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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.
di sproportion ation of xy lene form ed and tetTameth yl dry air, dea lumin ated morde nite treated under we t air
benzene are fo rmed by di sproporti onatio n of trimeth yl and a sa mpl e of fiu ori na ted al umin a have also been
benzene thu s fo rmed. T hu s, di sporporti onat ion of reported II.
produ cts is al so envisaged. Apart from these side re-
acti ons, some amount of xyle nes also isomerize to give For all the mordenites, the reacti on ra te increases
eth ylbenzene. In the di sproporti onati on process, theo- with increase in hyd rogen press ure. However, with
reticall y there is no loss of hydrocarbons as there is fiu orin ated alumin a, the tolu ene disp roporti onatio n
no methan e fo rma ti o n, as see n in th e case of ra te does not change with the hydroge n pressu re.
hyd rodealkyl ati on process . 95-96 vo lume per cent of Effect of Zeolite Preparation M ethod
liqui d produ cts are ob ta in ed in co nt ras t to th e
Doubl e structure catalys ts compris ing ZS M-S and
hydrodealkylation process where the li qui d yield is
boros ili cate cores were prepared 12 with a shell made
limi ted to about 82 vo lume per cent, due to the ac-
of silicate with no acid ic properties and havi ng a uni-
companying loss of the meth yl group in the fo rm of
form pore size of 6A. Thi s catalys t showed hi gher 1)-
meth ane.
se lecti vit y in compariso n to ZS M-5 Iy pe catalysts at
The disproportionati on process is usuall y carried the sa me co nversion level. The resul ts sugges t that jJ-
our in the vapour phase over solid acid catalysts such selec ti vity could be enh anced by 'electively in acti-
as sili ca-a lumin a and zeo li tes at elevated temperatures. vating the ex ternal acid sites withou t chang ing the pore
Mordenite, fa uj as ite 3 and va ri ous form s ofmo rde ni te~ mouth size. The catalysts were prepared by the kn ow n
incl udin g dea lumini zed modi fica ti ons"' are know n to method ".
be superior in many res pects to silica-a lu mi na. Other
Doubl e stru cture ca talys ts were prepared by mi x-
zeoli te catalys ts which include mordeni te 6.7 , rare-earth
ing Na-ZS M-5 and Na-bo ros ili ca te seeds wi th fumed
exchanged X- zeo lites 8,9 and ca tio n excha nged Y -
sili ca, NaOH , distill ed water and TPAB r, an d sti rring
zeo lites 8, 10 possess high acti vity. Unfo rtu nately, these
the mix ture until it became homogeneous (pH 10. 24h
cata lysts deacti va te qu ic kl y due to coke depos ition
and crys talli sation do ne at l70 0 e for 48h). The fina l
within a few hours on stream and also show low se-
do uble stru cture catalys ts of ZS M-5 type cores and
lecti vity for di sporporti onati on. Us ing ZSM-5 zeo lite
sili ca lite shell (weight rati o I: I of shell to core), H-
as catalyst, the product distri buti on can be directed to
ZSM-5/s ili ca li te, and H-boros ili cate/s ili ca lite were
the selective fo rm ation of p-xy lene, the mos t va lu -
prepared by a simil ar procedu re.
abie isomer, modi fyi ng the shape selecti vity of the zeo-
lite. 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-
Subsequentl y the efi'ect of various pa rameters such
gated by many researc h e rsl~ -16. It was show n th at the
as temperature, press ure, surface acid ity, crys tallin -
product distributi on in thi s reac ti on sys tem is particu-
ity, SiO/A I2 0 J rati o, and carrier gas on the selective
larl y sensiti ve to the interacti on of intracrystalline dif-
disporportion ation of toluene to prod uce benze ne an d
fusion and reacti on. Pentas il zeo li tes were generally
p-xy lene is summ arized.
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
Effect of Pressure conta ining organic bases such as tetrapropyl-ammo-
nium hydroxide/halide l7 and 1-6-diaminohexane lx. 1-
The rate of disproportionation reaction is usually 3-diaminopropane I9 . Pentasil zeolites can also be pre-
reported to increase with increasing pressure of the pared in the absence of an organic templating agent 20·
reaction. The effect of hydrogen pressure on toluene 21
d ispro p o rti onation using different samples of
morde nite viz., ammonia exchanged mord e nite, The catalyti c activity of pentasi l zeolites in the
mordenite dealuminated wi th HCI and treated under di sproportionation of toluene at near steady stale af-
KAREEM el at.: DISPROPORTIONATION OFTOLUENE 321
ter initial partial deactivation is almost proportional activity is also related to its lower crystallinity in co m-
to the AI-content, independent of the nature of the tem- parison to another sample with SiO 2/ AI 20 3 rati o of 15
plate used for zeolite synthesis. The ratio of benzene and crystallinity 100 per cent .,...
to xylenes in the products depends only on toluene
conversion, independent of composition or synthesis With the decrease in silica-to-alumina ratio , the drop
mode of zeolite and of reaction temperature. 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
Effect of Surface Acidity of Zeolites
dealkylation). For ZSM-5 catalyst with s ilica-to
The hydrocarbon reactions take place on Bronsted alumina ratio 15 , xylene disproportionation was also
acid sites which are formed on zeolites . The nature, an important reaction , which explains the relati ve ly
strength and number of these sites can be detected by higher percentage of trimethylbenzenes obtained in
IR, magic angle spinning NMR and temperature pro- the product. Thus, although the two zeolites with SiO/
grammed desorption (tpd) of ammonia 22•2H . One of the AIP 3ratios of 15 and 37 show different tolue ne co,;-
important factors for the variation in acid sites is the version and selectivity to disproportionation , th e ir
ratio of Si0 2 and AIP1 in the zeolite sample. The acid xylene yield is quite similar 35.36 . It has been po inted
sites in H-ZSM-5 zeolite of varying SiO 2/ AI 20 1 ratios out that dealkylation reactions take place on stronger
have been well characterized 29 . The tpd studies have acid sites than toluene disproportionation , hen ce the
shown that the number of ammonia molecules per unit acid strength of ZSM-5 increases with the aluminum
cell which are equivalent to the number of acid sites content.
per unit cell are directly proportional to the number
The number of molecules of toluene that underGo
of aluminium atoms per unit cell. The catalytic data b
tion than the values initially obtained in the primary The deposition of alkoxide was performed us ing
product is expected since its least minimum diam al- an apparatus consisted of a vacuum system equipped
lows a faster diffu sion than the other two isomers. with a conventional quartz spring bal ance4 ,! . HZSM-S
was set in a quartz baske t hun g on the balance a nd
The p-selectivity enhancement and the decrease in evacuated at 673 K until there was no decrease in
toluene .conversion observed in the modified zeolites we ight and then the alkoxide was deposited at S93 K
can be related with the fo llowing roles of the modi- through CVD method. For the high ly depos ited zeo-
fier agent: lite, the alkoxide deposition was repeated after the
evacuation of the gas phase. After the deposition , the
• Pore blockage occurs by deposition of modifi er
zeolite was calcined in situ in 26.7 kPa of oxygen at
agents. Tortuosity of the channel system is in-
673 K to remove coke formed on the zeolite through
creased, which delays the diffusion of the differ-
the deposition.
ent molecules associated with the reaction.
• Linkage or deposition of the modifer age nt to the Toluene di sproportionation over HZSM-S zeolites.
unselective acid sites located on the external sur- mod ified by chemical vapour deposition of silicon
face of the zeolite crystals, avoids the external alkoxide, also predicts that as the si lica amount in-
iso merization of the primary product. creased, {he selectivity to m-and o-xy lenes decreas ed ,
whereas that of p-xylene increased 50 . The deposition
p-xylene selectivity was enhanced 4 2·4.1 by impreg- of 'ilica did not change selectiviti es to benzene and
nat ion with phosphorous and boron compounds and xylenes. The fraction of the p -isome r in xylenes in-
by coating the catalyst surface with polymers. The phe- creased to more than 98 per cent. From adsorption
nomenon was explained on the basis that the pores in meas urements and test reactions, it was found that thi s
the ZSM-S zeolite are approximately 7-8A in diam, modification resulted in the narrowi ng of the pore-
which permit the rapid diffusion of tolu ene and p-xy- opening size and the inactivation of the external su r-
lene with molecular diam 6.3A but severely retard the face . Primarily the narrowing of the pore-opening size
diffusion of 0- and m-xylenes with molecular diam of caused the high p-selectivity.
6.9A 45 .
gas with pressures greater than 0.1 MPa ll . A similar ing diameter of the gas atom or molecule with nitro-
effect has been reported for the ethyl benzene gen being an exception. Hydrogen, the carrier gas
disproportionation using hydrogen 51. Ekloff e t al hav ing the smallest mol ecules, gave least toluen e co n-
(1981) (Ref 52) have studied the effect of carrier gases; version. The observed dec re ase in the activity of
hydrogen, argon, nitroger. , helium and oxygen on the di sproportionation reaction was discu ssed in te rm s of
toluene disproportionation using shape selective zeo- either a decrease in Bronsted aciditySl or a decrease in
lite HZSM-5 with pressure between 0.1-1 MPa. Oxy- the concentration of interm e diate benzyli c
gen is generally used for the removal of coke. The carbocations in the presence of hydrogen 11 ,55. The de-
nitrogen physisorption studies of the catalyst ZSM-5 pendence of the toluene conversion rate on the size of
(SiO/AIP1 =40) gave 21 molecules per unit cell and the atoms or molecules of the inert carrier gases, i.e.,
the scanning electron micrograph (SEM) reported an argon and helium could be due to the shielding of cata-
average zeolite particle size of around I iJm. The ac- lytically active sites.
tivity of toluen e conversion at 325°C was found to
decrease in the order: Ar (2.94) > N2(3.15) > He (2.65) Hydrogen has bee n re ported to decrease the deacti-
> H2 (2.34), where the values in parentheses are the vation of mordenites by reducing the rate of coke for-
diameters of the atoms or van der Waals diameters of mation and its toxicity II . The positive apparent order
the molecules 53. The average mass balance for the in hydrogen found with all the mordenites was ex-
products of toluene conversion in the different carrier plained by the regeneration of the active sites due to
gases was found to be very similar and yielded about the removal of the coke deposited on the catalysts 56.57 .
50 wt per cent xylenes, 30 wt per cent benzene and 20 Moreover, the initial activity of mordenite unde r at-
wt per cent methane. The distribution of the xylene mospheric press ure is of the same order of magnitude
isomers was found to be close to the thermodynamic and often higher than the values found under th e hi gh
equilibrium under all conditions used 54. In all the cases hydrogen pressure.
the toluene conversion at constant toluen e partial pres-
The experiments carried out under nitro ge n revea l
sure (lkPa) increased with increasing total press ure
that hydrog e n is not ne cessa ry for tolu ene
of the carrier gas (in the range 0.1- I MPa).
di sproportionat ion and its m ain role is to decrease
During the catalytic process, it has bee n generally mordenite deactivation by coking.
observed that the catalyst darkens presumably due to
coke deposition. The dark colour is removed, if oxy- Under nitrogen gas the mordenite catalyst deacti-
gen is used as a carrier gas. Subsequent to the use of vation was much more rapid as compared to hydro-
oxygen either as a carrier gas or as a pul se in other gen gas atmosphere 5~ . Mass spectrum studies of
carrier gases, the toluene conversion proceeds rapidly, des orbed products of the coked mordenite reported
if hydrogen is used as a carrier gas. Thi s high activity that the nature of the coke depends upon gaseous e n-
results mainly in the formation of large amounts of vironment 59 .
methane. The subsequent use of nitrogen resulted in
conversion rates and product distributions, which were Isomerization of o-and m- to p-xylene
similar to those obtained on fresh catalysts. However,
no effect of acceleration of the toluene conversion was Another route to obtain p-xylene is by 0 - or m-xy-
found by the use of oxygen as a carrier gas, if a fresh lene isomerization over the same catalysts. Unfortu-
catalyst was applied. The treatment of the catalyst with nately, only about 25 per cent of the initial substance
water vapour did not show any change in activity. can be converted to p-isomer by this reaction since
less than 25 per cent of the thermodynami c eq uilib-
The sizes of the molecules or atoms of the carrier rium mixture of xylenes consists of p-xylene (in the
gas can be correlated with the effect of the type of temperature range 300 - I 000K )45.
carrier gas on the toluene disproportionation activity. The isomerization of xylenes is known to be ca ta-
It was found th at the activity decreases with dec reas- 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- La ,_x Sr, Ni0 3 (0.3 < x < 0.7) revealed ex istence of
action model involving the adsorption of xy lene mol- NiO-and La z Ni0 4-phases in addition to the La Ni0 3
ecul es on the protonic sites of the cata lyst surface and perovskite structure. The surface of perovs kite-type
su bsequent intramo lecul ar 1,2 shifts of the meth yl oxides is highl y heterogeneous 65,6(,. Apart from NiO
groups to form the isomeric xylenes 6' . HZSM-5 zeo- and La 2 Ni0 4 phases, La,_xSrxNi0 3 also contains nickel
lite is active for the isomerization of xy lenes . It con- atom, whi ch interacts throu gh the che misorpti on of
tains two types of hydroxyl gro ups whi ch absorb at hydrogen. The transition metals of group VIII (N i, Pd ,
3600 and 3720 cny', respectivel y, in the IR reg ionZ7 and Pt) possess stron g hydroge n chemi sorptic ac ti v-
which can serve as potential Bronsted sites in acid ity67 and catalyti c acti vity for disproporti onati on re-
catalysed reaction s. acti on 65 . It was found that as x increases in the La ,-
Isomerization of o-xylene has been reported over xSrxNiOl (x>O), the amount of Ni O- and La 1 Ni0 4 -
SiHZSM-5 catalyst which was obtained by ch·e mi cal phases increase. The disproportionation products were
vapo ur depo sition (CV D) of sili co n a lkox ide on formed when either NiO , the mixture of NiO (50 per
HZSM-5(ref 50). The conversion of o-xy lene was dras- cent) and LaNi0 3 or the mi xture of La 2 Ni0 4 NiO (50
tically decreased by the depos ition of sili ca. p-xylene per cent) and LaNi01 as catal ys ts were used_A change
and m-xy lenes were main products along with littl e in the carrier gas from nitrogen to hel ium sho wed that
amounts of benzene, ethyl toluene and tri-methyl ben- ni trogen gas could react with the adsorbed oxygen and
zenes. As the silica content increased from 0 to 13.3 the latti ce oxygen on the catalys t surface, lead ing to a
wt per cent, the fraction of p-isomer (in 0 - and m- decrease in the di sproportionation reacti on rate.
xy lenes) increased from the equilibrium value (3 1.0
per cent at 673 K) to 98.68 per ce nt. In addition , Industrial Processes
selectiviti es to the formation of benzene, toluene and
ethy lbenze ne increased with si lica amount in the cata- Toluene di sproportionati on has been recognized as
lyst. The fo rm ati on of large trimethyl benzenes was an important indu stri al process. There are three ma-
completely suppressed. 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-
Perovskite-type Oxides As Catalysts nologies include: (i) the Tatoray Process (UOP) , (ii )
Perovskite -type oxides have the general formul a the Xylene-Plus Process (Atl antic Ri chfi eld), and (iii)
ABO, and have the ability to change and/or substitute the LTD, Low-Temperature Di sproportionati on Proc-
cation composition at sites A and B with mostly a ess (Mobil Chemi cal Co.). In our country, there is onl y
rare earth or alkali metal at site A and a tran si ti on one industry being run by Reliance group near Surat
metal at site B 6Z .63 . These mixed oxides are, therefore, in Gujarat, which is based on the UOP technology.
sui table materi als for the study of the stru cture-prop-
Between 1985 and 1993, nine plants commiss ioned
erty relationship of catalysts. Recently, oxides substi-
toluene disproportion ation units in the US that utili ze
tuted with Ai, having the formula AAB0 3 have at-
the Tatoray Process . The Low-Temperature Di spro-
tracted a lot of attenti on due to their excellent cata-
portionation Process is currentl y the most common
lytic actl vlty. Th e rea rr ange me nt and
process. Chalmette Refining , LLC, operated and par-
disproportionation of toluelle over La, _x SrxNi0 3 cata-
ti all y owned by Mobil Oil Company, in Chalmette,
lysts in the presence of oxygen and at one atmospheric
Loui siana utili zes a Toluene Di sproportionation Unit
pressure has been recently reported 64 • The reacti on
tending toward the selectivity ofp- xyiene. The Mobil
products include 0-, m- and p-xylenes, as well as some
MTDP-3 Technology is one of the most profitable
ethyl benzene. It was reported that the rearrangement
processes currently in use. This process minimi zes the
and disproportionation oholucne on the perovskite
excess hydroge n required to drive the reaction while
catalys ts were due to the NiO-and La1 Ni0 4-phases .
increas ing the se lectivity to the production of p-xy-
An examination of the X-ray diffraction patterns of
lene.
KAREEM e l al.: DlSPROPORTIONATION OF TOLUENE 325
The Tatoray process produces xylene and benzene These catalysts can be generated in various ways .
from toluene and C 9 aromatics reacting with hydro- Naturally occurring zeolites can be converted by pro-
gen over a noble-metal or rare-earth catalyst. This cedures known as base exchanging, steaming, alumina
process uses catalytic disproportionation with an ex- extraction , and calcination.
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 Conclusions
between 350-525 ° C and 10-15 atm. This reaction
The current research involves discovering and uti-
occurs through a high recycle rate of hydrogen over
lizing highly selective catalysts that allow for the pro-
the catalyst and the catalyst is regenerated. Current
duction of more desired product and less by-products.
technology allows the modification of this process.
Following conclusions can be drawn from the above
The Tatoray process results in a 38 per cent conver-
study.
sion of toluene.
Toluene disproportionation is an industrially im-
The LTD process (Low-Temperature portant reaction to produce valuable p-xylene and
Disproportionation) involves the formation of benzene benzene from less valuable toluene. Although this re-
and xylenes from liquid-phase tol uene action is being carried out industrially since long, there
disproportionation. This reaction occurs using a zeo- are many factors including the type of catalyst, effect
lite-based catalyst at approximately 260°C and of reaction variables and the carrier gas which play an
4 .5MPa. The catalyst life is approx 1.5 Y and is regen- important role in improving the product formation .
erated by burning the accumulated coke. The process
involves series of three distillation columns follow- Hydrogen is generally used as carrier gas for the
ing the reactor. These columns recover benzene, xy- reaction, but it has been suggested that nitrogen can
lene, and toluene where the toluene is recycled to the be more beneficial in giving higher amount of liquid
process feed. As the zeolite catalyst deactivates it may product as well as saving the catalyst from the active
cause a temperature rise in the reactor to approx. sites blockage, which takes place with hydrogen . A
3 15°C. The LTD Process yields approximately 85 per detailed study must be conducted to compare the ac-
cent p-xylene with a mixture of other xylene isomers. tivity, and liquid product yield using nitrogen as car-
rier gas with less coking hydrogen.
Over the years many of these original processes
have been modified to reflect the current technology. The effect of the type of catalyst, which is acti ve at
For example, vapour phase toluene disproportionation lower temperature and pressure and thereby result in
process has been modified where a zeolite catalyst lesser coke formation even with nitrogen as carrier
can be used with low hydrogen to hydrocarbon molar gas may be explored.
ratio. This process utilizes a crystalline aluminosilicate
Study also summarizes the effect of pressure on the
zeolite. The reaction takes place in the vapor phase
rate of toluene disproportionation . Usually the rate of
over a radial flow or fixed bed. It is also possible for
disproportionation reaction is reported to increase with
this reaction to take place in a batch process opera-
pressure. But there are a few exceptions , such as fluori-
tion. This zeolite comprises silica to alumina in the
nated alumina based catalysts, where the pressure has
ratio of 12. This catalyst is characterized as having a
no effect. Such catalysts may further be explored so
8- I 5 A pore opening containing Group VII metals ,
that the reaction is carried out at lower pressures,
hydrogen , and rare earth cations. This catalyst is of-
thereby saving precious energy. The mechanism of
ten referred to as ZSM-5. Other examples that meet
activity of such catalysts may also be explored .
the criteria for performing this reaction include ZSM-
I I , ZSM-12, ZSM-35 , and ZSM-38. These catalysts Efforts must be directed towards synthesis of dou-
are well known for their long life and resistance to ble structure catalysts, which have shown higher p-
high temperatures and coking. These catalysts are selectivity in comparison to ZSM-S type catal yst at
known to be extremely stable.
326 J SCIIND RES VOL 60 APRIL 200 1
the same conversion level. These catalysts have been 22 Haag, W 0 , Lago R M & Weisz P B, Nalllre, 309 ( 1984) 5X9.
shown to enhance p-selectivity by selective ly inacti- 23 Olson D H , Haag W 0 & Lago R M, J Cawl, 61 ( 1980) 390.
vati ng the external acid sites without changing pore 24 Jacobs P A & va n Ballmoos R J, J Phy.\" CheJll , 86 (1982) 3050.
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& Vander Velden G P M, J Phys Chell l, 88 ( 1984) 5.
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sition of silicon , magnesium, boron and phosphorus 27 Topsoe, NY, Pendensen K & Derouane E G,.1 Cawl, 70 ( 198 1)
act favourably in increas in gp-xy le ne selectivity up to 41.
99 per cent. However, maj or drawback of this tec h- 28 Ande rson J R , Fogel' K, Mol e T, Rajadhyaks ha R A & Sanders
J V, J Cawl, 58 ( 1979) 11 4.
nique is that the pe r cen t tolu e ne co nvers ion is drasti-
29 Mesh ram N R , Hegde S G & Kulkarni S B, Zeoliles. 6 ( 1986)
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may be attempted to obtain better p-xyl e ne yield . The 30 Derouane E G inlmeli k B, Naccuche C. Ben Taarit Y, Vedrine .l
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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.
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