10urnal of Scientific & Industria l Research

Vol. 60, April 200 I , pp 3 19-327

Disproportionation of Toluene to Produce Benzene

and p- Xylene - AReview

Abdal Kareem MA* , Shri Chand' and 1M Mishra

Department of Chemical Engineering, University of Roorkee, Roorkee- 247 667
Fa x: +91-1 332-73560

An increasing demand for benzene and xylenes as raw material s for polyester fi bres and sy nthetic resins in the rece nt past has
stimu lated newer development s in convertin g toluene to benzene and xylenes. Among the xylenes, fI-xylene is or co nsiderable
importance as raw material for terephthali c acid and dimethyl tereph th alate manufacture, required for polyester fibre and for the
synthesis of vitamins and other pharmaceuticals. The paper reviews the ac ti vity and selecti vity (towards fI- xy lene production ) of
various catalysts viz., amorpho us SiO/ Alp " X- and Y-zeolites , mordenite, faujasite, HZSM-S in its unmodified , modified, as
well as ion exchange forms. The effecls of preparatiun method uf the catalys ts, surface acidity, shape selecti vit y, and crystal size
orthe zeo lites as well as temperature, pressure , and carri er gas on the activilY and selectivity for p-xyl ene is discussed here. Th e
performance of perovski te based oxides as prospective ca tal ys t is also exp lored.

Introduction a lso as importan t feed stoc k to th e petrochemical in-

dustry . The la rge amo unt s of toluene produc ed
Di spropo rtion ation reaction is one of the recent
worl dover do not find mu ch use as a raw m ateria l fo r
techniques for the convers io n of less va lu ab le toluene
petroc hem ical industry except for the productions of
to more valuable benzene and xy lenes. Th e impor-
the TNT (trin itroto luene, a n exp los ive material) and
tance of the se co mpounds as feed stocks fo r petro-
benzoic ac id which req uire re lati ve ly smaller amounts.
chemical industry need not be stressed .
Bulk of th e tolu ene produced is used as a reagent and
The re levance of disproportionation process, espe- as a solvent for paint indu stry.
c iall y with reference to our country is enormous w hen
This reaction to produce equ imo lar amounts of ben-
we look into the avai lable toluene as well as the short
zene and xylene is a well known reactio n. Eq uil ib-
suppl y of benzene and xy lene for the petrochem ical
rium co nstants for this reaction are not c ha nged sig-
industry. In the recent past, the re has been a phenom-
nificantly by shiftin g f ro m liqui d to va pour phase or
e nal growth in the use of benzene and xy le nes in or-
by large c hanges in te mpe rature I .:! . The reaction is
ga nic synthesis. Benzene is the aromatic hydrocarbon
norm ally carri ed out in the presence of hydroge n. Tol u-
having divergent uses fo r the production of petro-
ene and hydrogen are mi xed together and are passed
chemi cals, synthetic fibe rs, sy nth etic detergents , plas-
over a cata lys t. H yd roge n is emp loyed to s uppress
tics , e las to me rs, phenolic res ins, lube oi l add iti ves,
crack in g and to preserve the activ ity of the catalyst.
and in secticides.
Since hydrogen is also a compo ne nt in the feed stream.
Paraxylene finds its use in the production of dime- toluen e will have a tende ncy to co mbine with hydro-
thyl terep hth alate and terephthalic ac id whic h are in- gen in the presence of a ca ta lyst to g ive benzene and
termediates in the production of po lyeste r fibres, and methane, i.e., dealkylation of toluene.

Some amount of tri-and tetramethylbenzene may

* Author to whom all the correspo ndences shuu ld be add ressed
** AI-Balqa ' App li ed University, AI-Husn Pulytechnic. Irbid, Jor- a lso be formed during to luene disproportionation with
dan certain cata lysts. Tri-methyl benzene are fo rm ed by
320 J SCI INO RES VOL 60 APR IL 200 1
di sproportion ation of xy lene form ed and tetTameth yl
benzene are fo rmed by di sproporti onatio n of trimeth yl
benzene thu s fo rmed. T hu s, di sporporti onat ion of
produ cts is al so envisaged. Apart from these side re-
acti ons, some amount of xyle nes also isomerize to give
eth ylbenzene. In the di sproporti onati on process, theo-
reticall y there is no loss of hydrocarbons as there is
no methan e fo rma ti o n, as see n in th e case of
hyd rodealkyl ati on process . 95-96 vo lume per cent of
liqui d produ cts are ob ta in ed in co nt ras t to th e
hydrodealkylation process where the li qui d yield is
limi ted to about 82 vo lume per cent, due to the ac-
companying loss of the meth yl group in the fo rm of
meth ane.
The disproportionati on process is usuall y carried
our in the vapour phase over solid acid catalysts such
as sili ca-a lumin a and zeo li tes at elevated temperatures.
Mordenite, fa uj as ite 3 and va ri ous form s ofmo rde ni te~
incl udin g dea lumini zed modi fica ti ons"' are know n to
be superior in many res pects to silica-a lu mi na. Other
zeoli te catalys ts which include mordeni te 6.7 , rare-earth
exchanged X- zeo lites 8,9 and ca tio n excha nged Y -
zeo lites 8, 10 possess high acti vity. Unfo rtu nately, these
cata lysts deacti va te qu ic kl y due to coke depos ition
within a few hours on stream and also show low se-
lecti vity for di sporporti onati on. Us ing ZSM-5 zeo lite
as catalyst, the product distri buti on can be directed to
the selective fo rm ation of p-xy lene, the mos t va lu -
abie isomer, modi fyi ng the shape selecti vity of the zeo-
lite.
Subsequentl y the efi'ect of various pa rameters such
as temperature, press ure, surface acid ity, crys tallin -
ity, SiO/A I2 0 J rati o, and carrier gas on the selective
disporportion ation of toluene to prod uce benze ne an d
p-xy lene is summ arized.
Effect of Pressure
The rate of disproportionation reaction is usually
reported to increase with increasing pressure of the
reaction. The effect of hydrogen pressure on toluene
d ispro p o rti onation using different samples of
morde nite viz., ammonia exchanged mord e nite,
mordenite dealuminated wi th HCI and treated under
dry air, dea lumin ated morde nite treated under we t air
and a sa mpl e of fiu ori na ted al umin a have also been
reported II.
For all the mordenites, the reacti on ra te increases
with increase in hyd rogen press ure. However, with
fiu orin ated alumin a, the tolu ene disp roporti onatio n
ra te does not change with the hydroge n pressu re.
Effect of Zeolite Preparation M ethod
Doubl e structure catalys ts compris ing ZS M-S and
boros ili cate cores were prepared 12 with a shell made
of silicate with no acid ic properties and havi ng a uni-
form pore size of 6A. Thi s catalys t showed hi gher 1)-
se lecti vit y in compariso n to ZS M-5 Iy pe catalysts at
the sa me co nversion level. The resul ts sugges t that jJ-
selec ti vity could be enh anced by 'electively in acti-
vating the ex ternal acid sites withou t chang ing the pore
mouth size. The catalysts were prepared by the kn ow n
method ".
Doubl e stru cture ca talys ts were prepared by mi x-
ing Na-ZS M-5 and Na-bo ros ili ca te seeds wi th fumed
sili ca, NaOH , distill ed water and TPAB r, an d sti rring
the mix ture until it became homogeneous (pH 10. 24h
and crys talli sation do ne at l70 0 e for 48h). The fina l
do uble stru cture catalys ts of ZS M-5 type cores and
sili ca lite shell (weight rati o I: I of shell to core), H-
ZSM-5/s ili ca li te, and H-boros ili cate/s ili ca lite were
prepared by a simil ar procedu re.
T he di sp roporti onati o n of tolu ene catalyzed by
zeo lites of the pentasi l type has already been in vesti-
gated by many researc h e rsl~ -16. It was show n th at the
product distributi on in thi s reac ti on sys tem is particu-
larl y sensiti ve to the interacti on of intracrystalline dif-
fusion and reacti on. Pentas il zeo li tes were generally
prepared by the crystall izati on of alumi nosi li cate gel
in the presence of organi c temp late. The common
templating agen ts used in the synthesis are nitroge n
conta ining organic bases such as tetrapropyl-ammo-
nium hydroxide/halide l7 and 1-6-diaminohexane lx. 1-
3-diaminopropane I9 . Pentasil zeolites can also be pre-
pared in the absence of an organic templating agent 20·
21
The catalyti c activity of pentasi l zeolites in the
di sproportionation of toluene at near steady stale af-
 KAREEM el at.: DISPROPORTIONATION OFTOLUENE
ter initial partial deactivation is almost proportional
to the AI-content, independent of the nature of the tem-
plate used for zeolite synthesis. The ratio of benzene
to xylenes in the products depends only on toluene
conversion, independent of composition or synthesis
mode of zeolite and of reaction temperature.
Effect of Surface Acidity of Zeolites
The hydrocarbon reactions take place on Bronsted
acid sites which are formed on zeolites . The nature,
strength and number of these sites can be detected by
IR, magic angle spinning NMR and temperature pro-
grammed desorption (tpd) of ammonia 22•2H . One of the
important factors for the variation in acid sites is the
ratio of Si0 2 and AIP1 in the zeolite sample. The acid
sites in H-ZSM-5 zeolite of varying SiO 2/ AI 20 1 ratios
have been well characterized 29 . The tpd studies have
shown that the number of ammonia molecules per unit
cell which are equivalent to the number of acid sites
per unit cell are directly proportional to the number
of aluminium atoms per unit cell. The catalytic data
for toluene disporportionation show that the toluene
conversion and the number of acid sites both increase
with increasing aluminium content in H-ZSM-5
zeolites, indicating the surface acid sites as active cen-
tres for the reaction. In the absence of side reaction s
such as dealkylation and cracking the selectivity for
toluene disporportionation (defined as benzene/xylene
molar ratio in the product which should be unity) in-
creases with decrease in strength of acid sites.
Among the different types of zeolites used as cata-
lysts (mordenite, faujasites, and pentasil ), ZSM-5 zeo-
lite possesses several advantages, showing a higher
selectivity to toluene disproportionation with slower
aging by coke deposition due to its peculiar acidi c
distribution and shape se lectivity.lo.31. On the othe r
hand, mordenite is also an important commercial cata-
lyst since it can convert the bulky trimethyl benzenes
to xylenes 12,33 .
At high silicon-to-aluminum ratios tolue ne conver-
sion decreases as it was ex pected due to the fewer
number of acid sites linked to aluminum atoms, al-
though for the ZSM-5 sample with SiO 2/Al 20 J rati o
of 37 (a nd crystallinity 74 per cent), its low catalyti c
321
activity is also related to its lower crystallinity in co m-
parison to another sample with SiO 2/ AI 20 3 rati o of 15
and crystallinity 100 per cent .,...
With the decrease in silica-to-alumina ratio , the drop
in selectivity to toluene disproportionation may be be-
cause of different secondary reactions favoured by a
higher a lumina content ( tolu e ne and xy le ne
dealkylation). For ZSM-5 catalyst with s ilica-to
alumina ratio 15 , xylene disproportionation was also
an important reaction , which explains the relati ve ly
higher percentage of trimethylbenzenes obtained in
the product. Thus, although the two zeolites with SiO/
AIP 3ratios of 15 and 37 show different tolue ne co,;-
version and selectivity to disproportionation , th e ir
xylene yield is quite similar 35.36 . It has been po inted
out that dealkylation reactions take place on stronger
acid sites than toluene disproportionation , hen ce the
acid strength of ZSM-5 increases with the aluminum
content.
The number of molecules of toluene that underGo
b
disproportionation reaction/s/uni t cell of the zeo l i te
were correlated with the conce ntration of the va ri o us
acidic sites 1?, i.e. , strong acid sites (tpd peak max i-
mum at 620-670 K) , medium acid sites (peak at 420-
470K), and weak acid sites (peak at 373 K). The spe-
cific catalytic activity was found to increase with the
concentration of both the strong an~ medium acid sites,
suggesting that both types of sites are active in th e
disproportionation reaction.
Shape Selectivity of Zeolite Catalysts
It is known that ZSM-5 modification by trea tnl ent
with different agents and by mea ns of several proce-
dures leads to an enhancement of the selectivity to p-
xy Iene .38-4 1,0 btallllll
. . g a proportIOn
. of p-xylene rathe r
higher than the thermodynamic equilibrium valu e (24
mol per cent p-xylene). Tolue ne disproportionati on
inside the zeolite structure yields benzene and a xy-
lene mixture kn ow n as initi a l product. This product,
tgen diffu ses out of the pores but simultaneously it
undergoes ' iso me rization reac tion s which tak e place
within the zeolite c rystal. A hi ghe r p- xy le ne propor-
322 J SCI J D RES VOL 60 APRIL 200 I
tion than the values initially obtained in the primary
product is expected since its least minimum diam al-
lows a faster diffu sion than the other two isomers.
The p-selectivity enhancement and the decrease in
toluene .conversion observed in the modified zeolites
can be related with the fo llowing roles of the modi-
fier agent:
• Pore blockage occurs by deposition of modifi er
agents. Tortuosity of the channel system is in-
creased, which delays the diffusion of the differ-
ent molecules associated with the reaction.
• Linkage or deposition of the modifer age nt to the
unselective acid sites located on the external sur-
face of the zeolite crystals, avoids the external
iso merization of the primary product.
p-xylene selectivity was enhanced 4 2·4.1 by impreg-
nat ion with phosphorous and boron compounds and
by coating the catalyst surface with polymers. The phe-
nomenon was explained on the basis that the pores in
the ZSM-S zeolite are approximately 7-8A in diam,
which permit the rapid diffusion of tolu ene and p-xy-
lene with molecular diam 6.3A but severely retard the
diffusion of 0- and m-xylenes with molecular diam of
6.9A 45 .
Results indicate an enhancement up to 88-97 per
cent in the p -selectivity using modified zeolite cata-
lys ts 46 . Modification with phosphorus was made by
impregnating (8.S per cent phosphorus) the zeolite
crystals with trimethyl phosphite 47 , or, aqueous phos-
phoric acid. The magnesium-modified cata lyst was
prepared by impregnating with aqueous magnesium
acetate and had a magnesium content of - 11 per cent
by weight. In another experiment boron modified cata-
lyst was prepared by impregnating HZSM-S with a
solution of aqueous boric acid.
Chemical vapour deposi tion (CVD) of silicon
alkoxide is also an useful method for controlling pore
opening size of zeolites. This method was applied to
mordenite 4 8 and HZSM-S (ref. 49), and their
selectivities were effec tively improved in the toluene
disproportionation up to 97 per cent of p-isomer in
xylene product.
The deposition of alkoxide was performed us ing
an apparatus consisted of a vacuum system equipped
with a conventional quartz spring bal ance4 ,! . HZSM-S
was set in a quartz baske t hun g on the balance a nd
evacuated at 673 K until there was no decrease in
we ight and then the alkoxide was deposited at S93 K
through CVD method. For the high ly depos ited zeo-
lite, the alkoxide deposition was repeated after the
evacuation of the gas phase. After the deposition , the
zeolite was calcined in situ in 26.7 kPa of oxygen at
673 K to remove coke formed on the zeolite through
the deposition.
Toluene di sproportionation over HZSM-S zeolites.
mod ified by chemical vapour deposition of silicon
alkoxide, also predicts that as the si lica amount in-
creased, {he selectivity to m-and o-xy lenes decreas ed ,
whereas that of p-xylene increased 50 . The deposition
of 'ilica did not change selectiviti es to benzene and
xylenes. The fraction of the p -isome r in xylenes in-
creased to more than 98 per cent. From adsorption
meas urements and test reactions, it was found that thi s
modification resulted in the narrowi ng of the pore-
opening size and the inactivation of the external su r-
face . Primarily the narrowing of the pore-opening size
caused the high p-selectivity.
Effect of Crystal Size of Zeolite
The activities of two ZSM-S zeoli tes wi th different
crystal sizes of7.4 and 14 11m (having SiO/A I2 0 , ra-
tio of 29 and 3 I and crystallinity of tOo per cent and
8S pe r cent respectively) have shown 34 that in both
the cases the benzene to xylene molar ratio in the ef-
fluent is higher than one, with a selectivity over 80
per cent. The larger crystal size zeolite hard ly modi-
fie s the toluene disproportionation ra te and favours
slightly p-xylene formation, although it is not deter-
minant in achieving a p-select ivity in achieving a
clearly higher than the equilibrium value .
Effect of Carrier Gases
Toluene disproportion ation has been reported to de-
celerate on mordenites if hydrogen is used as a carrier
 KAREEM el al.: DISPROPORTIONATION OF TOLUENE
gas with pressures greater than 0.1 MPa ll . A similar
effect has been reported for the ethyl benzene
disproportionation using hydrogen 51. Ekloff e t al
(1981) (Ref 52) have studied the effect of carrier gases;
hydrogen, argon, nitroger. , helium and oxygen on the
toluene disproportionation using shape selective zeo-
lite HZSM-5 with pressure between 0.1-1 MPa. Oxy-
gen is generally used for the removal of coke. The
nitrogen physisorption studies of the catalyst ZSM-5
(SiO/AIP1 =40) gave 21 molecules per unit cell and
the scanning electron micrograph (SEM) reported an
average zeolite particle size of around I iJm. The ac-
tivity of toluen e conversion at 325°C was found to
decrease in the order: Ar (2.94) > N2(3.15) > He (2.65)
> H2 (2.34), where the values in parentheses are the
diameters of the atoms or van der Waals diameters of
the molecules 53. The average mass balance for the
products of toluene conversion in the different carrier
gases was found to be very similar and yielded about
50 wt per cent xylenes, 30 wt per cent benzene and 20
wt per cent methane. The distribution of the xylene
isomers was found to be close to the thermodynamic
equilibrium under all conditions used 54. In all the cases
the toluene conversion at constant toluen e partial pres-
sure (lkPa) increased with increasing total press ure
of the carrier gas (in the range 0.1- I MPa).
During the catalytic process, it has bee n generally
observed that the catalyst darkens presumably due to
coke deposition. The dark colour is removed, if oxy-
gen is used as a carrier gas. Subsequent to the use of
oxygen either as a carrier gas or as a pul se in other
carrier gases, the toluene conversion proceeds rapidly,
if hydrogen is used as a carrier gas. Thi s high activity
results mainly in the formation of large amounts of
methane. The subsequent use of nitrogen resulted in
conversion rates and product distributions, which were
similar to those obtained on fresh catalysts. However,
no effect of acceleration of the toluene conversion was
found by the use of oxygen as a carrier gas, if a fresh
catalyst was applied. The treatment of the catalyst with
water vapour did not show any change in activity.
The sizes of the molecules or atoms of the carrier
gas can be correlated with the effect of the type of
carrier gas on the toluene disproportionation activity.
It was found th at the activity decreases with dec reas-
323
ing diameter of the gas atom or molecule with nitro-
gen being an exception. Hydrogen, the carrier gas
hav ing the smallest mol ecules, gave least toluen e co n-
version. The observed dec re ase in the activity of
di sproportionation reaction was discu ssed in te rm s of
either a decrease in Bronsted aciditySl or a decrease in
the concentration of interm e diate benzyli c
carbocations in the presence of hydrogen 11 ,55. The de-
pendence of the toluene conversion rate on the size of
the atoms or molecules of the inert carrier gases, i.e.,
argon and helium could be due to the shielding of cata-
lytically active sites.
Hydrogen has bee n re ported to decrease the deacti-
vation of mordenites by reducing the rate of coke for-
mation and its toxicity II . The positive apparent order
in hydrogen found with all the mordenites was ex-
plained by the regeneration of the active sites due to
the removal of the coke deposited on the catalysts 56.57 .
Moreover, the initial activity of mordenite unde r at-
mospheric press ure is of the same order of magnitude
and often higher than the values found under th e hi gh
hydrogen pressure.
The experiments carried out under nitro ge n revea l
that hydrog e n is not ne cessa ry for tolu ene
di sproportionat ion and its m ain role is to decrease
mordenite deactivation by coking.
Under nitrogen gas the mordenite catalyst deacti-
vation was much more rapid as compared to hydro-
gen gas atmosphere 5~ . Mass spectrum studies of
des orbed products of the coked mordenite reported
that the nature of the coke depends upon gaseous e n-
vironment 59 .
Isomerization of o-and m- to p-xylene
Another route to obtain p-xylene is by 0 - or m-xy-
lene isomerization over the same catalysts. Unfortu-
nately, only about 25 per cent of the initial substance
can be converted to p-isomer by this reaction since
less than 25 per cent of the thermodynami c eq uilib-
rium mixture of xylenes consists of p-xylene (in the
temperature range 300 - I 000K )45.
The isomerization of xylenes is known to be ca ta-
lysed by Bronsted rath er than Lewi s ac id sites 60. It is
324 J SCIIND RES VOL 60 APR IL 2001
an unimolecul ar process and follows a single-site re-
action model involving the adsorption of xy lene mol-
ecul es on the protonic sites of the cata lyst surface and
su bsequent intramo lecul ar 1,2 shifts of the meth yl
groups to form the isomeric xylenes 6' . HZSM-5 zeo-
lite is active for the isomerization of xy lenes . It con-
tains two types of hydroxyl gro ups whi ch absorb at
3600 and 3720 cny', respectivel y, in the IR reg ionZ7
which can serve as potential Bronsted sites in acid
catalysed reaction s.
Isomerization of o-xylene has been reported over
SiHZSM-5 catalyst which was obtained by ch·e mi cal
vapo ur depo sition (CV D) of sili co n a lkox ide on
HZSM-5(ref 50). The conversion of o-xy lene was dras-
tically decreased by the depos ition of sili ca. p-xylene
and m-xy lenes were main products along with littl e
amounts of benzene, ethyl toluene and tri-methyl ben-
zenes. As the silica content increased from 0 to 13.3
wt per cent, the fraction of p-isomer (in 0 - and m-
xy lenes) increased from the equilibrium value (3 1.0
per cent at 673 K) to 98.68 per ce nt. In addition ,
selectiviti es to the formation of benzene, toluene and
ethy lbenze ne increased with si lica amount in the cata-
lyst. The fo rm ati on of large trimethyl benzenes was
completely suppressed.
Perovskite-type Oxides As Catalysts
Perovskite -type oxides have the general formul a
ABO, and have the ability to change and/or substitute
cation composition at sites A and B with mostly a
rare earth or alkali metal at site A and a tran si ti on
metal at site B 6Z .63 . These mixed oxides are, therefore,
sui table materi als for the study of the stru cture-prop-
erty relationship of catalysts. Recently, oxides substi-
tuted with Ai, having the formula AAB0 3 have at-
tracted a lot of attenti on due to their excellent cata-
lytic actl vlty. Th e rea rr ange me nt and
disproportionation of toluelle over La, _x SrxNi0 3 cata-
lysts in the presence of oxygen and at one atmospheric
pressure has been recently reported 64 • The reacti on
products include 0-, m- and p-xylenes, as well as some
ethyl benzene. It was reported that the rearrangement
and disproportionation oholucne on the perovskite
catalys ts were due to the NiO-and La1 Ni0 4-phases .
An examination of the X-ray diffraction patterns of
La ,_x Sr, Ni0 3 (0.3 < x < 0.7) revealed ex istence of
NiO-and La z Ni0 4-phases in addition to the La Ni0 3
perovskite structure. The surface of perovs kite-type
oxides is highl y heterogeneous 65,6(,. Apart from NiO
and La 2 Ni0 4 phases, La,_xSrxNi0 3 also contains nickel
atom, whi ch interacts throu gh the che misorpti on of
hydrogen. The transition metals of group VIII (N i, Pd ,
and Pt) possess stron g hydroge n chemi sorptic ac ti v-
ity67 and catalyti c acti vity for disproporti onati on re-
acti on 65 . It was found that as x increases in the La ,-
xSrxNiOl (x>O), the amount of Ni O- and La 1 Ni0 4 -
phases increase. The disproportionation products were
formed when either NiO , the mixture of NiO (50 per
cent) and LaNi0 3 or the mi xture of La 2 Ni0 4 NiO (50
per cent) and LaNi01 as catal ys ts were used_A change
in the carrier gas from nitrogen to hel ium sho wed that
ni trogen gas could react with the adsorbed oxygen and
the latti ce oxygen on the catalys t surface, lead ing to a
decrease in the di sproportionation reacti on rate.
Industrial Processes
Toluene di sproportionati on has been recognized as
an important indu stri al process. There are three ma-
j or processes that are currentl y used within industry.
Each of these technologies in volves different operat-
ing conditions, process units, and catalysts. These tech-
nologies include: (i) the Tatoray Process (UOP) , (ii )
the Xylene-Plus Process (Atl antic Ri chfi eld), and (iii)
the LTD, Low-Temperature Di sproportionati on Proc-
ess (Mobil Chemi cal Co.). In our country, there is onl y
one industry being run by Reliance group near Surat
in Gujarat, which is based on the UOP technology.
Between 1985 and 1993, nine plants commiss ioned
toluene disproportion ation units in the US that utili ze
the Tatoray Process . The Low-Temperature Di spro-
portionation Process is currentl y the most common
process. Chalmette Refining , LLC, operated and par-
ti all y owned by Mobil Oil Company, in Chalmette,
Loui siana utili zes a Toluene Di sproportionation Unit
tending toward the selectivity ofp- xyiene. The Mobil
MTDP-3 Technology is one of the most profitable
processes currently in use. This process minimi zes the
excess hydroge n required to drive the reaction while
increas ing the se lectivity to the production of p-xy-
lene.
 KAREEM e l al.: DlSPROPORTIONATION OF TOLUENE
The Tatoray process produces xylene and benzene
from toluene and C 9 aromatics reacting with hydro-
gen over a noble-metal or rare-earth catalyst. This
process uses catalytic disproportionation with an ex-
cess feed of toluene and C 9 aromatics in the presence
of hydrogen. Hydrocarbons are fed in 9: I molar ratio
in comparison to hydrogen. The process takes place
between 350-525 ° C and 10-15 atm. This reaction
occurs through a high recycle rate of hydrogen over
the catalyst and the catalyst is regenerated. Current
technology allows the modification of this process.
The Tatoray process results in a 38 per cent conver-
sion of toluene.
The LTD process (Low-Temperature
Disproportionation) involves the formation of benzene
and xylenes from liquid-phase tol uene
disproportionation. This reaction occurs using a zeo-
lite-based catalyst at approximately 260°C and
4 .5MPa. The catalyst life is approx 1.5 Y and is regen-
erated by burning the accumulated coke. The process
involves series of three distillation columns follow-
ing the reactor. These columns recover benzene, xy-
lene, and toluene where the toluene is recycled to the
process feed. As the zeolite catalyst deactivates it may
cause a temperature rise in the reactor to approx.
3 15°C. The LTD Process yields approximately 85 per
cent p-xylene with a mixture of other xylene isomers.
Over the years many of these original processes
have been modified to reflect the current technology.
For example, vapour phase toluene disproportionation
process has been modified where a zeolite catalyst
can be used with low hydrogen to hydrocarbon molar
ratio. This process utilizes a crystalline aluminosilicate
zeolite. The reaction takes place in the vapor phase
over a radial flow or fixed bed. It is also possible for
this reaction to take place in a batch process opera-
tion. This zeolite comprises silica to alumina in the
ratio of 12. This catalyst is characterized as having a
8- I 5 A pore opening containing Group VII metals ,
hydrogen , and rare earth cations. This catalyst is of-
ten referred to as ZSM-5. Other examples that meet
the criteria for performing this reaction include ZSM-
I I , ZSM-12, ZSM-35 , and ZSM-38. These catalysts
are well known for their long life and resistance to
high temperatures and coking. These catalysts are
known to be extremely stable.
325
These catalysts can be generated in various ways .
Naturally occurring zeolites can be converted by pro-
cedures known as base exchanging, steaming, alumina
extraction , and calcination.
Conclusions
The current research involves discovering and uti-
lizing highly selective catalysts that allow for the pro-
duction of more desired product and less by-products.
Following conclusions can be drawn from the above
study.
Toluene disproportionation is an industrially im-
portant reaction to produce valuable p-xylene and
benzene from less valuable toluene. Although this re-
action is being carried out industrially since long, there
are many factors including the type of catalyst, effect
of reaction variables and the carrier gas which play an
important role in improving the product formation .
Hydrogen is generally used as carrier gas for the
reaction, but it has been suggested that nitrogen can
be more beneficial in giving higher amount of liquid
product as well as saving the catalyst from the active
sites blockage, which takes place with hydrogen . A
detailed study must be conducted to compare the ac-
tivity, and liquid product yield using nitrogen as car-
rier gas with less coking hydrogen.
The effect of the type of catalyst, which is acti ve at
lower temperature and pressure and thereby result in
lesser coke formation even with nitrogen as carrier
gas may be explored.
Study also summarizes the effect of pressure on the
rate of toluene disproportionation . Usually the rate of
disproportionation reaction is reported to increase with
pressure. But there are a few exceptions , such as fluori-
nated alumina based catalysts, where the pressure has
no effect. Such catalysts may further be explored so
that the reaction is carried out at lower pressures,
thereby saving precious energy. The mechanism of
activity of such catalysts may also be explored .
Efforts must be directed towards synthesis of dou-
ble structure catalysts, which have shown higher p-
selectivity in comparison to ZSM-S type catal yst at
326 J SCIIND RES VOL 60 APRIL 200 1

the same conversion level. These catalysts have been 22
shown to enhance p-selectivity by selective ly inacti- 23
vati ng the external acid sites without changing pore 24
mouth size. 25
It has been pointed out that the chemical vapor depo- 26
sition of silicon , magnesium, boron and phosphorus 27
act favourably in increas in gp-xy le ne selectivity up to
99 per cent. However, maj or drawback of this tec h- 28
nique is that the pe r cen t tolu e ne co nvers ion is drasti-
29
call y reduced. Other techniques, suc h as , ion-exc hange
may be attempted to obtain better p-xyl e ne yield . The 30
effect of the nature of various exchange catio ns o n
activity selectivity for p-xylene in xylenes product, 3 1 Beltrame P , Peltrame P L, Carniti P, Forni L & Zuretti G,
overall selectivity of disproportionation reaction with
Haag, W 0 , Lago R M & Weisz P B, Nalllre, 309 ( 1984) 5X9.
Olson D H , Haag W 0 & Lago R M, J Cawl, 61 ( 1980) 390.
Jacobs P A & va n Ballmoos R J, J Phy.\" CheJll , 86 (1982) 3050.
Scholl e K F M G J , Kentgens A PM , Vee man W S, Frenken P
& Vander Velden G P M, J Phys Chell l, 88 ( 1984) 5.
Dessau R M & Kerr G T, Zeoliles, 4 ( 1984) 3 15.
Topsoe, NY, Pendensen K & Derouane E G,.1 Cawl, 70 ( 198 1)
41.
Ande rson J R , Fogel' K, Mol e T, Rajadhyaks ha R A & Sanders
J V, J Cawl, 58 ( 1979) 11 4.
Mesh ram N R , Hegde S G & Kulkarni S B, Zeoliles. 6 ( 1986)
434.
Derouane E G inlmeli k B, Naccuche C. Ben Taarit Y, Vedrine .l
C, Coudurier G & Prali aud H, SllId Sill/Sci Cawl, 5, (1980) 5.
Zeo!iles, 5 ( 1985) 400.

reference to other side reactions and the e xtent of cok- 32 Bhavikatti S S & Patwardh an S R, "u! EI/ g Chelll Prod Res
Dev, 20 ( 198 1) 102.
ing should be critically studied .
33 Wu J C & L J Leu, Allpl Ca/al, 7 ( 1983) 283 .
34 Uguina M A , Sotelo J L & Serrano D P, AI'I'I Cawl, 76 ( 1991 )
183.
References 35 Meshram N R , Kulkarni S G & Rutnasamy , Appl Ca/al. 59
( 1986) 434.
I Pitzer K S & SCOlt D W, J Alii Ch em Soc, 65 ( 1943) 803.
36 Aneke L E ,Gerrit sen L A, Van den Berg P J & de Jong W A , .1
2 Has tings S H & Nicholson D E J, J Chem Eng Dala , 6 ( I% I) I.
Calal, 59 ( 1979) 26.
3 Wi se J S, Sril Pal l , 143,9 13 ( 1969).
37 Mesh ram N R , Hegde S G, Kulk arni S B & Ratnasamy P. AI'I'!
4 Benesi H A & Dvore tzkg, US Pal 3, 28 1,483 ( 1966).
Cawl, 8 ( 1983) 359.
5 Pollitzer E L , Ger Offell 1,946, 187 ( 1970).
38 Kaeding, W W & ButterS A, US Pal 3, 9 /1, 04 ! ( 1975). ci ted
6 Benesi H A , J Cawi 8 ( 1967) 368. from In d Eng CheJll Res, 31 (1992) 1875.
7 Narayanan S , Trails Faraday Soc ( 1979) 434. 39 Derewinski M , Haber J, Ptaszgusk i J, Shi va lkar V P & Dzwiga
8 Malsumota, H & Morit a Y, Inl CheJll Eng, 8 ( I 96l::l) 364. S, Sun! SlIIfSci Ca lal , 18 ( 1984) 209 .
9 Venuto P B , Hamilton L A, Landi s P S & Wi se J J, J Cawi, 5 40 Kaeding W W , Chu C, Young L B, Weinstein B & BUller SA ,
( 1966) 81. J Appl Po lYIIl SYIl1P, 36 ( 1981) 209 .
10 Wang K M & Lunsford J H, J Caw l 24, ( 1972) 262. 4 1 Meshram N R, J Ch em Techno l Bio lechnol, 37 (1987) I II .
II Gnep N S & Gui snet M, Appi Cawl, 1 ( 1981) 329. 42 Yashima T, Ahmad H, Yamazak i K, Katsu ta M & Ham N, J
12 Lee C S , Park T J & Lee W Y, Appl Cala i A : G elle ral, 96 Calal, 16 ( 1970) 273.
( 1993) 151. 43 Yas hima T, J Calal 26 ( 1972) 303.
13 Kl otz M R, U S Pat 4,269,813 ( 198 1) cited from Appl Cawl A: 44 Chen, N Y, Kaed ing W W & Dwye r F G . .I Alii Chelll Soc, 101
General, 96( 1993 ) 151. ( 1979) 6783 .
14 Kaeding W W , Chu C, Young L B & Butter S A, .I Cawl, 69 45 Kaed ing W W, Chu C, Young L B, Well1stein B & Butter SA . .1
( 1981) 392. Ca lal, 67 ( 198 1) 159.
15 Young L B , Butter S A, Kaeding W W, J Cawl76 ( 1982) 4 18. 46 Chen NY, Kaed ing W W & Dwye r F G , .1 Am Chelll Soc, 101
16 Nayak V S , Rickert L, Appl Cawl, 23 ( 1986) 403. : 22, ( 1979) 6783 .
17 Argauer R T & Landold t G R, US Pa l 3, 702 ,886 ( 1972),cited 47 Kaeding W W , Chu C, Young L B & Bu tter S A, .I Caw!, 69
from J Cawl, 61 ( 1980) 155. ( 1981) 382.
18 Marosi L , Stabenow T & Schwarz mann M, Ger Pa l DOS 48 Niwa M , KalO S, Hattori T & Murakami Y, .I Chelll Soc Fara-
2,830,787 ( 1980), cited from Appl Ca fct!, 23( 1986) 403. day TrailS, 1 ( 198 1) 2757.
19 Marosi L , Stabenow T & Schwarzmanll M, Ge l' Pa l DOS 49 Niwa M , Kato S, Hattori T & Murakam i Y. .I PIn's ClII:III . 90
3,006,47 / ( 198 1), cited fro m App/ Caut!. 23 ( 1986) 403 . ( 1986) 623 3.
20 Grose, R W & Flanigen E M, S el Pal 7,70 / , 115 ( 1977), cit ed 50 Hi bino T , Niwa M & Mu ra kami y , J Ca/a l, 128 (1993) 551.
from Appl Calal , 23( 1986) 403. 5 1 Karge H G , Sarbak Z, Hatada K, Weit kamp J & Jacobs P A , .1
21 Naya k V S & Ri ekert L, A cw Phys CheJll , 31 ( 1985) 157. Cala /, 82 ( 1983) 236.
 KAREEM 1'101.: DISPROPORTIONATION OFTOLUENE 327

52 Ekloff G S , Jaege r N I, Vl adov C & Petro v L, Appl Calal, 33
(1987) 73 .
53 Handb ook of Chemislry and Physics, edited by R C West (
Chemi cal Rubber Co, Press, Cleveland) 1974.
54 Tay lor W J , Wag man D D, Willi ams M G, Pitze r K S & Rossini
R D, J Res Nal BlIr Slalldards, 37 ( 1946) 95.
55 Guisnet M, J Calal, 88 ( 1984) 249.
56 Gnep N S , Martin de Armando M L, Marcill y C, Ha B H &
Guisnet M, S/tidies in SUlface Science alld C{lwlvsis, C(lw l.l'SI
Deacli va liolt ', edited by B Delmon and G F Froment (Elsevier,
Amsterdam), 6, 1980,79.
57 Gnep N S , Martin de Armando M L & Gui snet M, Reaci Kin el
Calal Lell, 13 ( 1980) 183.
59 Minac hev, Kh , Garanin V I, Isakova T, Kh arlamov V V. Mo-
lecu lar Sieve Zeolites -II , Advances in Chemi stry Series 102 ,
Am Chem Soc, Washinglon, D C ( 197 1) 44 1.
60 Ward , J W & Hansford R C, J CalC/ I, 13 ( 1969) 154.
6 1 Cortes, A & Corma A, J Cow l, 51 ( 1978) 338.
62 Voorhoeve, R J H, Advanced Mal erials ill Calalysis (Academic
Press , New York) 1977, 129.
63 Voorhoeve, R J H , Johnson D W( Jr ), Remeika J P &Gallagher
P K , Perovskile Oxides: Mal erials Science in Ca/a /rsis Sci-
ence, ( 1977) 827.
64 Li ang J J & Weng H S, J Cala l, 140 ( 1993) 302.
65 Gonzal ez T L , Rochester C H . Fierro J L G & Tascon. .I Chl'/II
Soc Faraday Trails, 80 ( 1984) 1089.
66 Fierro J L G , Tasco n J M D & Gon zalez T L, .I Cawl,
89( 1984 )209.

58 Bharati S P & S Bhatia, Ind Eng Chem Res, 26 ( 1987) 1854. 67 Sinfell J H ,Adv Calal, 23 ( 1973) 9 1.