Chemical Engineering Communications

ISSN: 0098-6445 (Print) 1563-5201 (Online) Journal homepage: http://www.tandfonline.com/loi/gcec20

Kinetic Investigation in Transalkylation of 1,2,4

Trimethylbenzene with Toluene over Rare Earth
Metal-Modified Large Pore Zeolite

Ruchika Thakur, Sanghamitra Barman & Raj K. Gupta

To cite this article: Ruchika Thakur, Sanghamitra Barman & Raj K. Gupta (2017) Kinetic
Investigation in Transalkylation of 1,2,4 Trimethylbenzene with Toluene over Rare Earth Metal-
Modified Large Pore Zeolite, Chemical Engineering Communications, 204:2, 254-264, DOI:
10.1080/00986445.2016.1263620

To link to this article: http://dx.doi.org/10.1080/00986445.2016.1263620

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Nov 2016.
Published online: 28 Nov 2016.

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Chemical Engineering Communications, 204:254–264, 2017
Copyright © Taylor & Francis Group, LLC
ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986445.2016.1263620

Kinetic Investigation in Transalkylation of 1,2,4 Trimethylbenzene

with Toluene over Rare Earth Metal-Modified Large Pore Zeolite
RUCHIKA THAKUR1, SANGHAMITRA BARMAN2, and RAJ K. GUPTA2
1
School of Chemistry and Biochemistry, Thapar University, Patiala, Punjab, India
2
Department of Chemical Engineering, Thapar University, Patiala, Punjab, India

Gas-phase transalkylation of 1,2,4 trimethylbenzene (1,2,4-TMB) with toluene was carried out for the production of xylene in a fixed-bed
reactor at 1 atm pressure over cerium-modified NaX zeolites. The modified zeolites were characterized by Energy Dispersive Spectra,
X-ray Diffraction, and Scanning Electron Microscopy. The acidic properties of metal-modified zeolites were studied using the Temperature
Programmed Desorption profile of ammonia. The effects of various parameters like cerium content, catalyst loading, temperature, reactant mole
ratio, and space-time were investigated to select the optimum process conditions to maximize the specific product of transalkylation. NaX
zeolite modified with cerium exhibited higher activity and stability than the unmodified zeolite in time-on-stream study. Maximum toluene
conversion of 44.96% and xylene selectivity of 55.13% were obtained over CeX10 (X zeolite exchanged with 10% ceric ammonium nitrate
solution) at 723 K, reactant mole ratio 2.5, and space-time 4.44 kg · h/kmol. Experimental data was fitted in the Langmuir–Hinshelwood–
Hougen–Watson (LHHW) model based on dual-site, single-site, and stoichiometric equations. The kinetic and adsorption parameters for toluene
conversion were calculated using nonlinear regression. The activation energy for this transalkylation reaction was found to be 60.3 kJ/mol.
Keywords: Cerium; Kinetic study; NaX zeolite; Transalkylation; Xylene

Introduction Transalkylation of toluene with trimethylbenzene (TMB) is

The global demand for para-xylene remains at a very high level
and its market is expected to increase at 5% per year in the near
future. In the past decades, the overall production coming from
industries has not kept pace with the ever-increasing demand of
para-xylene. Currently, almost all industrial plants are already
operating at their fullest extent; further increase in demand
may require some modification in the production system. Devel-
opment in process technology is the key alternative route to
enable low-cost expansions that can be executed quickly (Boon
et al., 2002; Stachelczyk, 2000). Xylene is used for the pro-
duction of a number of useful products. Terephthalic acid, which
is mainly (about 70%) derived from the oxidation of para-
xylene, is the main component in the polyester industry and is
used in polyester terephthalate (PET) and polyester fiber manu-
facturing. Besides these, xylene has numerous applications as a
key raw material for the production of films, resins, fibers, plas-
ticizers, and dimethylterephthalate in petrochemical industries
(Hanika et al., 2003; Serra et al., 2005). The term transalkylation
basically refers to the reaction of aromatics moieties, which
involve the transfer of alkyl groups and the formation of mono
or dialkylated aromatics of higher value (Krejci et al., 2010).
Address correspondence to Dr. Sanghamitra Barman, Associate
Professor, Department of Chemical Engineering, Thapar University,
Patiala 147004, Punjab, India. E-mail: sbarman@thapar.edu
Color versions of one or more figures in the article can be
found online at www.tandfonline.com/gcec.
often desirable and is considered as a promising catalytic pro-
cess for converting these low-valued by-products to commercial
value-added products such as xylene (Hanika et al., 2003; Tsai
et al., 2002; Dumitriu et al., 2002). The transalkylation of
toluene with TMB forms mixed xylene, which consists of three
isomers such as para-xylene, ortho-xylene, and meta-xylene
(Hanika et al., 2003; Tsai et al., 2002).
Effects of pore structures on catalytic activity were investi-
gated in Zeolite Socony Mobil-5 (ZSM-5), Mordenite (MOR),
Beta, and Ultra stable Y (USY) for the transalkylation of toluene
with 1,2,4-trimethylbenzene (1,2,4-TMB) (Li et al., 2015).
Dual-zeolite (MOR-MFI) catalyst for the dealkylation-trans-
alkylation of alkylaromatics has been investigated (Ali et al.,
2015). In this study, the authors reported that the reduction in
micropore volume in dual-zeolite catalyst prevents undesired
secondary reactions. The addition of 20% toluene to heavy
reformates resulted in further increase in xylenes yield.
Diffusion of TMBs and xylenes in beta zeolites through
12- and 10-membered ring channels was studied (Toda et al.,
2016). The authors reported the optimum temperature for trans-
alkylation reaction to be 450°C. The increase in reaction press-
ure also has a positive effect on the catalytic activity of
transalkylation (Yachun et al., 2016).
Transalkylation of a blend of toluene–trimethylbenzene–
tetramethylbenzene has also been carried out (Khattaf et al.,
2015). Kinetic modeling of toluene–TeMB (tetramethylbenzene)
transalkylation, toluene disproportionation, and toluene–TMB
transalkylation was carried out. The authors reported the rate of
Xylene Production Using Modified Zeolite Catalyst 255

toluene–TeMB transalkylation reaction to be 50% higher than the

toluene–TMB transalkylation reaction; however, toluene dispro-
portionation was slower than transalkylation reactions. The
activation energy of dispropotionation reaction is reported to be
higher than the transalkylation reaction (Al-Mubaiyedh et al.,
2012). The kinetics of dealkylation and transalkylation of C9 of
alkyl aromatics over zeolites of different structures are reported
(Ali et al., 2013). The results showed that transalkylation was
significantly better than dispropotionation reactions.
The most important technique used to modify the zeolites is
ion exchange. Metal ions belonging to the groups like alkali and
alkaline earth, transition, and rare earth elements are often
regarded as promoters for zeolite catalysts (Rahimi and
Karimzadeh, 2011). Modification by metal ions is reported to
enhance the activity, selectivity, and stability of zeolites.
Metal-modified zeolites are used in a number of chemical
reactions (Srilatha et al., 2012). Metal-modified zeolites are also
extensively used for transalkylation reactions (Serra et al.,
2005). Zeolites modified with rare earth metals such as La,
Ce, Pr, Nd, Sm, and Eu have been extensively studied as
catalysts for various reactions such as acylation (Gaare and
Fig. 1. Preparation of cerium-modified zeolite catalyst.
Akporiave, 1996; Jin et al., 2007), absorption (Jung et al.,
2014), cracking (Castillo et al., 2005), conversion (Lu et al.,
2009), and hydromerization (Ping et al., 2011). Mumbai, India. All chemicals used in the study were of high
The industrial transalkylation process utilizes HF, H2SO4, Lewis purity (>99%). Toluene was supplied by Merck, India. The
acids (BF3, AlCl3), silica alumina-based catalyst, clays, or zeolites ion exchange in NaX zeolite was carried out using ceric
(Tsai et al., 1999; Pradhan and Rao, 1993; Bandyopadhyay et al., ammonium nitrate, which was supplied by CDH Chemicals
1998; Forni et al., 1995; Lee et al., 1998; Chao and Leu, 1989; India. Grade-I nitrogen gas (99.999% purity) was procured
Dumitriu et al., 1996; Das et al., 1994; Halgeri and Das, 1999). from Sigma Gases and Services, India.
In recent years, a variety of zeolite catalysts has been applied for
the transalkylation of toluene with TMB (Aitani et al., 2010; Wang Catalyst Modification (Barman et al., 2005)
et al., 2010). However, it is notable that only large-pore zeolites
Sodium ions of NaX zeolite were exchanged with cerium ions
favor the TMB transalkylation reaction due to the formation of
using ceric ammonium nitrate solution. A simple refluxing
bulky intermediates during the transalkylation reaction (Wang and
apparatus was used to carry out the exchange process. Before
Tsai, 1990; Khattaf et al., 2007). Mordenite, Faujasite Y, and H-beta
cerium exchange, the catalyst was refluxed with ammonium
were found to be effective for this reaction due to their pore size and
nitrate solution in order to exchange sodium ion by hydrogen
structure. Studies revealed that pore size, Si/Al ratio, and geometry
ions. The hydrogen form of zeolite was treated with the required
of the zeolites affect the conversion of the reactant and the selec-
amount of cerium nitrate solution to change the hydrogen
tivity of the product (Wang et al., 2010; Khattaf et al., 2007).
form. Modification was done following the procedure given in
Available literature revealed that two categories of zeolite-
Figure 1.
based catalysts have been used for transalkylation; one is the
hydrogen or sodium form and the other is the noble or transition
metal form of zeolite. It is well known that substitution of sodium
or hydrogen ions with rare earth metal cations (La, Ce, etc.)
imparts superior catalytic activity to a zeolite, leading to higher
conversion and selectivity (Aitani et al., 2010; Barman et al.,
2005). The improvement in the activity of the catalyst is due to
an increase in acidity of the zeolite caused by the higher level
of exchange made by polyvalent cations. In the present work,
the effect of the exchange of sodium ions with polyvalent cerium
ions on the catalytic activity of the large-pore zeolite, NaX, for
the transalkylation of toluene and TMB to xylene is investigated.

Experimental Section
Materials and Reagents
Commercially available NaX zeolite, in the form of extrudates
(1.5 mm catalyst particle size), was obtained from Fresia zeolite, Fig. 2. EDS of cerium X zeolite.
256
Fig. 3. XRD of NaX and cerium-modified X.
Catalyst Characterization
The zeolites modified with different concentrations of cerium
are designated as CeX6, CeX8, CeX10, and CeX12. To find the
elemental composition, Energy Dispersive Spectroscopy
(EDS) of the samples was carried out using Quanta 200FEG.
The results showed that the NaX zeolite modified with 10%
ceric ammonium nitrate solution contains 7.8 wt% of cerium
(Figure 2).
The crystallinity of the powder zeolite samples was deter-
mined using X-ray diffraction patterns recorded using Bruker
Angle X-Ray Scattering, Diffractometer D8, Germany, equipped
with Ni-filtered Cu K-α radiation source. The XRD of the
Fig. 4. SEM of cerium-modified X zeolite (a) NaX and (b) CeX8, CeX10, CeX12.
R. Thakur et al.
samples was carried out at a 2θ value in the range of 5°–60°.
Gentle grinding of the solid into a fine powder was performed
to prepare the sample for the X-ray analysis. Approximately
0.1–0.2 g of the sample was taken into the sample holder with
a slight compression to make it flat and tight. The XRD patterns
of parent and cerium-exchanged NaX zeolite show that there is
no major structural change during the cerium modification of
the NaX zeolite as shown in Figure 3. NaX zeolite shows a high
intense peak at the 2θ value of 6.15°. The crystallinity of all the
modified zeolites was found to be approximately around 90%.
The intensity of the peaks was found to decrease with increase
in the cerium content of the zeolite catalyst. No additional
peaks of cerium oxide were found in the XRD pattern of
cerium-loaded zeolites with low loading, which show that at
low loading, cerium has been completely exchanged; however,
at high loading some cerium appeared on the surface of the
catalyst as cerium oxide. The surface morphology and particle
size were determined from SEM (LEO 435 VP). The
SEM image (Figure 4) shows that the catalyst particles are of
irregular octahedral shape. The average particle size was found
to be 1 µm. The acidity of the catalyst was determined using
temperature-programmed ammonia desorption (CHEM-BET
3000 instrument, Quantachrome). For acidity determination,
the catalyst sample (0.1 g) was degassed at 723 K for 1 h under
inert atmosphere using nitrogen followed by cooling to 273 K.
Nitrogen–ammonia gas mixture (1 mol% ammonia) was then
passed through the sample for 1 h. The catalyst was then heated
to 372 K until the equilibrium was attained; thereafter, the
temperature of the sample was raised up to 1173 K at a heating
rate of 10 K/min and then the desorbed ammonia was detected
by a thermal conductivity detector analyzer. Temperature-
programmed desorption of ammonia was studied with NaX
Xylene Production Using Modified Zeolite Catalyst 257

%Selectivity of Xylene
ðXylene in product mixtureÞ
¼
Aromatics in product excluding Toluene and Trimethylbenzene
× 100
ð2Þ

The transalkylation of toluene with TMB was accompanied with

disproportionation and isomerization. These reactions are as
follows.
Primary reaction:

Fig. 5. TPD of NaX and cerium-modified X zeolite.

and CeX zeolites of different cerium loadings. Desorption of

ammonia corresponding to different peaks shows the energy Secondary reactions:
levels at which ammonia is bound to the acid site. The profile i) Disproportionation reactions:
shows that the catalysts contain mainly two types of acid sites
as shown in Figure 5. In case of NaX zeolite, the peaks are
exhibited at lower temperature, whereas in case of CeX zeolite
the peak shifted toward higher temperature, which showed that
increase in acidic strength at higher temperature is due to the
increase in the cerium content in zeolite. Moreover, the number
of acid sites also increases as the peak area increases with
cerium exchange. The increased acidity in cerium-modified
zeolite is due to the exchange of monovalent cations (Naþ or
Hþ) with polyvalent Ce4þ ions, which lead to the formation
of concentrated acidic sites rather than dispersed acidic sites.
Cerium being polyvalent (þ4) can balance four anionic sites
of the framework, thus increasing the acidity and stability of
the zeolites. Acidity increases due to the higher level of
exchange. The acidity of NaX zeolite was found to be
0.25 mmol/g and that of CeX10 zeolite was 1.27 mmol/gm.

Experimental Procedure
Kinetic runs were carried out in a fixed-bed, continuous, Isomerization reactions:
down-flow reactor (SS 316) in the vapor phase at 1 atm. Before
conducting the experiments, the catalyst was activated using
nitrogen at a flow rate of 0.565 L/h (at 100 K higher than the
reaction temperature) for 3 h. A dosing pump was used to intro-
duce the reactant feed mixture into the reactor via a preheater.
During all the experimental runs, the nitrogen to feed flow rate
ratio was kept constant at 0.2. The liquid product samples were
collected by condensing the product vapors in a condenser.
These samples were analyzed in a gas chromatograph equipped
with FID detector. The conversion of toluene and the selectivity
of xylene were calculated according to the following formula:

%Conversion of Toluene
ðToluene in Feed Toluene in product mixtureÞ ð1Þ
¼
Toluene in feed
258 R. Thakur et al.

Results and Discussion

Effect of Cerium Loading on Product Distribution
Effect of cerium loading on NaX zeolite catalyst on product
distribution is shown in Table I. The results show that modified
zeolite shows better toluene conversion, xylene yield, and selec-
tivity than NaX zeolite. From the product distribution, it is seen
that the disproportionation of toluene is less favorable than the
disproportionation of TMB, which produces TeMB. Further-
more, isomerization of TMB yields 1,3,5-TMB as the major
product rather than 1,2,3-TMB. Owing to steric hindrance of
the alkyl groups 1,2,3-TMB is not stable as a product. Similar
results are obtained in case of xylene isomers as para-xylene
isomer, a sterically favored product, is formed in larger amounts
than its ortho-isomer.
Figure 6 shows that xylene yield and toluene conversion
increase with increase in cerium loading in the catalyst. How-
ever, it was observed that the xylene selectivity decreases for Fig. 6. Activity of catalyst on transalkylation reaction. Reaction con-
cerium loading beyond 10% of ceric ammonium nitrate sol- ditions: pressure, 1 atm; temperature, 723 K; reactant mole ratio, 2.5;
ution. This may be because the generated acid sites are very space-time, 4.44 kg · h/kmol; catalyst, 2 g; N2: feed flow rate, 0.74.
strong and initiate disproportionation and isomerization reac-
tions, thereby leading to an increase in the formation of side pro- presence of a large number of active sites available for the reac-
ducts and thus decreasing the yield and selectivity of xylene. tants. However, at catalyst loading above 7.66%, the increase in
Therefore, further study was performed using CeX10 catalyst. toluene conversion is negligible due to the shortage of limiting
reactant despite having available surface area. The xylene yield
and selectivity are also found to increase with increase in
Effect of Catalyst Loading in the Reactor catalyst loading, as shown in Figure 8.
Catalyst loading was varied from 1.91% to 11.50% (w/w) of
the reactants. The conversion of reactant is found to increase
with increase in catalyst loading from 1.91% to 11.5% Effect of Reaction Temperature
(Figure 7). It is observed that up to the catalyst loading of
7.66%, conversion of toluene increases sharply due to the The reaction temperature can strongly influence the rate of reac-
tion and yield of products as intrinsic rate constant is a function
of reaction temperature. To find the optimum temperature for
Table I. Product distribution over different zeolite catalysts
the maximum conversion of reactants and product selectivity,
Catalyst
Product
Distribution (wt%) NaX Ce-X6 Ce-X8 Ce-X10 Ce-X12
Benzene 1.79 1.81 1.86 1.88 1.93
Toluene 18.45 15.5 14.7 12.90 11.97
Xylene
Para 7.54 9.92 11.53 15.28 13.97
Ortho 2.75 4.95 5.45 5.78 5.46
TMB
1,3,5- 8.21 8.01 7.95 7.66 7.41
1,2,4- 54.31 52.38 51.83 48.9 48.23
1,2,3- 3.27 3.79 4.01 4.97 6.25
TeMB 3.68 3.64 2.67 2.63 3.85
Toluene conv. (wt%) 21.28 33.90 37.28 44.96 48.95
Xylene yield (wt%) 10.29 14.87 16.98 21.06 20.43
Xylene selectivity (wt%) 37.77 46.29 50.73 55.13 52.55
1,2,3 and 1,3,5 TMB 11.48 11.80 11.96 12.63 13.66
isomers yield (wt%)
1,3,5 TMB/1,2,3 2.51 2.20 1.98 1.54 1.18
TMB (wt%)
Para/ortho-xylene (wt%) 2.74 2.00 2.11 2.64 2.55 Fig. 7. Effect of catalyst loading on toluene conversion in 3 h time
Reaction conditions: pressure, 1 atm; temperature, 723 K; reactant on stream. Reaction conditions: pressure, 1 atm; temperature, 723
mole ratio, 2.5; space-time, 4.44 kg · h/kmol; catalyst, 2 g CeX10; K; reactant mole ratio, 2.5; space-time, 4.44 kg · h/kmol; catalyst,
N2: feed flow rate, 0.74, time-on-stream, 30 min. 2 g CeX10; N2: feed flow rate, 0.74.
Xylene Production Using Modified Zeolite Catalyst 259

Fig. 8. Effect of catalyst loading on xylene yield and selectivity.

Reaction conditions: pressure, 1 atm; temperature, 723 K; reactant
mole ratio, 2.5; space-time, 4.44 kg · h/kmol; catalyst, 2 g CeX10;
N2: feed flow rate, 0.74.
reactions were carried out at different temperatures in the range
of 573–773 K over 2 g of CeX10 zeolite catalyst. The product
distribution at the different temperature is summarized in
Table II, which shows that the reaction temperature has a signifi-
cant effect on product distribution. The conversion of toluene
first increases with the rise in temperature and after reaching
maxima of 45% at a temperature of 723 K it decreases. At
higher temperatures, active sites on the catalyst surface are
blocked by a faster coke formation rate, which deactivates the
catalyst faster, thus decreasing the activity of the catalyst and
hence the overall conversion also decreases. Xylene selectivity
Fig. 9. Effect of temperature on isomers distribution. Reaction
conditions: pressure, 1 atm; reactant mole ratio, 2.5; space-time,
4.44 kg · h/kmol; catalyst, 2 g CeX10; N2: feed flow rate, 0.74.
is found to increase as the temperature is raised from 573 to
673 K, thereby decreasing the selectivity of other side-products.
At higher temperature, benzene and TeMB yield increases due
to favored disproportionation and isomerization reaction. The
1,3,5-TMB/1,2,3 TMB-ratio decreases with increase in tempera-
ture, as shown in Figure 9. For isomerization of 1,2,4-TMB, low
temperature favors sterically stable products, whereas high
temperature provides sufficient activation energy to the reactant
to overcome steric hindrance, which leads to the formation of
1,2,3-TMB.

Table II. Product distributions from the transalkylation of toluene

and 1,2,4 trimethylbenzene over different temperatures Effect of Reactant Mole Ratio

Temperature (K) The transalkylation reactions were carried out by varying the
Product distribution TMB to toluene mole ratio from 0.45 to 3.1 at a reaction
(wt%) 573 623 673 723 773 temperature of 723 K and a space-time of 4.44 kg · h/kmol. As
Benzene 0.90 1.21 1.39 1.88 1.91 shown in Figure 10, the toluene conversion passes through a
Toluene 19.24 15.21 14.32 12.90 13.39 maximum at a reactant mole ratio of 2.5. Above this mole ratio
Xylene of TMB to toluene, excess reactant covers the maximum number
Para 9.97 14.00 13.97 15.28 16.56 of active sites of the catalysts. Toluene, the limiting reactant, is
Ortho 1.33 2.12 5.21 5.78 6.34 less available at catalytic sites, which lead to a decrease in the
TMB conversion of toluene at higher mole ratio. Xylene selectivity
1,3,5- 6.23 6.31 6.46 7.66 7.73 and yield are found to be maximum around equimolar TMB
1,2,4- 57.91 55.26 52.45 48.9 46.26 to toluene ratio. This shows that xylene yield is due to the
1,2,3- 3.02 3.83 4.01 4.97 5.11 transalkylation of toluene and TMB rather than the disproportio-
TeMB 1.40 1.97 2.19 2.63 2.7 nation of TMB. The number of alkyl groups increases in the
Conversion (wt%) 18.00 35.11 38.90 44.96 42.87 reaction system with a higher amount of TMB in the feed, which
Toluene conv. 24.37 27.83 31.49 36.12 39.57 leads to the formation of side-products like TeMB. Moreover,
TMB conv. increase in 1,2,4-TMB molecules causes an increase in isomer-
Xylene yield (wt%) 11.30 16.12 19.18 21.06 22.90 ization products (1,3,5-TMB and 1,2,3-TMB), which leads to
Xylene selectivity (wt%) 49.45 54.75 57.71 55.13 57.96 decrease in xylene selectivity and yield. 1,3,5/1,2,3-TMB and
1,2,3- and 1,3,5-TMB isomers 9.22 10.14 10.47 12.63 12.84 para/ortho-xylene ratio are found to decrease with increase in
yield (wt%) TMB in the feedstock. It is observed that transalkylation is
Reaction conditions: pressure, 1 atm; reactant mole ratio, 2.5; favored at TMB/toluene molar ratio less than or equal to 1,
space-time, 4.44 kg · h/kmol; catalyst, 2 g CeX10; N2: feed flow whereas an increase in reactant ratio favors disproportionation
rate, 0.74; time-on-stream, 30 min. and isomerization.
260 R. Thakur et al.

Table III. Product distribution from the transalkylation of toluene

and 1,2,4 trimethylbenzene at different space-time at 723 K

Space-time (kg · h/kmol)

Product distribution (wt%) 1.19 2.70 3.47 4.16 4.44
Benzene 1.12 1.23 1.45 1.69 1.88
Toluene 17.83 16.50 14.80 13.7 12.90
Xylene
Para 6.79 9.82 10.9 12.47 15.94
Ortho 1.23 2.19 3.54 4.53 5.12
TMB
1,3,5- 5.67 6.14 6.90 7.23 7.66
1,2,4- 62.54 58.46 56.13 53.47 48.9
1,2,3- 2.93 3.56 3.98 4.42 4.97
TeMB 1.89 2.10 2.30 2.49 2.63
Conversion (wt%)
Toluene conv. 23.90 29.6 36.86 41.76 44.96
TMB conv. 18.31 23.64 26.68 30.15 36.12
Fig. 10. Effect of reactant ratio on product distribution. Reaction Xylene yield (wt%) 8.02 12.01 14.44 17.00 21.06
conditions: pressure, 1 atm; temperature, 723 K; space-time, 4.44 Xylene selectivity (wt%) 40.85 47.96 49.67 51.78 55.13
kg · h/kmol; catalyst, 2 g CeX10; N2: feed flow rate, 0.74. Reaction conditions: pressure, 1 atm; temperature, 723 K; reactant
mole ratio, 2.5; catalyst, 2 g CeX10; N2: feed flow rate, 0.74; time-
Effect of Space-Time on-stream, 30 min.

The effect of space-time was studied by varying the flow rate rate. From the intra-particle diffusional study, it was observed
of the reactant feed mixture. The range chosen for study was that with change in particle size, there was no change in the
1.19–4.44 kg · h/kmol at a temperature of 723 K and a reactant reaction rate, which confirmed that the reaction was occurring
ratio of 2.5. Toluene conversion is found to increase with in the pore diffusion resistance-free regime.
increase in space-time. The higher contact time allows the reac-
tant molecules to stay over the catalyst for a long time, which
allows the reactants to react with each other, resulting in a
higher yield of products at higher space-time. The product dis- Kinetic Study
tribution is given in Table III. With increase in space-time, the To study the reaction kinetics, transalkylation reaction was per-
product yield from the isomerization and disproportionation formed in the presence of CeX10 catalyst at different reaction
reactions increases due to the increase in the yield of TMB
isomers and benzene. As xylene is produced by the disproportio-
nation of TMB in addition to transalkylation with toluene,
xylene yield and selectivity both increased with increase in con-
tact time. Effects of space-time on toluene conversion at various
temperatures were also studied and are represented in Figure 11.

Kinetics of Transalkylation
Mass Transfer Considerations
In any kinetic study, the effect of external and internal mass
transfer resistances should be negligible. To investigate the
external diffusional effects, experiments were carried out over
different weights of catalyst (2 and 4 g) at constant space-time.
Feed rates were varied during the reaction to keep the space-
time constant. The results are represented in Figure 12. The
results showed that toluene conversion remains almost the same
in both the cases, which confirm the complete absence of exter-
nal diffusional resistance.
Internal diffusional resistance to mass transfer inside the
catalyst pore slows down the reaction rate (Figure 13). In case
of the pore diffusion control regime, the rate of reaction is influ- Fig. 11. Effect of space-time on toluene conversion at various tem-
enced by the size of the catalyst particle as the pore length peratures. Reaction conditions: pressure, 1 atm; temperature, 723 K;
increases with the particle size, causing a decline in the reaction reactant mole ratio, 2.5; catalyst, 2 g CeX10; N2: feed flow rate, 0.74.
Xylene Production Using Modified Zeolite Catalyst 261

Fig. 14. Plots of –ln(1–XT) versus time at different temperatures.

Fig. 12. Effect of external diffusion. Condition: reaction tempera-
ture, 623 K; reactant mole ratio, 2.5:1; catalyst, CeX10; N2 to feed
ratio, 0.74. was plotted and is shown in Figure 14. The linear nature of these
plots supported that the (pseudo)-first-order kinetics fits the data
reasonably well. From the slope of each line data value of rate
temperatures (573–748 K). For all kinetic runs, the TMB to tolu-
constant was calculated at different temperatures. The kinetic
ene molar ratio was kept constant at 2.5, whereas the nitrogen to
constants derived were used to find the activation energy, using
FeedTol ratio was maintained at 0.74. For each temperature, the
the following Arrhenius equation. Activation energy (Ea) was
W/FTol(space-time) was varied by keeping the catalyst weight
evaluated from the slope of the graph between ln k versus 1/T
constant and changing the flow rate of the feed. As seen from
(Figure 15). The values of Ea and A (Frequency factor) from
Figure 11, toluene conversion increases with W/FTol at all four
the plot were found to be 59.2 kJ/mol and 2.1 × 107,
temperatures. In the first attempt, the simplest available corre-
respectively.
lation for rate expression was obtained by choosing the nth order
kinetics to represent the surface kinetics. In the present case, ln k ¼ ln A Ea =RT ð3Þ
since TMB in the feed is in excess, irreversible pseudo-first-
order reaction was assumed based on toluene. Following the
pseudo-first-order kinetics, the graph of – ln(1 – XT) versus t Langmuir–Hinshelwood–Hougen–Watson Model
The experimental data was fitted in the Langmuir–Hinshel
wood–Hougen–Watson (LHHW) model to evaluate various rate

Fig. 13. Effect of internal diffusion. Reaction conditions: pressure

1 atm; temperature 623 K; reactant mole ratio, 2.5; catalyst, 2 g
CeX10; N2: feed flow rate, 0.74. Fig. 15. Arrehenius plot.
262 R. Thakur et al.

constants of the reaction. The following rate expression using

the LHHW model with surface reaction as a rate-controlling
step and dual-site (both reactant adsorbed on catalyst) mech-
anism was found to fit the kinetic data significantly better than
the other models.
�
rT ¼ dXT =dτ ¼ k1 KT KTMB pT pTMB þ k2 KT2 p2T =Z 2 ð4Þ

where Z ¼ 1 þ KTMB pTMB þ KT pT ð5Þ

The partial pressures in the above equations were calculated
using the fractional conversions and total pressure P as given by
the following expressions:
pT ¼ ð1 XT ÞP=6:09 ð6Þ

pTmb ¼ ð2:5 XTmb ÞP=6:09 ð7Þ

�
pp xyl ¼ Xp xyl P=6:09 ð8Þ
�
po xyl ¼ Xo xyl P=6:09 ð9Þ Fig. 16. Experimental versus predicted values of reaction rate.
�
p1;3;5TMB ¼ X1;3;5TMB P=6:09 ð10Þ Table V. Activation energy and pre-exponential factors of different
� reactions
p1;2;3TMB ¼ X1;2;3TMB P=6:09 ð11Þ
Reaction Eact (kJ/mol) Pre-exponential factor
pTeMB ¼ ðXTeMB ÞP=6:09 ð12Þ
Transalkylation reaction 60.3 0.8 × 106
In the reaction system, the total number of moles of different Toluene disproportionation 67.7 1.5 × 106
components was found to be 6.09, which consist of 2.5 moles of
TMB, 1 mole of toluene, and 2.59 moles of nitrogen. The model
Thermodynamic adsorption parameters such as enthalpy and
parameters were estimated using nonlinear regression. The opti-
entropy of adsorption were calculated using the following
mum value of the parameters was estimated by minimizing the equation:
objective function given by the equation. The kinetic and
adsorption constants were evaluated and are shown in Table IV. ΔH ΔS
ln k ¼ þ ð14Þ
RT R
f ¼ ∑ni¼1 ½ðRate predicted Þi ðrate experimentalÞi�2 ð13Þ
The values of enthalpy and entropy change are reported in
The standard error of estimate for the rate of disappearance of Table VI. The adsorption equilibrium constants are plotted in
toluene was 3.0 × 10 4, which was calculated using the values Figure 17, which shows a satisfactory trend.
of constants from Table IV. Figure 16 shows the experimental
and predicted rates are quite comparable, having an R2 value Deactivation Kinetics
of 0.96.
The activation energies for transalkylation reaction and dis- For the differential reactor, the deactivation constant may be
proportionation reaction are reported in Table V. The values of assumed to be independent of reactant concentration. For a
activation energy, for m-diethylbenzene transalkylation in the batch of solid (catalyst) and plug flow of the fluid, the following
temperature range 483–543 K over beta zeolite, are reported in equation may be used for determining the deactivation constant:
the range of 46–104.6 kJ/mol (Forni et al., 1995). � � ��
CA0 �
ln ln ¼ ln kτ′ kd t ð15Þ
CA
Table IV. Kinetic and adsorption parameters A plot of ln[ln(CA0/CA)] versus t at four different temperatures
is shown in Figure 18; the slopes of the lines at different tem-
Kinetic and Temperature (K) peratures represent the deactivation constant kd at the tempera-
adsorption ture under consideration. The value of the deactivation
parameters 573 623 673 723 constant was found to be lower than the reaction rate constants.
k1 (kmol/kg · h) 1.50 6.93 10.54 25.99
k2 (kmol/kg · h) 0.81 4.54 7.12 17.48 Table VI. Thermodynamic adsorption parameters for toluene and
KT (atm 1) 1.04 0.92 0.81 0.769 1,2,4-TMB
KTMB (atm 1) 0.57 0.20 0.09 0.034
Average deviation 2.5 × 10 4
3.6 × 10 4
1.8 × 10 4
4.2 × 10 4 Reactants ΔHads (kJ/mol) ΔSads (J/mol K)
for estimation Toluene 7.0 12.0
of rate 1,2,4 TMB 13.9 28.2
Xylene Production Using Modified Zeolite Catalyst
Fig. 17. Arrhenius plot for adsorption equilibrium constants.
Fig. 18. Plots of ln[ln(CAO/CA)] versus time at different
temperatures.
The values of ln kd were plotted against 1/T to find the apparent
activation energy for deactivation of the catalyst, which was
found to be 14.3 kJ/kmol, which is much lower than that for
the main reaction. In case of alkylation and transalkylation reac-
tions, the coke formed is olefinic in nature and hence is formed
faster, so the catalyst is more susceptible to pore blockage at low
temperatures (Sridevi et al., 2001).
Conclusion
Transalkylation of TMB with toluene was carried out over
cerium-modified NaX zeolite. Significant differences between
the catalytic activities of NaX zeolite and modified NaX zeolite
were observed in the time on stream study. The modification of
zeolite with cerium also brought significant improvement in the
product selectivity and stability of the catalyst. Cerium-modified
large-pore zeolite (CeX10) showed higher activity and less
263
deactivation at the temperature range of 573–723 K as compared
with 773 K. At high reaction temperature of 773 K, isomeriza-
tion and disproportionation of TMB are favored. Low reactant
ratio favored xylene yield and xylene selectivity.
Based on the product distribution, a reaction mechanism was
proposed for the disappearance of toluene along with a rate
expression following the LHHW approach. The kinetic and
the adsorption constants of the rate equation were estimated
by regression. The activation energy for the synthesis of xylene
was found to be around 60 kJ/mol. Catalyst deactivation con-
stant was found to be much lower than the reaction rate
constants.
Acknowledgment
One of the authors, Dr. Sanghamitra Barman, is thankful to the
Department of Science and Technology and Thapar University
for supporting the research work.
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