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The effect of Si/Al ratio on the catalytic performance of hierarchical
porous ZSM-5 for catalyzing benzene alkylation with methanol
Hualei Hu, Jinghui Lyu, Jiayao Rui, Jie Cen, Qunfeng Zhang, Qingtao Wang, Wenwen Han and
Xiaonian Li*
Published on 18 January 2016. Downloaded by Gazi Universitesi on 18/01/2016 11:57:32.

5 Received (in XXX, XXX) Xth XXXXXXXXX 20XX, Accepted Xth XXXXXXXXX 20XX
DOI: 10.1039/b000000x

Abstract: Ethylbenzene is the major side product in benzene alkylation with methanol and it is difficult to be suppressed over
hierarchical porous ZSM-5. Moreover, the separation of ethylbenzene from xylene yet remains as a great challenge. Our research
indicated that ethylbenzene formation could be highly suppressed by changing the Si/Al ratio of the catalyst. Hierarchical porous ZSM-5
10 catalysts with different Si/Al ratios were prepared via reducing the amount of Al in the solvent evaporation assisted dry gel conversion
method. In this method, tetra-n-propylammonium hydroxide was used as the direct-agent to create micropores, and
hexadecyltrimethoxysilane was added to create additional porosities by forming organic assemblies which occupied a certain space
between zeolitic walls. The catalyst with Si/Al ratio of 1800 could achieve the high benzene conversion (59.5%) and high xylene
selectivity (39.0%) as well as excellent suppression of ethylbenzene formation (<0.1%).

15 1. Introduction suppression of ethylbenzene was positively related to the

inhibition of methanol to olefins reaction. However, the degree of
Being an important chemical intermediate, xylene has been
50 such suppression over Mg or Zn modified catalysts was limited.
broadly used in industry for the production of fine chemicals.1
We also found that strong Brönsted acid played an important role
Currently, alkylation of benzene is receiving increased attentions
in catalyzing side reaction of methanol.16, 17 Metal nitrates could
in petrochemical industry duo to its nature as the good alternative
be used to adjust the acidity through impregnation method, but
20 to produce xylene from coal and natural gas.2, 3 ZSM-5 zeolite, a
the decrease of BET surface area was also observed.17, 18 It has
solid acid catalyst, has been widely used as an industrial catalyst
55 long been realized that the acid site is a substitutional defect
due to its excellent catalytic activity and shape selectivity
which is introduced by replacing a Si atom with an Al atom in the
characteristics.4 However, the intrinsic micropores in
framework of zeolites.19 Therefore, the direct adjustment of Si/Al
conventional ZSM-5 inhibit the diffusion of bulky substrates,
ratio of hierarchical porous ZSM-5 is expected to improve the
25 which results in low conversion of benzene and low selectivity of
catalytic performance and avoid the adverse effects of
xylene.5, 6 Moreover, ethylbenzene formed via benzene alkylation
60 impregnation method.
with ethylene is a major side product and it is either hard to be
In present work, we synthesized hierarchical porous ZSM-5
suppressed or separated from xylene.7, 8
with different Si/Al ratios by solvent evaporation assisted dry gel
Recently, hierarchical porous ZSM-5 showed excellent
conversion method. The effect of Si/Al ratio on the textural
30 catalytic properties in benzene alkylation reactions. It was the
properties was characterized by various techniques (including
result of enhancing the diffusion by introducing the mesopores
65 XRD, Nitrogen sorption isotherms, SEM, TEM, NMR, NH3-TPD,
into zeolite material as well as retaining the catalytic feature of
Py-IR and TG). It was observed that increasing the Si/Al ratio by
zeolitic micropores.5, 6, 9 However, ethylbenzene formation still
decreasing the Al amount in the synthesis process could
remains as a problem.6 Although modifying the catalyst with Pt
effectively reduce the acidity of catalyst. The hierarchical porous
35 could effectively lower the formation of ethylbenzene by
ZSM-5 catalyst with Si/Al ratio of 1800 was considered to
hydrogenating ethylene into ethane, the utilization rate of
70 exhibite the appropriate Brönsted acidity for the most effective
methanol decreased due to the lower conversion of methanol into
suppression of the side reaction of methanol to olefins which in
alkylaromatics.10 It should be noted that ethylene is generated
turn inhibited the formation of ethylbenzene and coke.
from the reaction of methanol to olefins.8, 11 Therefore, inhibiting
40 methanol turning into olefins would help to fundamentally
2. Experimental
suppress the formation of ethylbenzene.
Great efforts have been made previously to suppress the side
2.1. Catalyst preparation.
reaction of methanol to olefins.12-17 Adebajo et al introduced Na
into ZSM-5 by ion exchange and observed that ZSM-5 with less 75 Hierarchical porous ZSM-5 was prepared via solvent
45 Brönsted acidity could minimize the occurrence of such evaporation assisted dry gel conversion route.15, 20 In each
reaction.14 In our previous research, we modified the hierarchical synthesis, tetraethylorthosilicate (TEOS, Shanghai Chemical
porous ZSM-5 with Zn and Mg and confirmed that the

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Reagent Co.), aluminum isopropoxide (AIP, Sinopharm 55 at room temperature. For pyridine adsorption (Py-IR), pyridine
Chemical Reagent Co., Ltd.), tetra-n-propylammonium hydroxide vapour was introduced into the cell at room temperature for 1 h;
(TPAOH, Aladdin Industrial Inc.), hexadecyltrimethoxysilane the spectra were then recorded after evacuation at 400°C for 1 h.
(HTS, Aladdin Industrial Inc.) and ethanol (EtOH, Anhui Ante The concentrations of Brönsted acid (B) and Lewis acid (L) were

Catalysis Science & Technology Accepted Manuscript

5 Food Company Co., Ltd.) were mixed under stirring to form a
solution with molar ratio of 1SiO2: xAl2O3: 0.2TPAOH: 0.05HTS:
15EtOH (where x=0.0028, 0.00224, 0.00168, 0.00112, 0.00056,
0.00028, 0.00014, 0). The resulted gel mixture was aged at room
temperature for 24 h and placed into a PTFE cup before
10 transferring into the Teflon-lined autoclave. A small amount of
water was added outside the PTFE cup to create steam. The
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calculated from the peak areas of adsorbed pyridine at around
60 1540 and 1450 cm−1, and the extinction coefficients of ε(B) and
ε(L) was 1.88 and 1.42 cm.mmol−1, respectively.22
2.3. Catalytic activity test.
All evaluation experiments were carried out in a continuous-
flow fixed-bed reactor with a stainless steel tube (8-mm i.d.) at

autoclave was heated at 180°C for 72 h. After crystallization, the

65 atmospheric pressure. In each test, 0.5 g catalyst diluted with 5.0
product was washed and filtrated without ion-exchange steps and g inert quartz sand were loaded in the middle of the tube reactor.
calcined at 550°C for 7 h (heating rate of 10°C/min) to obtain H- The catalyst was heat-treated in situ from ambient temperature to
15 form hierarchical porous ZSM-5. 400°C at 10°C/min and maintained at 400°C for 1 h in N2 flow
with a space velocity of 2400 h−1. Benzene and methanol mixture
2.2. Catalyst characterization. 70 (B/M molar ratio = 1:1) was then fed into the reactor (WHSV=2.0
X-ray diffraction (XRD) (SCINTAG X” TRA) was measured h−1) at 400°C with a co-feed N2 flow of 40 mL/min. The effluent
from the reactor was analyzed online by the gas chromatography
using Cu K-radiation (1542 A) at 30 mA and 40 kV with
(Fuli GC9790) with a DB-1capillary column (30 m × 0.25 mm ×
scanning angle (2θ) from 5 to 80°. An X-ray fluorescence
1.00 µm) and a flame ionization detector. In order to ensure all of
20 instrument from Thermo Fisher (model ARL ADVANT' X
75 the products were in gas phase, the temperature of the effluent
IntelliPower TM 4200) was used to examine the elements and
line was maintained at 200 °C by heating belt.
determine their quantities in the samples.21 Each sample was
prepared with polypropylene film and analyzed in vacuum. Solid-
3. Results and discussion
state 27Al MAS NMR were carried out on a Bruker AVANCE III
25 600 spectrometer at a resonance frequency of 156.4 MHz. A 4
3.1. Catalyst characterization.
mm HX double-resonance MAS probe was used and a sample
spinning rate of was set at 14 kHz. The chemical shift of 27Al was Fig. 1 showed the XRD patterns of synthesized hierarchical
referenced to 1 M aqueous Al(NO3)3. 27Al MAS NMR spectra 80 porous ZSM-5 catalysts. All the samples exhibited the typical
were recorded by small-flip angle technique with a pulse length characteristic patterns with peaks observed at 2θ of 7.9°, 8.8°,
30 of 0.5 µs (<π/12) and a 1s recycle delay. The nitrogen sorption 23.1°, 23.9°, and 24.3° which corresponded to the structure of
isotherms were measured using Micromeritics ASAP-2020 MFI topology.23, 24 Moreover, the similar diffraction peaks of the
system. The samples were outgassed at 180°C for 10h before the samples indicated that the adjust of Si/Al ratio in the synthesis
measurements. The total surface areas were determined by the 85 process did not have significant influence on the framework of
Brunauer–Emmett–Teller (BET) method. The micropore volumes hierarchical porous ZSM-5.
35 were calculated by the t-plot method and total pore volumes were The textural properties of the synthesized samples were
estimated from the amount of N2 adsorbed at p/p0 = 0.99. Meso- characterized by N2 adsorption/desorption. As shown in Table 1,
/macro- pore volumes were calculated by subtracting micropore besides a micropore volume (~0.14 cm3/g), the macropore &
volumes from total pore volumes. The pore-size distribution was 90 mesopore volumes of all modified catalysts with different Si/Al
calculated using the Barrett-Joyner-Halenda (BJH) model. The ratios were ~ 0.24 cm3/g. In addition, the interconnectivity
40 differential thermal analysis (TG-DTA) was evaluated by
Netzsch STA 449 C apparatus using a temperature ramp from 30
to 800°C with a heating rate of 10°C /min in oxygen atmosphere.
NH3 temperature-programmed desorption (TPD) of the catalysts
was carried out using a Tianjin XQ TP-5076 chemisorption
45 instrument equipped with thermal conductivity detector (TCD).
The sample was evacuated at 400°C for 1 h in the flow of He
before cooling down to 50°C. The adsorption of NH3 was
performed with the flow of 10 vol% NH3/Ar at 50°C. The NH3
desorption was conducted between 100 and 650°C with a heating
50 rate of 10°C/min. The TCD signals were calibrated using 10 µL
of NH3 as standard. Fourier transform infrared (FT-IR) spectra
were measured on a VERTEX 70 FT-IR spectrometer. The
sample was firstly pressed into a wafer, and then heat-treated in
He flow (100 ml/min) at 400°C for 1 h. IR spectra were recorded
Fig. 1 XRD patterns of synthesized hierarchical porous ZSM-5 catalysts.

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Table 1 Compositional and textural properties of synthesized hierarchical

porous ZSM-5 catalysts.

Si/Al ratio Si/Al ratio SBET Vmicro Vmeso+macro

in gel in zeolitesa (m2/g) (cm3/g)b (cm3/g)c

Catalysis Science & Technology Accepted Manuscript

180 172 400 0.14 0.25
225 200 392 0.14 0.24
300 283 395 0.14 0.24
450 437 389 0.15 0.24
900 896 385 0.15 0.23
1800 1726 390 0.14 0.24
3600 2995 383 0.14 0.23
a
Si/Al ratio in zeolites was determined by XRF. b Micropore volume
was estimated using the t-plot method. c Mesopore macropore volume
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was calculated by subtracting micropore volumes from total pore

volumes estimated from the amount of N2 adsorbed at P/P0 = 0.99.
Fig. 3 SEM image (a) (b) and TEM image (c) (d) of synthesized
35 hierarchical porous ZSM-5 (Si/Al ratio of 1800).

Fig. 2 Nitrogen adsorption-desorption isotherms of synthesized

5 hierarchical porous ZSM-5 (Si/Al ratio of 1800) (Inset: pore-size
distribution deduced from the adsorption branch of the isotherm). Fig. 4 Catalytic performances of synthesized hierarchical porous ZSM-5
in benzene alkylation with methanol.
between micro- and meso/macro pores of the catalyst which was
prepared by the same method in this work was proved by Zhang Si/Al ratio from 180 to 1800, the conversion of benzene and the
et al.20 Thus, we concluded that all the synthesized samples were 40 selectivity to xylene increased gradually from 51.5 to 59.5 % and
10 hierarchically porous. 33.6 to 39.0 %, respectively. Moreover, the selectivity to
The N2 physisorption isotherms and SEM and TEM images of ethylbenzene decreased from 3.5 to 0.09 %, indicating that the
synthesized hierarchical porous ZSM-5 were carefully compared catalyst with Si/Al ratio of 1800 could suppress the formation of
and little difference between the samples with different Si/Al ethylbenzene more effectively.
ratios was observed. Here, the sample with Si/Al ratio of 1800 45 Further increasing the Si/Al ratio to 3600, the performance of
15 was used as a representative. As seen in Fig. 2, the sample the catalyst deteriorated distinctly. Therefore, 1800 was
exhibited the characteristic features of type-IV isotherm, a considered as the optimum Si/Al ratio for hierarchical porous
hysteresis loop which was associated with capillary condensation
taking place in mesopores and the limiting uptake over a range of
high P/P0. The pore size distribution of hierarchical porous ZSM-
20 5 was obtained through the BJH method (Fig. 2 inset), a broad
pore size between 5 and 30 nm centered at 12 nm was observed.
Similar results were also reported by Zhu et al.20
The SEM images in Fig. 3a and 3b showed the crystal
morphology of synthesized hierarchical porous ZSM-5 (Si/Al
25 ratio 1800). It can be seen that the shape of sample crystal is
roughly ellipsoidal with a size of about 200-300 nm. The TEM
images in Fig. 3c and 3d clearly showed that the aggregates were
made of crystalline nanoparticles ranging from 10 to 50 nm.
3.2. Catalyst Tests.
30 Fig. 4 showed the catalytic performance of synthesized
hierarchical porous ZSM-5 with different Si/Al ratios in benzene Fig. 5 The stability of hierarchical porous ZSM-5 (Si/Al ratio of 180 and
alkylation with methanol. It can be seen that with the increase of 50 1800) in benzene alkylation with methanol.

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Fig. 6 TG profile of hierarchical porous ZSM-5 (Si/Al ratio of 180 and Fig. 7 Solid-state 27Al MAS NMR spectra of hierarchical porous ZSM-5
1800) after successive reaction time (50 h). (Si/Al ratio of 180, 450 and 1800).

ZSM-5 in catalyzing benzene alkylation with methanol. In order on the hierarchical porous ZSM-5 with Si/Al ratio of1800.
5 to prove the reproducibility of the performance of the catalyst 35 Moreover, we noted that in the reaction products of both catalysts,
with Si/Al of 1800, we synthesized and evaluated the catalyst for methanol and dimethyl ether were not detected meaning the
several times (see in Fig. S3 and S4) and the result indicated that complete conversion of reactant methanol. With the side reaction
the data in Fig 4 was reliable. of methanol suppressed, more proportion of methanol was indeed
The stability of hierarchical porous ZSM-5 catalysts (Si/Al converted into alkylaromatics on the catalyst with Si/Al ratio of
10 ratio of 180 and 1800) was also investigated. As seen in Fig. 5, 40 1800. More conversion of methanol into alkylaromatics clearly
both catalysts were stable in the investigated reaction time period, improved the utilization of methanol.
but a higher benzene conversion was obtained on the catalyst It was clear that Brönsted acidity of the catalyst was closely
with Si/Al ratio of 1800. related to the suppression of side reaction of methanol,12, 16, 17 so
It should be noted that olefins was the main precursor of coke. the suppression mechanism of hierarchical porous ZSM-5
15 Thus, it is necessary to investigate the suppression effect of the 45 catalysts was investigated by focusing on the effect of the
modified catalysts on the reaction of methanol to olefins through Brönsted acidity of hierarchical porous ZSM-5 with different
the change in coke content and product distributions. The TG Si/Al ratios. Fig 7 displayed solid-state 27Al MAS NMR spectra
profiles (Fig. 6) clearly exhibited that the coke content on used of hierarchical porous ZSM-5 (Si/Al ratio of 180, 450 and 1800).
hierarchical porous ZSM-5 catalyst with Si/Al ratio of 1800 These spectra were used to determine the local chemical
20 (1.8%) was lower than that of the catalyst with Si/Al ratio of 180 50 environment around the Al atoms of these samples. For all
(3.36%). Furthermore, as compared to hierarchical porous ZSM- samples, a large signal at ∼54 ppm corresponding to the
5 with Si/Al ratio of 180, the content of light hydrocarbons (<C6) tetrahedral-coordinated framework Al with four Al-O-Si bonds
on hierarchical porous ZSM-5 with Si/Al ratio of 1800 was much was observed. In addition, a negligible peak at 0 ppm was
less. Considering the change of coke content and light observed which could be attributed to the existence of a small
25 hydrocarbons content, it was reasonable to conclude that the side 55 amount of extra-framework octahedral Al. Based on these spectra,
reaction of methanol to olefins was more effectively suppressed we could conclude that all samples contained similar tetrahedral
coordinated framework Al species.
Table 2 Products distribution of benzene alkylation with methanol on
hierarchical porous ZSM-5 (Si/Al ratio of 180 and 1800)
Content wt%
Components
Si/Al ratio of 180 Si/Al ratio of 1800
Methane 0.02 0.01
Ethylene 0.08 0.06
Ethane 0.06 0.02
C3 0.64 0.13
C4 0.21 0.05
C5 0.10 0.05
Benzene 38.04 32.01
Toulene 22.27 27.51
Ethylbenzene 1.90 0.06
Xylene 19.66 24.95
Trimethylbenzene 5.55 6.65
Other 11.47 8.9
Utilization efficiency
93.1 98.2
of methanol (%)
30 Reaction condition: 400°C, 0.1MPa, 2h-1, nbenzen/nmethanol=1:1. Fig. 8 NH3-TPD profiles of hierarchical porous ZSM-5 (Si/Al ratio of 180,
60 450 and 1800).

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Fig. 9 FT-IR spectra of pyridine adsorption on hierarchical porous ZSM-5
(Si/Al ratio of 180, 450 and 1800).
Fig. 8 showed the NH3-TPD profiles of hierarchical porous
5 ZSM-5 (Si/Al ratio of 180, 450 and 1800). The amount of
ammonia desorbed from the sample surface can be stated via
TPD peak areas. It could be observed that all the samples
exhibited two desorption peaks, named as low-temperature peak
(located below 200°C) and high-temperature peak (located above
10 300°C), which could be ascribed to the ammonia adsorbing onto
the weak and strong acid sites, respectively. As shown in Fig. 8,
with the increase of Si/Al ratio, the peak areas of weak and strong
acid sites both reduced, indicating the decrease of the total
amount of acid sites. Moreover, the pyridine-adsorbed IR spectra
15 of samples (Fig 9) showed that with the increase of Si/Al ratio,
both the peak areas of Brönsted acid sites and Lewis acid sites
decreased with little change in the ratio of B/L. The Brönsted acid
site was a substitutional defect which was introduced by
replacing a Si atom with an Al atom in the framework of zeolites,
20 and the Lewis acid sites was coordinative unsaturated Al3+. Thus,
reducing the amount of Al would lead to the decrease of both
Brönsted acid site and Lewis acid sites and in turn the decrease of
total acid sites. It should be noted that the amount of Lewis acid
sites increased by modifying hierarchical porous ZSM-5 with Mg
25 and while decreased by adjusting the Si/Al ratio of hierarchical
porous ZSM-5, the side reaction of methanol to olefins was
suppressed in both cases.17 This could suggest that the role of
Lewis acid sites was negligible.7, 25
Based on above discussions, it was reasonable to conclude that
30 appropriate Brönsted acidity which hierarchical porous ZSM-5
with Si/Al ratio of 1800 obtained may well be the key reason why
methanol to olefins reaction was highly suppressed. In this case,
high inhibition of ethylbenzene formation can be achieved by
simply adjusting the Si/Al ratio. As compared to the addition of
35 noble metal (Pt and Pd), this method can contribute greatly in
simplifying the preparation process of catalyst and reducing the
cost of xylene production.
4. Conclusions
In this work, hierarchical porous ZSM-5 catalysts with
40 different Si/Al ratios were prepared via reducing the amount of
Al in the synthesis process directly. The results indicated that by
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directly adjusting the Si/Al ratio of catalyst can successfully
suppress ethylbenzene formation by suppressing the side reaction
of methanol to olefins. The reason could be that the side reaction
45 of methanol was inhibited by the precise control of Brönsted
Catalysis Science & Technology Accepted Manuscript
acidity. Most importantly, as compared to the addition of noble
metal to suppress ethylbenzene formation by hydrogenation, this
method would help to improve the commercial viability of the
alkylation of benzene with methanol for industrial production of
50 xylene.
Acknowledgments
We acknowledge financial support from the National Natural
Science Foundation of China (NSFC-21476207) and National
Basic Research Program of China (973 Program) (No.
55 2011CB710800).
Notes
Industrial Catalysis Institute of Zhejiang University of Technology, State
Key Laboratory Breeding Base of Green Chemistry Synthesis Technology,
Hangzhou, 310032, P. R. China,
60 *Corresponding author. E-mail: xnli@zjut.edu.cn.
References
(1) W. Alabi, L. Atanda, R. Jermy and S. Al-Khattaf, Chem.Eng. J., 2012,
195-196, 276-288.
(2) A.A. Rownaghi and J. Hedlund, Ind. Eng. Chem. Res., 2011, 50,
65 11872-11878.
(3) X. M. Wang, J. Xu, G.D. Qi, B.J Li, C. Wang and F. Deng, J. Phys.
Chem. C., 2013, 117 , 4018-4023.
(4) S. Inagaki, S. Shinoda, Y. Kaneko, K. Takechi, R. Komatsu, Y.
Tsuboi, H. Yamazaki, J.N. Kondo and Y. Kubota, ACS Catal., 2013, 3,
70 74-78.
(5) C. H. Christensen, K. Johannsen, I. Schmidt and C. H. Christensen, J.
Am. Chem. Soc., 2003, 125, 13370-13371.
(6) H. L. Hu, Q. F. Zhang, J. Cen and X. N. Li, Catal. Lett., 2015, 145,
715-722.
75 (7) J. R. Anderson, T. Mole and V. Christov, J. Catal., 1980, 61, 477-484.
(8) W. W. Kaeding, J. Catal., 1988, 114, 271-276.
(9) C. H. Christensen, K. Johannsen, E. Tőrnqvist, I. Schmidt, H. Topsøe
and C. H. Christensen, Catal.Today., 2007, 128, 117-122.
(10) H. L. Hu, Q. F. Zhang, J. Cen and X.N. Li, Catal. Commun., 2014,
80 57, 129-133.
(11) Y. Zhao, W. Tan, H. Y. Wu, A. F. Zhang, M. Liu, G. M. Li, X. S.
Wang, C. S. Song and X. W. Guo, Catal. Today, 2011, 160, 179-183.
(12) M. O. Adebajo and M. A. Long, Catal. Commun., 2003, 4, 71–76.
(13) M. O. Adebajo, M. A. Long and R. L. Frost, Catal. Commun., 2004,
85 5, 125–130.
(14) M. O. Adebajo, R. F. Howe and M. A. Long, Catal. Today, 2000, 63
471–478.
(15) W. Deng, X. He, C. Zhang, Y. Y. Gao, X. D. Zhu, K. K. Zhu, Q. S.
Huo and Z. J. Zhou, Chin. J. Chem. Eng. 2014, 22, 921–929.
90 (16) H. L. Hu, J. H. Lyu, Q. T. Wang, Q. F. Zhang, J. Cen and X. N. Li,
RSC Adv., 2015, 5, 32679-32684.
(17) H. L. Hu, J. H. Lyu, J. Cen, Q. F. Zhang, Q. T. Wang,W. W. Han,
J. Y. Rui and X. N. Li, RSC Adv., 2015, 5, 63044–63049.
(18) D. S. Mao, W. M. Yang, J. C. Xia, B. Zhang, Q. Y. Song and Q. L.
95 Chen, J. Catal., 2005, 230, 140–149.
(19) S. L. C. Moors. K. D. Wispelaere, J. V. Mynsbrugge, M. Waroquier
and V. V. Speybroeck, ACS Catal., 2013, 3, 2556-2567.
(20) K. K. Zhu, J. M. Sun, J. Liu, L. Q. Wang, H. Y. Wan, J. Z. Hu, Y.
Wang, C. H. F. Peden and Z. M. Nie, ACS Catal., 2011, 1, 682-690.
Journal Name, [year], [vol], 00–00 | 5
 Catalysis Science & Technology Page 6 of 7
View Article Online
DOI: 10.1039/C5CY01976A

(21)J. M. Müller, G. C. Mesquita, S. M. Franco, L. D. Borges, J. L.

Macedo, J. A. Dias, S. C. L. Dias, Micropor. Mesopor. Mater., 2015, 204,
50-57.
(22) C. A. Emeis, J. Catal., 1993, 141, 347–354.
5 (23) A. Gervasini, Appl. Catal., A, 1999, 180, 71-82.

Catalysis Science & Technology Accepted Manuscript

(24) H. V. Koningsveld, J. C. Jansen, H. V. Bekkum, Zeolites, 1990, 10,
235-242.
(25) S. Müller, Y. Liu, M. Vishnuvarthan, X. Y. Sun, A. C. Veen, G. L.
Haller, M. Sanchez-Sanchez, J. A. Lercher, J. Catal. 2015, 325, 48–59.
10
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Graphic Abstract

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High suppression of ethylbenzene formation could be successfully achieved by

adjusting the Si/Al ratio of hierarchical porous ZSM-5.