Journal of Molecular Catalysis A: Chemical 407 (2015) 147–151

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Journal of Molecular Catalysis A: Chemical

journal homepage: www.elsevier.com/locate/molcata

Selective hydrodealkylation of C9 + aromatics to benzene, toluene, and

xylenes (BTX) over a Pt/H-ZSM-5 catalyst
Dongwook Lim, Jaeyong Jang, Taewoo Kim, Sang Eun Shim, Sung-Hyeon Baeck ∗
Department of Chemistry and Chemical Engineering, Center for Design and Applications of Molecular Catalysts, Inha University, Incheon 402-751, South
Korea

a r t i c l e i n f o a b s t r a c t

Article history: Pt/H-ZSM-5 zeolites (Si/Al ratio of 50) with a Pt loading of 0.28 wt.% were successfully synthesized
Received 23 June 2015 and employed as catalysts for the selective hydrodealkylation of C9 + aromatics to benzene, toluene,
Accepted 27 June 2015 and xylenes (BTX). Five different crystallite sizes (40, 20, 10, 5, 2 ␮m) were prepared using different
Available online 2 July 2015
aging times before crystallization. The influence of crystallite size on catalytic activity was investigated,
and the catalysts synthesized were physicochemically characterized by XRD, BET, SEM, and ICP-OES.
Keywords:
Hydrodealkylation was performed in a conventional fixed bed reactor, and the influences of crystal-
Pt/H-ZSM-5
lite size on ethyltoluene (ET) isomer conversion and on the recovery yields of trimethylbenzene (TMB)
Hydrodealkylation
C9 + aromatics
isomers were examined. Conversion of ET isomers was always higher than that of TMB isomers. The dis-
BTX tribution of products obtained was strongly influenced by Pt/H-ZSM-5 crystallite size, that is, ET isomer
Crystallite size conversion decreased and TMB isomer recovery yield increased with crystallite size. Catalyst crystallite
size was found to dictate catalytic activity with respect to selective hydrodealkylation. Pt/H-ZSM-5 with
a crystallite size of 5 ␮m exhibited the best catalytic performance for the selective hydrodealkylation of
C9 + aromatics to BTX.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Zeolites have been broadly used as heterogeneous catalysts
in the oil refining and petrochemical industries [1]. In particular,
ZSM-5 type zeolites are known as shape selective catalysts due
to their distinctive channel structures formed by 10-membered
rings [2,3]. For this reason, large molecules cannot diffuse effi-
ciently through these microporous materials because of their small
pore sizes [4]. Furthermore, ZSM-5 catalysts show much greater
selectivity for para-isomers than ortho- or meta-isomers during
xylene isomerization, the alkylation of toluene by methanol, and
toluene disproportionation [5]. Moreover, Pt treated ZSM-5 cat-
alysts are suitable for the hydrodealkylation of aromatics to BTX
[6].
Aromatic compounds have been widely applied in the petro-
chemical and fine chemical industries, and C9 + aromatics, which
consist of small amount of xylene isomers, ET isomers, TMB iso-
mers, and tetramethylbenzene (TeMB) isomers, can be converted
∗ Corresponding author. Fax: +82 32 872 0959.
E-mail address: shbaeck@inha.ac.kr (S.-H. Baeck).
to BTX, useful raw materials [7]. In addition, 1,3,5-TMB and 1,2,4-
TMB (both C9 + aromatics) are useful industrially. 1,3,5-TMB is a
major reaction intermediate in the preparation of trimesic acid
(or 1,3,5-benzenetricarboxylic acid), and, possibly in the form
of its anhydride, is used to produce plasticizers for polymers
and polymidic, epoxy, and polyester resins [8]. On the other
hand, 1,2,4-TMB is used mainly as the raw material for the pro-
duction of trimellitic anhydride, and is also used to produce
pharmaceuticals and dyes [9]. 1,2,4-TMB is obtained by distilla-
tion from reforming hydrocarbon streams, in which it is present
at high concentrations. However, 1,3,5-TMB cannot be recov-
ered in the same way, because of presence of other organics,
such as, methylethylbenzene (MEB) isomers, with similar volatil-
ities. For this reason, selective removal of alkyl group bonded to
benzene ring by MFI based catalysts has been actively studied
[10–13].
In this study, a series of Pt/H-ZSM-5 catalysts with different crys-
tallite sizes were synthesized and characterized by SEM, BET, XRD,
and ICP-OES, and subjected to catalytic performance tests for the
selective hydrodealkylation of C9 + aromatics to BTX. We focused on
both ET conversion and TMB recovery yields and we discuss rela-
tionships between the crystallite sizes of the as-prepared catalysts
and their catalytic activities.

http://dx.doi.org/10.1016/j.molcata.2015.06.035
1381-1169/© 2015 Elsevier B.V. All rights reserved.
148 D. Lim et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 147–151
Fig. 1. Schematic diagram of a continuous flow fixed reactor.
2. Experimental
2.1. Synthesis of Pt/H-ZSM-5
1 g NaOH (98 wt.%, Samchun) was dissolved in 120 ml of water,
and to this solution, 6 g of TPABr (98 wt.%, Sigma–Aldrich) was
added with stirring. Sodium aluminate (0.8 g; 53 wt% Al2 O3 , 43 wt%
Na2 O, Sigma–Aldrich) was dissolved in this mixture over 30 min,
and then 25.2 g of silica (91.8% SiO2 , Zeosil 77, KoFran) was added
slowly. The mixture was then aged by stirring at 500 rpm for 0,
0.5, 12, 24, and 96 h at 70 ◦ C. The slurry obtained was transferred
to a Teflon-lined stainless-steel autoclave, and crystallized in an
autoclave at 170 ◦ C for 24 h. As-synthesized samples were washed
several times with distilled water to remove impurities. The sodium
form of zeolite obtained was then converted into the protonic form
by ammonium exchange using an aqueous solution (0.04 wt.%) of
NH4 Cl at 80 ◦ C for 12 h, followed by washing and drying. Thereafter,
platinum was impregnated into synthesized zeolite using an aque-
ous solution of Pt(NH3 )4 Cl2 at 50 ◦ C for 8 h, as previously described
[10]. Finally, the of Pt/H-ZSM-5 zeolites were washed several times
with distilled water, and calcined calcined at 200 ◦ C for 16 h.
Synthesized Pt/H-ZSM-5 catalysts are denoted as Pt/H-ZSM-5(X)
(where X = 0 ∼ 96), according to aging time.
2.2. Physical characterization
The crystallinity of prepared samples was investigated by an
X-ray diffraction using Ni filtered Cu KK radiation (XRD, Rigaku,
D/max-2200), and their morphologies and crystallite sizes were
examined by scanning electron microscopy (SEM, Hitachi, S-4300).
Chemical compositions of the catalysts were determined by induc-
tively coupled plasma optical emission spectrometry (ICP-OES,
Optima 7300DV). Specific surface areas, pore volumes, and aver-
age pore size were determined using the N2 adsorption method
(Micromeritics, ASAP 2020) at 77 K.
2.3. Performance of catalysts
Selective hydrodealkylation of C9 + aromatics to BTX was carried
out in a conventional fixed bed reactor to evaluate the activities of
the Pt/H-ZSM-5 catalysts, as shown in Fig. 1.
Table 1
Composition of C9 + aromatic feedstock.
Xylene (%) ET isomer (%) TMB isomer (%)
P-ET O-ET 1,3,5-TMB 1,2,4-TMB
3.50 7.48 0.93 18.68 53.01
C9 + aromatic mixtures containing xylene, ET isomers, TMB iso-
mers, and TeMB isomers were used as feed stocks (Table 1).
Catalyst (171 mg) was loaded in the constant temperature zone
of a reactor using quartz wool. Prior to reaction, catalyst was acti-
vated at 400 ◦ C for 1.5 h under flowing of 4 ml/min hydrogen for
the reduction of Pt. And then, C9 + aromatics and hydrogen (1:2)
were injected in to the reactor at the constant pressure. The reac-
tion was conducted at various temperatures (370, 390, 410, 430,
and 450) and atmospheric pressure. Products were analyzed using
a gas chromatograph (Agilent, 6890A) equipped with a flame ion-
ization detector (FID). ET Conversion and TMB recovery yield were
calculated using the following equations.
ET in reactant − ET in product
ET conversion(%) = × 100
ET in reactant
TMB in product
TMB recovery yield(%) = × 100
TMB in reactant
3. Results and discussion
3.1. Characterization of Pt/H-ZSM-5 catalysts
SEM was used to determine the morphologies and crystallite
sizes of the prepared catalysts (Fig. 2). With respect to aging time,
that is, 0 min, 30 min, 12 h, 24 h, and 96 h, crystallite sizes were ca.
40, 20 10, 5, and 2 ␮m, respectively.
This result can be explained by the relation between aging time
and nucleation. In other words, as the aging time of the mixed slurry
before crystallization was increased, more nuclei formed, which
lead to the development of different crystallite sizes. Similar results
were observed by Alfaro et al. [14]. Whereas, no significant dif-
ference in crystallite shape was detected, variable crystallite sizes
were obtained by changing aging time, as confirmed in Fig. 2.
Table 2 summarizes Pt loading amount determined by ICP-OES
and average pore diameters, BET surface areas, internal surface
areas, external surface areas, micropore volumes, and mesopore
volumes with respect to crystallite sizes.
The Pt/H-ZSM-5 catalysts produced had almost the same
amount of Pt and BET surface areas. Furthermore, Pt loading amount
were in good agreement with the designed value, and BET sur-
face areas were consistent with typical values previously reported
[15,16]. The N2 adsorption revealed that external and internal sur-
face area were strongly dependent on crystallite sizes, that is, as
crystallite size decreased, external surface area was increased and
internal (pore) surface area decreased, which concurs with the find-
ings of a previous study [17].
The XRD patterns of the Pt/H-ZSM-5 catalysts with respect to
crystallite size are shown in Fig. 3.
All catalysts had the typical crystalline structure of ZSM-5 [18],
and no other phase was observed, indicating that Pt/H-ZSM-5 cata-
lysts were successfully synthesized. The crystallinity of Pt/H-ZSM-5
catalysts, as determined by diffraction peaks around 7.5–9.5◦ ,
reduced as crystallite size decreased probably due to disruption of
the microporous structure of ZSM-5 associated with a smaller crys-
tallite size. This finding is consistent with the observed decrease in
pore surface area and micro pore volume (Table 2).
TeMB isomer (%)
1,2,3-TMB 1,2,4,5-TeMB 1,2,3,5-TeMB 1,2,3,4-TeMB
7.27 3.38 4.52 1.23
 D. Lim et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 147–151 149

Fig. 2. SEM images of (a) Pt/H-ZSM-5(0), (b) Pt/H-ZSM-5(0.5), (c) Pt/H-ZSM-5(12), (d) Pt/H-ZSM-5(24), and (e) Pt/H-ZSM-5(96).

Table 2
Pt compositions and microstructure properties of Pt/H-ZSM-5 catalysts.

Samples Pta (wt.%) Microstructure properties

SBET b (m2 /g) Spore c (m2 /g) Sext c (m2 /g) Vmicro c (cm3 /g) Vmeso d (cm3 /g)

Pt/H-ZSM-5(0) 0.28 379.1 258.5 120.6 0.116 0.058

Pt/H-ZSM-5(0.5) 0.29 356.3 220.6 135.7 0.114 0.080
Pt/H-ZSM-5(24) 0.28 360.2 140.5 219.7 0.073 0.139
Pt/H-ZSM-5(96) 0.28 377.2 122.1 255.1 0.056 0.144
a
Measured by ICP-OES.
b
Total surface areas were determined by the BET method.
c
Determined by the t-plot method.
d
Vmeso = Vads, P/Po = 0.99 − Vmicro .

3.2. Catalytic activities of the Pt/H-ZSM-5 catalysts

The catalytic performances of Pt/H-ZSM-5(X) (X = 0.5 and 24)

catalysts as a function of reaction temperature for the selective
Pt/H-ZSM-5(0)
hydrodealkylation of C9 + aromatics to BTX performed over 3 h are
Intensity / a.u.

shown in Fig. 4(a) and (b), respectively.

Pt/H-ZSM-5(0.5) Both ET conversion and TMB recovery yield remained
unchanged with reaction temperature, but ET conversion of Pt/H-
Pt/H-ZSM-5(12) ZSM-5(0.5) was much lower than that of Pt/H-ZSM-5(24) at all
temperature ranges investigated. This is believed to have been
Pt/H-ZSM-5(24) caused by increases in the diffusion rates of ET isomers and in
external surface area caused by the smaller crystallite size of the
Pt/H-ZSM-5(96) Pt/H-ZSM-5. Also, since ortho-ET has a relatively large molecu-
lar diameter as compared with para-ET, diffusion of para-ET into
5 10 15 20 25 30 35 40 catalyst pores is more rapid [19]. Thus, Pt/H-ZSM-5(24) with a rel-
atively large external surface area exhibited higher ET conversion
2 theta / degree than Pt/H-ZSM-5(0.5).
Product distributions among benzene, toluene, and xylene
Fig. 3. X-ray diffraction patterns of Pt/H-ZSM-5 catalysts.
over Pt/H-ZSM-5(X) (X = 0.5 and 24) catalysts were analyzed

Fig. 4. ET conversion and TMB recovery yield over (a) Pt/H-ZSM-5(0.5) and (b) Pt/H-ZSM-5(24) catalysts as a function of reaction temperature at WHSV = 3 h−1 .
150 D. Lim et al. / Journal of Molecular Catalysis A: Chemical 407 (2015) 147–151
Fig. 5. Benzene, toluene, and xylene production over (a) Pt/H-ZSM-5(0.5) and (b) Pt/H-ZSM-5(24) catalysts as a function of reaction temperature at WHSV = 3 h−1 .
Fig. 6. ET conversion and TMB recovery yields over Pt/H-ZSM-5 as a function of
crystallite size at 410 ◦ C, and WHSV = 3 h−1 .
after a reaction time of 3 h and plotted as a function of reaction
temperature (Fig. 5).
Although, both ET conversion and TMB recovery yield were
almost same at different reaction temperatures (Fig. 4), the
BTX product distribution changed. As the reaction temperature
increased, the production of toluene and xylene decreased, and
benzene production increased. This result was ascribed to the
increase of dealkylation with reaction temperature, and concurs
with the findings of a previous study regarding the influence of tem-
perature on the formation of benzene and toluene during xylene
isomerization [20]. In addition, the sum of all BTX products for
the Pt/H-ZSM-5(24) was greater than that of Pt/H-ZSM-5(0.5) at
each reaction temperature due to the decrease in TMB recovery
yield, as shown in Fig 4. It can be concluded that BTX are produced
by not only the hydrodealkylation of ET but also dealkylation of
TMB, and BTX product distribution is strongly affected by reaction
temperature.
The correlation between catalyst crystallite size and catalytic
activity for the hydrodealkylation of C9 + aromatics at 410 ◦ C after
3 h reaction is shown in Fig. 6.
It was found that ET conversion increased and TMB recovery
yield decreased with decreasing crystallite size. These results imply
that ET conversion increased on increasing catalyst external surface
area by reducing crystallite size. However, undesirable dealkyla-
tion of TMB also increased with increasing catalyst external surface
area, resulting in reduced TMB recovery yields. Furthermore, TMB
conversion was found to be lower than ET conversion, which can
be explained by two factors. (1) TMB isomers could not diffuse
as rapidly into the pores of ZSM-5 [19] and (2) the difference
between the dissociation energies of alkyl groups on the benzene
ring. Although cleavage off an ethyl cation, which is subsequently
rapidly deprotonated to ethene and hydrogenated to ethane over
Pt, from protonated ET is viable, no methyl cation can be split off
protonated toluene or protonated ET due to the poor stability of the
carbenium ion [21]. Therefore, the hydrodealkylation of ET isomers
to toluene and ethane is kinetically strongly preferred, as has been
reported by Serra et al. [22]. Consequently, the optimum crystal-
lite size of the catalyst was found to be about 5 ␮m, at which ET
conversion was 94.3% and TMB recovery yield was 92.3%.
4. Conclusions
A series of Pt/H-ZSM-5 catalysts with different crystallite sizes
(40, 20 10, 5, and 2 ␮m) were prepared and then used for the selec-
tive hydrodealkylation of C9 + aromatics to BTX.
External and internal surface areas were strongly dependent on
crystallite size, and external surface area was increased and inter-
nal (pore) surface area decreased with the decrease of crystallite
size. ET conversion over Pt/H-ZSM-5 increased as crystallite size
decreased, whereas TMB isomer recovery yields decreased. Crys-
tallite size was found to determine catalytic performance for the
selective hydrodealkylation of C9 + aromatics to BTX, and the opti-
mum crystallite size of the catalyst was found to be about 5 ␮m,
considering both ET conversion and TMB recovery yield.
Acknowledgments
This work was supported by the National Research Foundation
of Korea (NRF) funded by the Korean Government (MEST) (NRF-
2013R1A2A2A04013913). Also the authors wish to acknowledge
support from the S-OIL Corporation.
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