracks

straight chain paraffins se lective ly using a metal (Ni )
impregnated in a small pore zeo lite (ZSM-5 or
Eri onite) at 25 atmos pressure, hydrogen-tohydrocarbon rati o o f 7 and temperatures around
600K . Co mme rc ial li ce nso rs of si milar processes
Exxo nM obil
(Mfo rmin g)
and
UOP
include
(Se lec to formin g).
Aromat ics Production and Olefinic Feedstock
Upgrading
Ca ta lyti c re formers wi th these obj ecti ves process
very narrow feed cuts in th e range of 333-363K for
benzene production and 383-4 13 K for toluene and
xyl ene producti on with th e ex act cut po ints dependin g
on crude so urce. Gas o lin e produ ction requires full
ran ge naphtha. These re fo rmers operate at hi gh
severity to ma x imi ze aro mati cs prod uction. Some of

J SCI IND RES VOL 62 OCTOBER 2003

976

Mtlyear
400 - , - - - - - - - - - - - - -- - - - -- - - - - - - -- - - - - i

-------11..1-----_1-----_1-----_1-- _.- -__- '___.--_

350

. ----

Reforming

300
250
200

Alkylation

150

,/+-----

100

.------+/
50
A-

/ ..K-

----t-- "

..-..- ~

Etherification

Isomerization
..

___ ___e__--e -

_---A- - -A
-0\- - ......-~ - -A- - "'~_.._---e

. - -- - e --

--e- - -e- --e

O +.----'==~-~-----~i---_.---_.---_.----~

1988

1990

1992
Figure 8 -

1994

1996

1998

2000

2002

Oil ret1ning birth th roug h 2000(ref.36)

the well-known processes available towards these

objecti ves include M2Forming (from ExxonMobil )
which processes olefinic feedstocks and thermally
cracked nap htha a( low pressures a nd hig h
temperatures, Aroforming (from Salutec, Australia
and IFP, France) usi ng a Ga impregnated ZSM-5
catalyst to convert LPG and li ght naphtha to
aromatic s (w ith no hydrogen recycle), and the BPUOP Cycl ar process, quite similar to Aroforming. The
Cyclar process has had some succesS in the past but
has not been very popu la r of late'o.

Beyond Environmen!l:al Regulations

The Clean Air Act Amendments o f 1990
impacted cata lytic reforming by layi ng restricti ons on
fuel qua lity to improve e mi ss ion standards_ Limits on
benze ne to a I volume per cent maximum amd
reduced Re id Vapor Pressure (RVP) have forced a
compl ete rethink of the process and is the bi ggest
challenge facing reforming. The offset in octane
number caused by reduc tion in benzene was to be met
by the addition of oxygenates such as methyl tertbutyl ether (MTBE) which has a RON of 117. Thi s
has, however, received a major setback with the
recent deci sions to stop using MTBE as an octalnee nhanci n bcr additive becau se of its groundwate r
polluting potenti al.

With these developme nts , the re is a reduced

emphasis o n the use of benzen o for octane
e nhanceme nt a nd deve lo pme nt of cata lysts and
techn o logies wh ic h a lkylate benzene an d to lu e ne to
xylenes and Co) aromatics woul d be the new
c ha ll enges for the re finin g indu stry_ Ex isting
re forming cata lysts have to be modified o r new postreformin g processes added or di scovered, to meet this
c ha ll e nge. Thi s would also lead to reluctance in
processing full range nap hth a to avo id benzene
production . For octa ne numbe r enh ance ment , the
thru st shall be o n cata lysts and technologies that
isomerize the li g hte r C 6 and C 7 paraffins to branched
isome rs w ith hi g he r RON.
RVP constra ints will res ult in e li m inating butane
from gasoline: excess butane being ava ilabl e for
convers io n into iso-buta ne and iso-bu ty le ne, w hic h, in
particular, is an important feedstock fo r sy nth es is of
MTB E . Thi s is particularly important in countries
like, India and China, which have to cope up with the
Clean Air Act and are sti ll llsing M T BE but face an
acu te shortage of iso-butylene as its feedstock .
Petrochemical capaci ti es are on the ri se g loba ll y
and espec ia ll y in the Asia-Pacific w here the per capita
co nsumpti o n of petrochemical produc ts is less than
European and the US va lues by an order of

977

T URAGA et al.: CAT ALYTI C NAPHTH A RE f-a R M ING

. d e'11-1417
'
. f or
ermg
t he a b ove scenano
magmtu
. ' . C onsl'd
the petrochemica l industry and the product pattern
in volving LPG' o, it is expected that major reforming
units would now be built in the Asia-Pacific'7, which
not onl y require aromati cs, but also huge amounts of
LPG. It would be idea l if reformers could produce
onl y aromati cs and hydrogen but thi s is an unlikely
scenari o in the near future and so the preferred
product di stributi on would be aromatic s and LPG.
Thus, on an overall basis, catalyti c reformin g is
expected to increase sli ghtl y or plateau out (F igu re 8)
fo r octane enhancement objecti ves but has a strong
outl ook as far as aromati cs producti on IS
concerned, 4.37.

He in e ma nn H, Handb ook of' heterogeneo us ca talysis, ed ited

by G Ert l, H Kn tizinge r a nd J We itka mp (YC H, We inh eim)
1997 .

Peer R L. Bennett RW & Fe lch D E, UOP P latfo rmi ng

lead in g octane tec hno logy illl o the 1990' s. Ca tal Todav, 18
( 1994) 473.

S infe lt J H, Billl etallic cata ll'sts: Discoveries. concepts, and

application.\' (W il ey, Ne w Yark ) 19 83.

Bourn o nvill e Jea n-Paul & Fra nck Jean-Pi erre, H vdrogen
effects in cata lysis, edited by Z Paa l and P G Meno n, (M arcel
Dekker. New York ) 19 88.

Gates B C , Katze r J R & Sc huit G C A. Chemistry of

ca talytic p rocesses (M cGraw Hill. New Yo rk) 1979.

Sinklt J H, Bifu nc lio na l cal a lys is. Ad" Chelll En g, 5 (1964)

37.

10

W e isz P B & Sweg lcr E W , Stepw ise reac ti on o n di ffe re nt

catalyti c cent e rs: iso me rizatio n o f saturated hydrocarbo ns,
Science, 126 ( 1957 ) 3 1.

II

Mart in o G , Co urt y P & Ma rc illy G , Handbook of

heterogeneolls cata lvsis, ed ited by G Ertl. H Kntizin ger. and
J We itkamp (YC H, We in he im) 199 7.

12

Sinfe lt J H, Po lymeta lli c c luster co mpos itions useful as

hyd roca rbo n co nversio n ca la lys ts, US Pm , 3 953368, 1976.

13

S infe lt J H, Co mb inati o n re fo rmin g. US Pa t, 379196 1.1974 .

14

Bo nd G C , Hundbook (!f' heterogeneo lls ('a talvsis , ed ited by

G Ertl. H Kn tiz in ger an d .J We it b mf1 (YC H. We in he im)
1997.

15

Bo iti aux J P, Deves J M . Di d ill o n B & Marcill y C R ,

Ca talytic naphtha re{!lImin g: Science and technology, ed ited
by G .J Antos , A M Ait a ni a nd J M Pa re ra (M arcel Dekk e r,
Ne w Yo rk ) 1995.

16

O ' Co nno r C T , HandlJOo k (~f' heierogeneoll,\' calalysis, edited

by G Ertl , H Kn tiz in ger a nd J We it ka mp (YC H, We inh eim)
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Acknowledgements

17

Co rm a A, Tra nsfo rm alion of hydrocarbo ns on zeo li te

cata lysts. Cata l Lell , 3 ( 1993) 22.

Uday Turaga is grateful to Jingyan Shao, We ilin

Wang, Semih Eser, Anil Oroskar, and Mat Mall adi for
useful suggesti ons in preparati on of thi s paper.
Ramnarayanan Ramanath an ac know ledges M A
Vannice for stirring hi s enthu siasm in heterogeneous
catalysis by grad ing him top honors bottom-up and
stimul ating d isc uss ions with John Sinfe lt and Paul
Weisz.

18

Dero uane E C & Ya nde rveken D .I. Structu ral recogn iti o n
a nd preo rga ni zatio n in zeo li te ca la lys is: di rect aro mati zation
of hexane; o n zeo lit e-L based cat a lysts. AIIIII Ca tal. 45 ( 1988)

Conclusions
Benzene, toluene, and xy lene are critical
feedstocks for the petrochemi cal industry and we
ex pect th at they will be avail able to a large extent
fro m reforming units. We fee l th at there will be
renewed focus on reformin g as a process toward s
produ cti on of aromati cs and hydrogen. Catalyti c
reforming is by far the most effecti ve producer of
hydrogen who ' s most effic ient use is fo r produc ing
c lean fue ls in the refinery and thu s, hydrogen
consumpti on is expected to be very strong for quite
some time in the future. Hi gher hydrogen producti on
means operati ons of reformers at lower pressures and
many reforming li censors have processes avail able to
meet thi s requirement.

LIS .
19

Larsen G & Hall e r G L, Meta l-s<lppo n effects in pl atin um/ Lzeo li te cata lysts, Caw l LCII, 4 ( 1990) 375 .

20

Prasada Rao T S R , C K Mllo hy mCl/ lO ria l lectll re , Ind ian

Insti tute o f C hc mica l Eng in ee ring , Hyd c rabad , 19 9 1.

21

Creyghto n E J & Dow ning R S, Sha pe-selective

hydrogenati o n and hyd rogen tra nsfc r reacti o ns ove r zeo lite
ca talysts, .I Mol Caw l A: Chelli. 134 ( 199 8) 47 .

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