Applied Catalysis A: General 266 (2004) 203210

Transformation of mixtures of benzene and xylenes into

toluene by transalkylation on zeolites
Rafael Roldn, Francisco J. Romero , Csar Jimnez1 , Victor Borau, Jos M. Marinas
Departamento de Qumica Orgnica, Universidad de Crdoba, Campus de Rabanales, Edificio Marie-Curie, Ctra. Nnal. IV, km 396, 14014 Crdoba, Spain
Received in revised form 10 February 2004; accepted 11 February 2004

Available online 9 April 2004

Abstract

The gas-phase transformation of mixtures of benzene and xylenes has been studied on several zeolites. Transalkylation between benzene and
xylenes and disproportionation and isomerization of xylenes are the main reactions in this process. Under the reaction conditions used, medium
pore zeolites (FER and ZSM-5) were inactive, whereas large pore zeolites (USY, BETA and MOR) yielded toluene and trimethylbenzenes on
a different extension. The catalytic activity has been related to the acid properties and so MOR(20) exhibited the highest overall conversion.
The relative contributions to the transalkylation and disproportionation reactions were found to be influenced by the feed composition (i.e.
the benzene to xylene ratio), the strength of the acid sites and the pore size and geometry of the catalysts. All zeolites underwent a substantial
deactivation by coke deposition, particularly when o-xylene was used as reactant. Pt-supported zeolites were used in order to improve the
stability of the catalysts.
2004 Elsevier B.V. All rights reserved.

Keywords: Benzene; Toluene; Xylenes; Trimethylbenzenes; BTX; Transalkylation; Xylene disproportionation; Xylene isomerization; Zeolites; Coke

1. Introduction with 10 MR pore opening [79]. Other materials, such as

Aromatic compounds constitute an important volume of
production in the petroleum refining industry. Among them,
benzene, toluene and xylenes, known as BTX, are of great
importance because they are raw materials to obtain many
derivatives. They are mainly produced in the catalytic re-
forming and naphtha pyrolysis processes, though the ther-
modynamic distribution for them (32:36:32) is different from
the market demand (55:11:34) [16]. Toluene has the low-
est demand and is used in several processes, which have
been reviewed by Wang et al. [7], for its conversion into the
others. They are mainly two: toluene disproportionation and
transalkylation with trimethylbenzenes, both requiring acid
catalysis. In the former, FriedelCrafts or silicaalumina cat-
alysts, among others, have been employed, but they have
been recently substituted by zeolites such as mordenite, beta,
Y and specially the medium-pore size zeolites, like ZSM-5,
Corresponding author. Tel.: +34-957-218-638/+34-957-212-065;
fax: +34-957-212-066.
E-mail addresses: qo2rosaf@uco.es (F.J. Romero),
qo1jisac@uco.es (C. Jimenez).
1 Co-corresponding author.
SAPOs [10,11] and MCM-22 [12] have been also investi-
gated as catalysts. This kind of reactions, which can be even
used as a good test for catalyst acidity [13], is greatly in-
fluenced by diffusion and adsorption phenomena. For this
reason, zeolites and mesoporous materials offer great possi-
bilities for the toluene or other aromatic compounds dispro-
portionation [14,15].
On the other hand, transalkylation needs the use of large
pore zeolites because aromatics A9 can not diffuse through
the 10 MR pores [7,8]. In some cases, dealumination can be
very useful to obtain stable catalysts by changing the acid
properties of the catalysts [1618].
Among the xylene isomers, there are differences as well
between the thermodynamic equilibrium (o-: m-: p- = 23 :
53 : 24) and their demand for industrial purposes (18:2:80).
The selectivity to the para-isomer is of great interest be-
cause it can be transformed into terephtalate, which is used
for the production of polyesters [37,19]. Ethylbenzene and
m-xylene are converted to p-xylene, by using zeolites as well
[2023]. Actually, m-xylene transformation is a test reaction
to characterize the porous system of zeolites [24,25]. The
mechanism can be either monomolecular, through benze-
nium ion intermediates, or bimolecular, by means of xylene

0926-860X/$ see front matter 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2004.02.008
204 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210
disproportionation, requiring two acid sites and subsequent
transalkylation [26,27].
The investigation on the interconversion of benzene and
methylated benzenes on shape-selective catalysts is of a high
practical interest for the production of the most useful chemi-
cal intermediates at each moment. Polymethylated benzenes
are observed among the main products in the methanol con-
version to hydrocarbons over several zeolites [2830]. The
selectivity to these compounds depends on the catalyst and
the reactions conditions used. Thus, beta zeolite favours the
formation of penta- and hexa-methylbenzene, whereas USY
and mordenite zeolites preferentially lead to tetramethyl-
benzenes. Higher temperatures increase the selectivity to
heavier aromatic compounds. Also, acetone can be trans-
formed into hydrocarbons under similar conditions [29]. In
this case, dimethylbenzenes are the most abundant aromatic
compounds.
Moreover, some of these aromatic compounds are present
in fuels in order to increase their octane number. Although
the total content of aromatic compounds in the so called re-
formulated gasolines is restricted (25 vol.%) due to their
toxicity, that of benzene must be specially low (<1%) [31].
For instance, a reforming naphtha feedstock contains ben-
zene in approximately 6% and xylenes in approximately
15%. As a consequence, the investigation on the reactions
affecting methylated benzenes is justified.
This paper reports on the activity and selectivity of var-
ious zeolites in the gas-phase reaction between benzene
and xylenes. Two main different mechanisms are involved:
transalkylation towards toluene and disproportionation of
xylenes to toluene and trimethylbenzenes. The effect of the
zeolite topology, their SiO2 /Al2 O3 ratio, temperature and
feed composition was studied.
2. Experimental
2.1. Catalysts
Zeolites of different topologies and SiO2 /Al2 O3 ra-
tios (indicated in brackets) [viz BETA(25), BETA(75),
BETA(150), MOR(20), MOR(90), USY(60), FER(55)
and ZSM-5(80)] were purchased from Zeolyst Int. (refs.
CP814E, CP811E-75, CP811E-150, CBV21A, CBV90A,
CBV760, CP914 and CBV8014, respectively). All these
zeolites were calcined in air at 580 C prior to the reaction,
in order to obtain their protonic form.
BETA(25) zeolite was also dealuminated by treatments
with nitric acid, BETA(25)-NA and oxalic acid, BETA(25)-
OA, following a procedure described elsewhere [32,33].
A supported Pt catalyst, Pt/MOR(20) (0.5 wt.% Pt), was
synthesized by the incipient wetness impregnation method
with an aqueous solution of Pt(NH3 )4 (NO3 )2 .
All solids were pretreated in situ in the reactor, being cal-
cined at 400 C in a nitrogen flow (30 ml min1 ) for 30 min.
The sample with platinum was later held at 400 C for 30 min
in a hydrogen flow (60 ml min1 ) to reduce the metal.
2.2. Characterization
All the catalysts have been already characterized by us-
ing several techniques. Analyses included XRD, specific
surface area (BET method) and determination of their
acid properties; the latter either by pyridine adsorption in
liquid-phase and its spectrophotometric determination or by
adsorption in the gas-phase and temperature-programmed
desorption (TPD) of the same chemical. These properties
were discussed in an earlier paper [32]. Chemical elemen-
tal analyses, measured by atomic absorption spectroscopy
(Service Central dAnalyse, CNRS, Vernaisson, France) are
presented too.
2.3. Catalytic reactions
The reactions were carried out in a continuous flow
fixed-bed reactor. 0.5 g of catalyst were packed inside a
stainless steel reactor (10 mm i.d.). A feed consisting of a
25% molar mixture of each component, benzene, o-xylene,
m-xylene and p-xylene (Aldrich), was conducted through
it by means of a Sage 351 propulsion pump and nitrogen
as carrier gas (60 ml min1 ). Three binary feeds of benzene
and each of the isomers of xylene in 50% molar composi-
tion were used in other runs. The reaction products were
analyzed and quantified in a gas chromatograph connected
on-line to the reaction system by using a methyl silicone
100 m 0.25 mm i.d. fused silica capillary column and a
linear temperature program (starting at 100 C for 15 min
and then increased to 115 C at 2 C min1 ). However, m-
and p-xylene were not resolved because of their very sim-
ilar boiling points. For this reason, both were considered
together for calculations. Preliminary blank runs without
catalyst were done, finding no conversion. The reaction
conditions used were WHSV 4.7 h1 (2.7 ml h1 for the
hydrocarbon feed), atmospheric pressure and temperatures
over the range 250350 C, with time on stream up to 5.5 h.
Calculations have been made defining either xylene con-
version (considering all the isomers grouped) and benzene
conversion (mol%). Isomerization of xylenes is independent
from the whole transalkylation process. Therefore, it is not
included in the xylene conversion and so it is separately
studied. In the same way, in experiments with binary feeds,
this side reaction has been excluded for the conversion data.
The products found in the reaction are toluene and 1,3,5-,
1,2,4- and 1,2,3-trimethylbenzenes; heavier aromatic com-
pounds were not detected except for tetramethylbenzenes in
some cases and in small amounts (<1%). Cracking products
were not observed.
3. Results and discussion
3.1. Characterization of the catalysts
The properties already determined for these catalysts are
presented in Table 1. All of them possess high specific
 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210 205

Table 1 50
Textural and chemical surface properties of the catalysts
Xylene Conversion (mol %)

Zeolite SBET Aciditya Acidityb SiO2 /Al2 O3 c 40

(m2 g1 ) (mol g1 ) (mol g1 ) ratio
BETA(25) 530 1010 910 24.4 30
BETA(75) 615 850 348 83.8
BETA(150) 583 690 74 176.0
MOR(20) 369 830 1158 21.4 20
MOR(90) 484 640 391 97.2
USY(60) 746 670 254 58.8
10
FER(55) 305 140 12 65.2
ZSM-5(80) 413 550 212 84.6
BETA(25)-NA 530 680 268 95.0 0
BETA(25)-OA 442 700 386 58.4
Benzene Conversion (mol %)

a Spectrophotometric method. 40
b TPD method.
c AAS. 30

surface areas. It is noteworthy that the most acidic solids are 20

MOR(20) and BETA(25), as determined by both the spec-
trophotometric and the TPD methods. The treatments with
10
nitric and oxalic acids over beta zeolite lead to dealuminated
zeolites (being dealumination higher in the first case), which
0
have a lower population of acid sites. 0 1 2 3 4 5 6

3.2. Catalytic activity Time on stream (h)

Fig. 1. Variation of the xylene and benzene conversions with the re-
Large pore zeolites are active towards the transformation action time at 300 C for catalysts: BETA(25) (); BETA(75) ();
of mixtures of benzene and xylenes (1:3) in the gas phase at BETA(150) (); MOR(20) (); MOR(90) (); USY (60) (); FER(55)
300 C (Fig. 1 and Table 2). This was the temperature cho- (); ZSM-5(80) (). Feed (mol%): benzene (25%), o-xylene (25%),
m-xylene (25%) and p-xylene (25%).
sen for comparison due to the lower conversions obtained
at 250 C and the stronger deactivation observed at 350 C.
These reactions are carried out on acid sites and so zeo- conversion was obtained with medium pore zeolites, i.e.
lites with a higher population and acid strength will provide ZSM-5 and ferrierite, irrespective of their acidity. The ab-
higher conversions. Thus, the conversion decreases in the sence of any activity for these zeolites can be explained in
order MOR(20) > MOR(90) > BETA(25) (see Fig. 1), the terms of the shape-selectivity due to the more restricted 10
former being the most acidic solid. Acid strength also plays MR pore openings of FER and ZSM-5, which hinder the
an important role as is evidenced by the fact that MOR(90) progress of this process. However, these catalysts have been
zeolite, with stronger acid sites, yields a higher conversion reported to be good catalysts for one of the reverse reactions,
than BETA(25) zeolite, with higher overall population of the toluene disproportionation [7].
acid sites. In addition, the moderately acidic BETA(75) and Dealumination of beta zeolite produces a loss in total
USY zeolites exhibit a low activity, whereas BETA(150) acidity (Table 1) which, in turn, makes the catalyst less active
was almost inactive for the reaction. On the other hand, no in the reaction (Fig. 2). Nitric acid gives rise to a higher
dealumination, as indicated by the SiO2 /Al2 O3 ratio and
the acid population, by leaching aluminium species to the
Table 2
Product distributions (mol%) for the transformation of a mixture of ben-
solution, while oxalic acid is expected to produce a higher
zene and xylenes (1:3) on several zeolites (T = 300 C; reaction time = amount of extra-framework aluminum during the treatment
15 min) [33].
MOR(20) MOR(90) BETA(25) BETA(75)
For a better understanding of this process, one should
keep in mind that there are different equilibria involved.
Benzene 15.3 19.5 22.8 23.8 As depicted in Scheme 1, we can distinguish two main
Toluene 32.7 21.1 14.5 4.8
m- + p- Xylene 29.9 34.8 40.0 48.9
reactions: (a) xylene disproportionation (Eq. 1), which is
o-Xylene 7.9 10.6 12.9 19.1 the opposite reaction to the transalkylation between toluene
1,3,5-Trimethylbenzene 4.0 3.7 3.0 1.1 and trimethylbenzene, used in industry; and (b) transalky-
1,2,4-Trimethylbenzene 8.5 8.3 6.6 2.5 lation between benzene and xylene (Eq. 2), which is the
1,2,3-Trimethylbenzene 1.0 1.0 0.7 0.2 opposite reaction to toluene disproportionation. Both reac-
Tetramethylbenzenes 1.0 1.0
tions involve only the reactants. The transalkylation between
206 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210

35
T(d) in the product (mol %)
Xylene Conversion (mol%)

30 20

25
15
20

15 10

10
5
5
0
0
T(t) in the product (mol %)

0 1 2 3 4 5 6
20
Time on stream (h)
15
Fig. 2. Variation of the xylene conversion with the reaction time for dealu-
minated beta zeolites: BETA(25) (); BETA(25)-NA (); BETA(25)-OA
(). Feed (mol%): benzene (25%), o-xylene (25%), m-xylene (25%) and 10
p-xylene (25%).
5

benzene and trimethylbenzene (Eq. 3) is unlikely, since it

implies the reaction between a reactant and a primary prod-
uct and so the latter should react again before diffusing out
of the pores. Moreover, reactions involving the formation of
tetramethylbenzenes are negligible. Finally, the isomeriza-
tion of xylenes also takes place. Equilibria 1 and 2 can be
collected in Eq. 4, giving rise to a stoichiometry of 1:3 for
the reactants, benzene and xylenes.
To evaluate the different extension of these reactions, we
have defined two parameters: toluene produced in xylene
disproportionation, T(d), and toluene produced in transalky-
lation between xylene and benzene, T(t). To calculate them
and considering that the contribution of Eq. (3) is negligible,
it should be established that:
T(d) = TMB; T(t) = TT T(d);
where TMB is the yield to trimethylbenzenes and TT is the
overall yield to toluene.
Plotting both parameters (Fig. 3) and the T(t)/TT ratio
(Fig. 4) versus the reaction time, the contribution of both
(CH3)2
0
0 1 2 3 4 5 6
Time on stream (h)
Fig. 3. Variation of T(d) and T(t) (mol%) in the product with time on stream
at 300 C for catalysts: BETA(25) (); BETA(75) (); BETA(150) ();
MOR(20) (); MOR(90) (); USY (60) (). Feed (mol%): benzene
(25%), o-xylene (25%), m-xylene (25%) and p-xylene (25%).
mechanisms and their variation during the reaction are ob-
tained. The higher this ratio the greater the participation of
Eq. 2 in the process, while the opposite implies that Eq. 1
prevails. The T(t)/TT ratio follows the order: MOR(20) >
MOR(90) > BETA(25) > BETA(75). The T(t)/TT values
at the same toluene yield (14%) for MOR(20), MOR
(90) and BETA(25) are 0.39, 0.32 and 0.28, respectively.
This ratio is 0.20 for BETA(25)-NA. At lower toluene
yields (5%), the values for BETA(25), BETA(25)-NA and
BETA(25)-OA are 0.25, 0.21 and 0.19, respectively. These
results are consistent with the total acidity determined for
these solids. The other catalysts afford no toluene or do it
only in very low level. MOR(20) presents higher yield to
(CH3)3

2 + Eq. 1
0,7

(CH3)2 0,6

+ 2 Eq. 2 0,5
T(t)/TT

0,4
(CH3)3 (CH3)2
0,3
+ + Eq. 3
0,2

0,1
(CH3)2 (CH3)3 0 1 2 3 4 5 6

+ 3 + 3 Eq. 4 Time on stream (h)

Fig. 4. T(t)/TT ratio versus time on stream for BETA(25) (), BETA(75)
Scheme 1. Equilibria between benzene, toluene and xylene in the gas (), MOR(20) () and MOR(90) (). Feed (mol%): benzene (25%),
phase. o-xylene (25%), m-xylene (25%) and p-xylene (25%).
 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210
toluene through the transalkylation reaction (T(t)/TT ratio
above 0.5) at short reaction times. With only this exception,
the disproportionation predominates with all the zeolites.
These behaviours can be explained by the existence of a
transition-state shape-selectivity presented by the different
channel systems of these zeolites. Mordenite pores consist
of unidimensional 12 MR channels (6.5 5.7 ), while
beta is three-dimensional with 12 MR channels of larger
pore openings (7.6 6.4 ). The former pore system could
hinder the formation of the diarylmethane intermediate for
the disproportionation of xylene, which is bulkier than that
for the transalkylation reaction. This explains why BETA
catalysts contribute in a higher extension to disproportiona-
tion than mordenites. In fact, none of these intermediates is
able to diffuse through 10 MR channels, which are preset in
FER or ZSM-5 zeolites. In agreement with the conclusions
drawn by Guisnet et al. [26,27], our results also indicate that
disproportionation is easier to produce. This is supported
by the fact that the electrophilic aromatic substitution is
easier for xylene than for benzene, since the carbenium
ion intermediate, with more electron-donating substituents,
is more stable. Thus, the stabilization of the intermediate
for the transalkylation reaction requires the presence of
stronger acid sites (e.g. MOR(20)). This explains why the
contribution of the disproportionation reaction is smaller
for MOR(20) than for MOR(90).
By comparing the xylene conversion versus time on
stream for the different zeolites (Fig. 1) in the conversion
of an equimolecular mixture of benzene and the three iso-
mers of xylene, a strong deactivation is observed (which is
higher at increased temperatures). The conversion tends to
stabilize after 2 h in the case of BETA(25) and after 46 h
in the case of mordenites. Guisnet et al. [34] demonstrated
that deactivation is initially due to poisoning of the protonic
sites, leading to blockage of the pores by coke deposits
at longer reaction times. This coke molecules are easily
formed from the diarylmethane intermediates. The loss of
activity should be higher for transalkylation than for dispro-
portionation, since the former reaction demands stronger
acid sites. In fact, Fig. 4 stands out that the deactivation
process contributes to increase the selectivity toward the
disproportionation reaction.
Monteiro et al. [35] have reported that the carrier gas, N2
or H2 , has a significant effect on the amount and composi-
tion of the coke formed during o-xylene transformation on
mordenites. Although we tested MOR(20) with hydrogen
as carrier gas, the same results of conversion and deactiva-
tion were obtained as with nitrogen. Trying to improve the
stability, a mordenite-supported platinum catalyst (0.5 wt.%
Pt) was used in order to investigate its resistance to deacti-
vation. As depicted in Fig. 5, deactivation is clearly higher
when nitrogen is the carrier gas but if hydrogen is used
instead, the loss of activity for Pt/MOR(20) is smaller. In
absence of H2 the metal may produce the dehydrocycliza-
tion of reactants and intermediates to form coke, which de-
activates the catalyst. However, the presence of H2 favours
207
Xylene Conversion (mol %)
50
40
30
20
10
0
Benzene Conversion (mol %)
50
40
30
20
10
0
0 1 2 3 4 5 6
Time on stream (h)
Fig. 5. Xylene and benzene conversions versus time on stream as a
function of the carrier gas: MOR(20), carrier N2 (); Pt/MOR(20), carrier
N2 (); Pt/MOR(20), carrier H2 (). Feed (mol%): benzene (25%),
o-xylene (25%), m-xylene (25%) and p-xylene (25%).
the hydrogenation of different intermediates, thus avoiding
the formation of coke precursors. Consequently, the zeolite
without supported metal is equally effective for this reaction
and so the hydrogen flow is not necessary. Hydrogen can
also produce dealkylation of methylbenzenes, so the use of
nitrogen as carrier gas is preferred [7].
Other feed compositions, consisting of a 50% molar mix-
ture of benzene and one of the xylene isomers, have been
also studied in order to compare the possible reactivity dif-
ferences among xylenes. MOR(20), the most active catalyst,
was selected for this purpose. BETA(25) was tested as well
with the feed containing benzene and o-xylene. The prod-
uct distributions are plotted in Fig. 6. Xylene and benzene
conversions are found to be almost identical with any of
the xylene isomers by using MOR(20) as catalyst (Fig. 7).
However, the decay in the xylene conversion is faster with
o-xylene, perhaps due to an easier formation of coke pre-
cursors.
Fig. 8 clearly indicates the predominance of the transalky-
lation reaction in MOR(20). For BETA(25), disproportion-
ation reaction is preferential but with a lower contribution
with this feed than with the previous one. The increase in
transalkylation in both cases is explained by the lower xylene
content in this feed, which favours transalkylation rather than
disproportionation. The higher deactivation with o-xylene
also produces a decrease in the transalkylation contribution,
due, as with the three-isomers feed, to the blockage of strong
acid sites.
Besides disproportionation and transalkylation, xylenes
undergo isomerization in every experiment. The ortho/(meta
208 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210

60 50
Product composition (mol %)

Product composition (mol %)

MOR(20) Benzene + o-xylene
50
40
MOR(20) Benzene + m-xylene
40
30
30
20
20

10
10

0 0
MOR(20) Benzene + p-xylene
Product composition (mol %)
Product composition (mol %)

50 50
BETA(25) Benzene + o-xylene
40 40

30 30

20 20

10 10

0 0
0 1 2 3 4 5 60 1 2 3 4 5 6

Time on stream (h) Time on stream (h)

Fig. 6. Product distributions (mol%) for the reactions with binary feeds (1:1): benzene (); m + p-xylenes (); o-xylene (); toluene (); trimethylbenzenes
().

+ para) ratio obtained with MOR(20) is around 0.28 (0.5 0.9

for the feed). This value is close to the thermodynamic ratio
0.8
(approximately 0.30) [7]. It is also obtained for ZSM-5(80),
though it increases up to 0.30, 0.32 and 0.39 for MOR(90), 0.7

BETA(25) and BETA(75), respectively. Fig. 9 depicts the

T(t)/TT

0.6
evolution of the o/(m+p) ratio versus the xylene conversion. 0.5

0.4

40 0.3
Xylene Conversion (mol %)

0.2
0 1 2 3 4 5 6
30
Time on stream (h)

20 Fig. 8. T(t)/TT ratio for MOR(20) and binary feeds consisting of benzene
and o-xylene (), m-xylene () or p-xylene () and for BETA(25) and
a feed consisting of benzene and o-xylene ().
10

48
ortho / (meta + para) (%)

0
Benzene Conversion (mol %)

44

30 40

36
20
32

10 28

24
0 0 10 20 30 40 50
0 1 2 3 4 5 6
Xylene conversion (%)
Time on stream (h)
Fig. 9. ortho/(meta + para) ratio of xylenes in the product versus xylene
Fig. 7. Xylene and benzene conversions for MOR(20) using binary feeds conversion for catalysts: MOR(20) (), MOR(90) (), BETA(25) ()
(1:1) of benzene and o-xylene (), m-xylene () or p-xylene (). and BETA(75) (). The o/(m + p) ratio on the feed was 0.5.
 R. Roldan et al. / Applied Catalysis A: General 266 (2004) 203210
On the other hand, dealuminated zeolites, BETA(25)-NA
and BETA(25)-OA, give values of 0.40 and 0.42, respec-
tively. USY(60), BETA(150) and FER(55) are almost inac-
tive for the xylene isomerisation, giving ratios of 0.47, 0.48
and 0.51, respectively. Taking into account that among 10
MR zeolites, ZSM-5 and FER, only the former is active for
xylene isomerisation, it can be asserted that this reaction
must proceed through a monomolecular mechanism, pro-
vided that the catalyst possesses a high acidity [27]. The for-
mation of bimolecular intermediates is hindered inside their
pores, which is supported by the fact that there is no con-
version in transalkylation or xylene disproportionation for
both zeolites. On the contrary, the bimolecular mechanism
predominates in 12 MR zeolites [36].
The results obtained for the binary feed containing
o-xylene indicate, in addition to a higher isomerization, an
enrichment in the ortho isomer with time on stream (the
ratio increases from 0.28 up to 0.55 in 6 h) for MOR(20).
BETA(25) zeolite, with lower population of strong acid
sites than mordenite [32], shows a lower activity to isomer-
ization, giving an o/m + p ratio of 0.94 (which increases
up to 2.94 in 6 h). All of this suggests that the the xylene
isomerization is catalysed mainly by the strongest acid
sites. Thus, the o/m + p ratio and so the strong acid sites
population follow the order: MOR(20) ZSM-5(80) >
MOR(90) BETA(25) > BETA(75) > USY(60)
BETA(150) > FER(55), which was previously found by
pyridine adsorption [32].
Regarding trimethylbenzenes, it is noteworthy that the ra-
tios between the three isomers, 1,3,5-, 1,2,4- and 1,2,3-TMB
remain constant for all zeolites, with values around 3.5:
8.5: 1.
4. Conclusions
Large pore USY, BETA and MOR zeolites are active in the
transalkylation between benzene and xylenes as well as for
the disproportionation of xylenes, showing different activi-
ties and selectivities depending on their acidity and pore ge-
ometry. However, medium pore ZSM-5 and FER zeolites are
practically inactive. The activity is directly related to the cat-
alyst acidity and so the most acidic zeolite, MOR(20), pro-
vides the best results, i.e. the highest conversions of xylenes
and benzene, above 40% at 300 C.
Transalkylation requires the presence of strong acid sites
on the catalyst due to the lower stability of the carbenium
ion intermediate relative to that of the disproportionation
reaction. Moreover, shape-selectivity plays an important
role through steric restrictions in the pores. The diaryl-
methane intermediate is bulkier for disproportionation
than for transalkylation. Thus, mordenite, which possesses
stronger acid sites and smaller pores than beta, favours the
transalkylation reaction. The transalkylation to dispropor-
tionation ratio decreases as the catalysts are deactivated,
which is explained by the blockage of the strongest acid
209
sites. Xylene isomerization also takes place, even in the
medium pore ZSM-5 zeolite through a monomolecular
mechanism. Under the reactions conditions, most of cata-
lysts lose activity with time on stream. o-Xylene was found
to produce a stronger deactivation than m- and p-xylenes.
Attempts to increase the stability were accomplished by
using Pt-supported zeolites. However, similar results were
obtained at long reaction times.
Acknowledgements
The authors wish to acknowledge funding of this research
by Spains DGI, Ministry of Science and Technology, within
the framework of Project BQU2001-2605, as well as by
Fondos Feder and Junta de Andaluca.
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