Catalytic benzene mono-alkylation over three catalysts: improving activity and selectivity with M-Y catalyst

Article abstract of DOI:10.1007/s10847-017-0771-z

Modified Y type catalyst (M-Y) shows great potential for the preparation of toluene attribute to catalyst topology and synergistic effect of Lewis acid and Br?nsted acid in the alkylation reaction. However, it still remains a big challenge to build a reaction mechanism. Thereby, based on the study of HZSM-5, H-beta and M-Y catalysts structure and physical properties, a plausible reaction mechanism was proposed. The samples were characterized by X-ray diffraction, N₂ adsorption/desorption, Fourier transform infrared absorption spectra and Pyridine adsorption infrared. The activity of catalysts was tested in benzene alkylation with methanol and was found to be in the following increasing order: Na-Y (no effect) < H-Y << HZSM-5 < H-beta < M-Y.

Full text of DOI:10.1007/s10847-017-0771-z

Journal of Inclusion Phenomena and Macrocyclic Chemistry
https://doi.org/10.1007/s10847-017-0771-z
SHORT COMMUNICATION
Catalytic benzene mono-alkylation over three catalysts: improving
activity and selectivity with M-Y catalyst
Peng Dong1,2 · Zeyu Li3 · Dong Ji1 · Xiaorui Wang2 · Hongfei Yun1 · Zhisong Du1 · Jie Bian1 · Guixian Li1
Received: 13 October 2017 / Accepted: 24 November 2017
© Springer Science+Business Media B.V., part of Springer Nature 2017
Abstract
Modified Y type catalyst (M-Y) shows great potential for the preparation of toluene attribute to catalyst topology and syn-
ergistic effect of Lewis acid and Brönsted acid in the alkylation reaction. However, it still remains a big challenge to build a
reaction mechanism. Thereby, based on the study of HZSM-5, H-beta and M-Y catalysts structure and physical properties,
a plausible reaction mechanism was proposed. The samples were characterized by X-ray diffraction, N2 adsorption/desorp-
tion, Fourier transform infrared absorption spectra and Pyridine adsorption infrared. The activity of catalysts was tested in
benzene alkylation with methanol and was found to be in the following increasing order: Na-Y (no effect)<H-Y<<HZSM
-5<H-beta<M-Y.
Keywords Benzene/methanol mono-alkylation · Toluene · Lewis/Brönsted acid · Synergistic effect · Catalyst topology
Introduction
catalyst mainly depended on the zeolites with suitable Brön-
sted acidity, which effectively minimized the side reaction
[5–7]. ZSM-5 catalyst modified with oxides could effec-
tively adjust acid sites of external surface, which in turn
enhance the selectivity of target product [8–10]. Ding et al.
discovered that Mg modified catalyst exhibited the highest
conversion of benzene and the best selectivity of ethylb-
enzene, which was confirmed to be attributed the proper
Lewis/Brönsted acid proportion [9]. General research is the
preparation of p-xylene, but toluene as the ultimate product
is a relatively difficult point.
Toluene is important solvent, gasoline additive and also the
important feedstock for industrial production of organic pig-
ment [1]. Meanwhile, because of the excessive production of
benzene in petrochemical industry and the production over-
capacity of methanol in coal chemical industry, it is impera-
tive that the technology of methanol-to-benzene reaction to
toluene is systematic researched to further implement the
coupling cycle development strategy of coal chemical indus-
try and petrochemical industry [2–4]. Nevertheless, it would
be of great importance that utilization of a suitable catalyst
could exploit the optimal path for the aromatics production
of behind the requirement.
The purpose of our study is to investigate a magical stand-
point where is synergistic effect of Lewis acid and Brönsted
acid and catalyst topology on the activity of catalysts for
the alkylation of benzene. The catalysts were characterized
by XRD, BET, FT-IR and Py-IR. The effect of the catalyst
properties for the performance of catalysts in alkylation of
benzene was deeply investigated. Furthermore, based on the
study of HZSM-5, H-beta and M-Y catalysts structure and
physical properties, a plausible reaction mechanism for the
selective formation of toluene was proposed.
Hence, the product of alkylation depends on the type of
catalyst. Based on the literatures, the selectivity of ZSM-5
* Guixian Li
lgxwyf@163.com
Peng Dong
dongpeng1227@163.com
1
College of Petrochemical Technology, Lanzhou University
of Technology, Lanzhou 730050, People’s Republic of China
2
Lanzhou Petrochemical College of Vocational Technology,
Lanzhou 730060, People’s Republic of China
3
College of Chemistry and Chemical Engineering, Lanzhou
University, Lanzhou 730000, People’s Republic of China
Vol.:(0123456789)
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
2010 instruments. Before measurement, the samples were
degassed under vacuum at 130 °C overnight.
Experimental
XRD patterns of catalysts were obtained with a D/MAX-
2400 X-ray diffractometer equipped with atmosphere and
temperature control stages and using Cu-Kα radiation
(λ=1.542 Å) operated at 40 kV and 50 mA. In these experi-
ments, XRD patterns were recorded every 50 °C with a ramp
rate of 10 °C/min up to 700 °C under 5% H2/N2.
Materials
Tetraethylorthosilicate (TEOS, SiO2 ≥ 24.7%), Tetrapro-
pylammonium hydroxide [TPAOH, 25% (by mass)
aqueous solution], Aluminium isopropoxide (AIP,
Al2O3 ≥ 24.7%) and Hexadecyltrimethoxysilane((HTS)
were obtained from Shanghai Aladdin Biochemical Tech-
nology Co., Ltd. Benzene (≥ 99.5%), Methanol (≥ 99.5%),
Ethanol (≥ 99.5%), Ammonium Carbonate (≥ 40%), Citric
acid (CA, ≥ 99.5%), conventional HZSM-5, H-beta and
Na-Y were purchased from the Catalyst Plant of Lanzhou
(China). All commercial chemicals were used directly
without further purifications.
FT-IR of the materials were acquired on a Nicolet Nexus
670 FT-IR spectrometer (Thermo Nicolet, USA) at room
temperature in KBr pellets over the range of 7400~350 cm−1
under the atmospheric conditions.
Pyridine adsorption measurements were performed by
infrared spectroscopy aiming to determine the nature of
acids sites (Brönsted and Lewis). Pyridine chemisorption
samples were obtained by passing pyridine vapour over the
catalysts at 373 K for 1 h in the flow system. After the pyri-
dine adsorption, the samples were stabilised in a N2 flow
for 30 min, then allowed to cool to room temperature and
subsequently used for IR analysis.
Catalyst preparation
Hierarchical ZSM-5 was prepared by means of solvent evap-
oration assisted dry-gel route which are similar to reported
[11] in many ways, but also differences. Firstly, NaOH, AIP,
1/2 of deionized water and TPABr were mixed together and
stirred until AIP was completely dissolved. Then TEOS,
HTS and the rest of deionized water were added to the solu-
tion and ultrasonic treatment for 30 min to obtain a gel. Then
the gel was placed into stainless steel autoclave equipped
with a PTFE liner. The synthesis temperature and time were
180 °C and 68 h, respectively. The resulting solid material
was obtained by filtration, then dried at 120 °C and calcined
at 550 °C for 4 h to obtain ZSM-5 sample. ZSM-5 sample
was treated with a solution of suitable concentration ammo-
nium carbonate (AC) and citric acid (CA) at 273 K for 1.5 h
under stir-ring, respectively. With that filtered, washed and
desiccated at 453 K. The desiccated sample was calcined at
823 K for 4 h in air to obtain HZSM-5 catalyst.
Catalytic activity tests
Catalytic activity of the samples was measured in a continu-
ous-flow jet bubbling reactor with a glass tube (8 mm i.d.) at
atmospheric pressure. The catalyst (0.5 g) was heat-treated
in situ from environmental temperature to 673 K at 10 K/
min. Then benzene/methanol mixture (1:1) were fed into the
reactor (WHSV=2.0 h−1).
Results and discussion
Catalyst characterizations
Both H-beta types displayed two distinct diffraction peaks
in 8° ~ 10° and 20° ~ 30°(2θ) ranges, which corresponded
to the structure of beta crystal structure [13] in comparison
with standard H-beta from Database of Zeolite Structures
in Fig. 1a. However, both H-beta types displayed two dis-
tinct diffraction peaks in 8°~ 10° were coincident and the
reason is probably small crystalline grain. The pattern of
H-beta after AC and CA is basically unchanged, which may
be due to buffer function of CA. The monitoring of samples
exhibited the typical characteristic patterns with peaks at 2θ
including typical diffraction peaks at 2θ=7.9°, 8.8°, 23.0°,
23.8° and 24.3°. All peaks were consistent with the typical
pattern of ZSM-5 crystal structure [14, 15] in comparison
with standard ZSM-5 from Database of Zeolite Structures in
Fig. 1b and were basically unchanged which was attributed
to the addition of CA. Figure 1c show XRD patterns of dif-
ferent Y type samples. All the samples remained topology
structures of faujasite zeolites (FAU) [16] in comparison
Conventional H-beta was treated with a solution of suit-
able concentration ammonium carbonate (AC) [12] and cit-
ric acid (CA) at 273 K for 1.5 h under stir-ring, respectively.
With that desiccated at 453 K. The desiccated sample was
calcined at 823 K for 4 h in air to obtain hierarchical H-beta
catalyst.
Na-Y was treated with a solution of suitable concentration
ammonium carbonate (AC) and citric acid (CA) at 273 K for
1.5 h under stir-ring, respectively. With that filtered, washed
and desiccated at 453 K. The desiccated sample was calcined
at 823 K for 4 h in air to obtain M-Y catalyst.
Catalyst characterization
BET surface areas of reduced catalysts were measured by N2
adsorption/desorption at 77 K using a Micromeritics ASAP
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
C
A
210
204
198
192
S
S
=698.53m2/g
BET
A-2
++
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
A-1
+
+
+
0
20
40
60
80
100
120
Pore Volume(cc/g)
B
+ ——Standard H-beta
=465.51m2/g
108
99
BET
+
+
+
+
+
+
+
+
+
+
+
+
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
10
20
30
40
50
2 Theta(degree)
90
B
0
20
40
60
80
100
120
140
160
Pore Volume(nm)
81
A
0.16
0.14
0.12
0.10
0.08
0.06
0.04
0.02
0.00
B-2
370
296
222
148
B-1
0
20
40
60
80
100
Pore Diameter(nm)
*
*
SBET=530.77m2/g
—Standard HZSM-5
*
*
*
*
*
*
*
*
*
*
*
0.0
0.5
1.0
*
*
*
*
*
Relative Pressure(P/P )
0
10
20
30
40
50
2 Theta(degree)
Fig. 2 Nitrogen adsorption/desorption of H-beta (a); Nitrogen
adsorption/desorption of HZSM-5 (b); Nitrogen adsorption/des-
orption of M-Y (c). (Inset: pore size distribution deduced from the
adsorption branch of the isotherm)
C
C-1
Ć
C-2
C-3
with standard Y zeolite from Database of Zeolite Struc-
tures. However, it is obvious that the peak height of M-Y
is increased by means of ion-exchange and roasting, which
could be due to impurities being burned down in the Na-Y.
N2 adsorption/desorption isotherms of H-beta, HZSM-5
and M-Y are displayed in Fig. 2. H-beta (A) exhibited the
characteristic features of a type-IV isotherm [11]. Both
adsorption and desorption branches at a relative pres-
sure>0.55 is caused by the capillary condensation of liquid
N2 inside mesopores, showing a large number of mesopores
present in these H-beta materials. A broad pore size between
3 and 30 nm centered at 4 nm was observed. In Fig. 2b the
N2 physisorption of HZSM-5 exhibits a type-IV isotherm,
in conformity with a wormhole-like mesostructure with
a network of interconnected pores. Pore size distribution
(inset) shows a very narrow distribution [11]. Figure 2c pre-
sents the N2 physisorption isotherms for M-Y tested. The
isotherm belongs to a transition between type I and type IV
[17]. The large slope at a relative pressure between 0.02 and
0.5 indicates that multilayer adsorption dominates for M-Y.
The large slope is consistent with the extraordinarily large
@
@
-Standard Y
@
@
@
@
@
@
@
@
@
@
@
@
10
20
30
40
50
2 Theta(degree)
Fig. 1 a XRD patterns of conventional H-beta (A-1) and hierarchical
H-beta catalyst (A-2), b XRD patterns of conventional HZSM-5 (B-1)
and hierarchical HZSM-5 catalyst (B-2), c XRD patterns of conven-
tional Na-Y catalyst (C-1)、M-Y (C-2)and conventional H-Y (C-3)
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
Table 1 Surface area and pore structure analyses from N2 physisorption
Catalyst
SBETa (m2/g)
Vtotal/cm3*g−1
Micropor. Vol./ Coking speed/colour
ml·g−1
Average pore
diameter/nm
Acidicb amount and
acidic distribution
L
B
HZSM-5
H-beta
H-Y
Na-Y
M-Y
465.51
530.77
701.92
663.91
698.53
0.37
0.58
0.34
0.33
0.34
0.18
Slow/gray
Easy/black
–
–
1.95
4.48
1.76
1.89
1.90
204.626
202.806
146.846
–
202.632
130.138
5.462
0.196
0.205
0.186
0.172
–
Easy/black
193.705
119.759
aSBET is specific surface area of the sample, which was obtained by BET method
bIR spectra of the samples after pyridine desorption at 350 °C
HZSM-5
H-beta
M-Y
NaY
1400
1450
1500
1550
1600
1650
1700
1750
Wavenumber(cm-1)
500
1000
1500
2000
2500
3000
3500
4000
Wave number(cm-1)
Fig. 4 IR spectra of the samples after pyridine desorption
Fig. 3 The FT-IR spectra of all the catalysts
active sites of Si and Al atoms located in the supercage
of zeolites Y, respectively. Bands at 3670 and 3528 cm−1
are attributed to the extra-framework aluminum hydroxyl
[Al(OH)2+]. The spectra of the framework absorption region
is 1600~400 cm−1 [18–20]. Figure 3 points out the differ-
ence about the FT-IR spectra of Na-Y and M-Y.
FAU surface area (698 m2 g−1) observed for this sample.
The hysteresis loop can be categorized into a H3 type [11],
implying that the additional pores belong to slit-shaped ones.
Obvious hysteresis loop of three catalysts which is associ-
ated with capillary condensation taking place in mesopores
and they can imply that the sample was retained the enriched
micropores and mesopores within the particles [2].
Notably, the difference is:
Remarkably, In Table 1 the average pore diam-
eter for the catalysts decreased in the sequence:
H-beta>HZSM-5≈M-Y. The smaller pore is beneficial to
generate relatively small toluene. The surface areas for the
catalysts decreased in the sequence H-Y, M-Y, Na-Y, H-beta,
HZSM-5. The coking speed for the catalysts decreased in
the sequence: M-Y≈H-beta>HZSM-5. This conclusion is
in good agreement with the results of acid sites.
1. The band at 1630 cm−1 has become stronger obviously
under the AC-CA-modification.
2. In the FT-IR spectra of the absorption region
(3000~3670 cm−1) becomes wider, assigned to asym-
metric stretching of the OH group is appeared after Na-Y
modified with AC-CA.
3. Correspondingly, bands of 2508 and 1407 cm−1 have
been observed, indicating that the protonation reaction
of the AC-CA molecules occurs.
The FT-IR of the samples was showed in Fig. 3. In the
FT-IR spectra of the absorption region (3000~3670 cm−1):
the bands at 3645 cm−1 are assigned to the terminal silanol
(Si–OH) active sites, and the bridging hydroxyl (OH)
The acidity of these catalysts was comparatively inves-
tigated by Py-IR spectroscopy in Fig. 4 and Table 1.
1 3

Journal of Inclusion Phenomena and Macrocyclic Chemistry
M-Y
H-beta
HZSM-5
toluene is found to be the predominant products over M-Y
catalyst. Other by-products such as ethylbenzene, trimeth-
ylbenzene, etc. are also detected in small amounts (sel.
% = 3.1 ~ 5.5%). The HZSM-5 catalyst showed conver-
sion (48.6%), but the selectivity to toluene was relatively
low (54.4%). The analysis showed the main products
were toluene and xylene, which may be due to the more
of Brönsted acid sites. The conversion of benzene with
H-Y catalyst was approximately 0.1 times than that of
M-Y catalyst. Moreover, Na-Y catalyst has no activity.
The reason may be that only Lewis acid sites about H-Y
catalyst and scarcely any acid sites for Na-Y catalyst in
Fig. 4. Fortunately, the M-Y catalyst exhibited the best
catalytic activity among all the catalysts. The conversion
of benzene was 43.9% and the selectivity to toluene was
87.7%. For the above catalysts, when toluene as the target
product, the order of the catalytic activity is M-Y > H-bet
a > HZSM-5 > > H-Y > Na-Y. When xylene was viewed as
the principal product, the HZSM-5 catalyst is an optimal
choice, and yet the M-Y catalyst must be an optimal choice
when toluene was viewed as the principal product. This
will be attributed to synergistic effect of Lewis/Brönsted
and pore structure.
100
90
80
70
60
50
70
60
50
40
30
20
10
40
30
20
10
Conversion
Selectivity of Toluene
Selectivity of p-x
40
1.0
1.1
1.2
1.3
1.4
1.5
1.6
1.7
L/B ratio
Fig. 5 Effects of L/B ratios on the catalytic performance in benzene
alkylation
Table 2 Products content of benzene alkylation with methanol over
the different catalysts
Catalysts Benzene
Conver-
Product selectivity/%
Toluene Xylene Tolu-
Others
sion/%
ene+Xylene
HZSM-5 48.6
54.4
74.6
79.3
–
41.2
19.9
16.3
–
95.5
4.5
5.5
4.4
–
To sum up, the reaction is initiated on Brönsted acid
sites where protons on zeolites attacks benzene to form
protonated benzene and Lewis acid sites activate metha-
nol to generate CH3+OH−, then protonated benzene and
H-beta
H-Y
42.5
4.3
0
94.5
95.6
–
Na-Y
M-Y
+
CH3 OH− generate toluene. Deprotonation regenerate the
43.9
87.7
9.2
96.9
3.1
Brönsted sites to its original state or regenerate the Lewis
acid sites Toluene can be alkylated further forming xylene
or tri-benzenes as suggested by the reaction network in
Fig. 6. The presence of benzyl group incurs toluene alkyla-
tion to ethylbenzene, which contribution from Lewis acid
sites will occur to afford benzyl group and others [23]. The
need energy of C+ generation is higher from activation of
hydrocarbon with Lewis acid sites. Therefore, adopt Brön-
sted acid sites for activation benzene alkylation reaction.
Due to Na-Y catalyst and H-Y catalyst have not originally
Brönsted acid sites in Fig. 4. Thus it is difficult to acti-
vate the reaction. Meanwhile, because HZSM-5 catalyst
and H-beta catalyst have too much Brönsted acid sites, in
addition, toluene is easier activated than benzene, so the
second reaction will be more likely to occur which reduces
the selectivity of toluene. The selectivity of toluene is
higher over H-beta catalyst because xylene and benzene
will regenerate toluene. At the same time can be seen from
the catalyst micro-structure. M-Y catalyst is conducive to
the formation of toluene. Therefore, the catalyst of alkyla-
tion reaction should have both Lewis acid and Brönsted
acid. Best result from this study is the synergistic effect of
Lewis acid and Brönsted acid in the process of reaction,
which makes the highest selectivity of toluene.
Reaction Condition: Catalyst=0.5 g; T=400 °C; Reaction time=3 h;
Pressure=the atmospheric, Feed (Benzene/Methanol) ratio=1:1
The amount of acid sites increased in the sequence:
Na-Y<H-Y<<M-Y<H-beta<HZSM-5. It is also known
by calculation that the sequence of L/B ratio is M-Y
(1.62) > H-beta (1.56) > HZSM-5 (1) in Fig. 5. Based on
above indicated that: the quantity of Brönsted acid sites
was good for enhancing the conversion of benzene and the
activity of catalysts [21, 22], while the higher Brönsted acid
of catalysts could prompt undesirable secondary reactions
in benzene alkylation reaction in Table 1. Moreover, only
Lewis acid or only Brönsted acid had nearly no effect on
alkylation reaction of benzene. Therefore, it was reasonable
to conclude that the appropriate ratio of Lewis/Brönsted
acidity exhibited may well be a key reason in methanol-to-
benzene reaction to toluene.
Catalytic performances
The catalytic test of HZSM-5, H-beta and M-Y catalysts
are presented in Table 2. Toluene and xylene are found
to be the predominant products after alkylation, but sig-
nificant difference was shown. The Best result especially
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Journal of Inclusion Phenomena and Macrocyclic Chemistry
Fig. 6 Plausible reaction mechanisms on HZSM-5, H-beta and M-Y catalysts
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modified hierarchical ZSM-5 catalysts in benzene alkylation with
methanol. Catal. Lett. 145, 715–722 (2015)
Conclusion
The performance of H-ZSM-5, H-beta and M-Y were inves-
tigated in benzene alkylation with methanol. M-Y catalyst
had commendable activity and the highest selectivity of
toluene. The reason is that large surface area, pore structure
and synergistic effect of Lewis/Brönsted acid of the catalyses
played a crucial role in benzene alkylation with methanol.
These technologies would help to improve the commercial
viability of the process of benzene alkylation with methanol
into toluene.
3. Alabi, W., Atanda, L.M., Jermy, R., Al-Khattaf, S.: Kinetics of
toluene alkylation with methanol catalyzed by pure and hybridized
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4. Hu, H.L., Lyu, J.H., Wang, Q.T., Zhang, Q.F., Cen, J., Li, X.N.:
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the science and technology support project of Gansu province
(1604GKCD026) (No. 2016GS09293).
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