International Journal of Advanced Engineering Research and Science (IJAERS) [Vol-7, Issue-6, Jun- 2020]

https://dx.doi.org/10.22161/ijaers.76.24 ISSN: 2349-6495(P) | 2456-1908(O)

Cheap zeolite catalyst (Na3PO4/NaX) for

toluene/methanol side chain alkylation
Faraz Ahmad1,#, Yueli Wen2,#, Bin Wang1*, Chunyao Hao1, Walzli Yousaf2,
Yuhua Liu1, Wei Huang1,3*
1Key Laboratory of Coal Science and Technology, Taiyuan University of Technology, Ministry of Education and Shanxi Province,
Taiyuan, 030024, Shanxi, China.
2College of Environmental Science and Engineering, Taiyuan University of Technology, Taiyuan, 030024, Shanxi, China.
3Coal Conversion Technology & Engineering Co., Ltd., Taiyuan University of Technology, Taiyuan, 030024, Shanxi, China.

#Faraz Ahmad and Yueli Wen are co-first authors who have equally contributed to this work.
*Corresponding author Email address: [email protected] (Bin Wang); [email protected] (Wei Huang)

Abstract— A new zeolite catalyst (Na3PO4/NaX), which is low in cost, environment-friendly and also gives
higher conversion of methanol, was prepared by the impregnation method and catalytic performance was
tested for side-chain alkylation of toluene with methanol. From the characterization of the catalysts by
Temperature-programmed desorption (TPD-CO2), X-ray diffraction (XRD), scanning electron microscopy
(SEM) and Brunauer-Emmett-Teller (BET) method we found that when the concentration of Na3PO4 was
0.1 mol/L, the yield of styrene and ethylbenzene, and conversion of methanol reached 39.4% and 100%. It
was determined that as the loading of Na3PO4 onto the NaX surface enhanced, the amount and the
strength of middle base sites significantly increased, which is favorable for the toluene/methanol side chain
alkylation.
Keywords— zeolite catalyst, side-chain alkylation, middle base sites, styrene.

I. INTRODUCTION dehydrogenation. Formaldehyde formed by the

Styrene is a significant chemical material that might be dehydrogenation of methanol acts as an actual alkylating
used to produce a wide range of polymers that are utilized agent for side-chain alkylation [12] and it can decompose
in many applications, including toys, food packaging, into CO and H2 on-basic sites [13,14]. A series of side
medical equipment, and paper coverings [1]. Sidorenko et reactions occur during toluene/methanol side chain
al. first reported styrene production by toluene/methanol alkylation process. Ethylbenzene was supposed to produce
side-chain alkylation [2]. Since then, this reaction has through the hydrogenation of styrene with hydrogen, which
involved wide-ranging attention because this method of in turn produced by methanol dehydrogenation to
producing styrene offered economic benefits [3,4] and was formaldehyde and auxiliary formaldehyde decomposition
supposed as a reliable one step substitute for the existing [15]. It was suggested from previous research that the main
two-step method over alkylation of benzene with ethylene reaction pathway for ethylbenzene formation is the
and followed by the catalytic dehydrogenation of hydrogenation of styrene with methanol [16]. Besides
ethylbenzene [5,6]. xylene formed through toluene disproportionation during
Many scientists have explored the mechanism of the ring alkylation with methanol that existed at acid sites
toluene/methanol side-chain alkylation reaction to invent must not be ignored either [17].
an efficient catalyst for the toluene/methanol side chain There has been extensive study of catalysts for
alkylation [7]. It is usually recognized that the alkylation of toluene/methanol side chain alkylation [18]. A noble
toluene with methanol over basic zeolites can catalyze catalyst for toluene/methanol side-chain alkylation was
side-chain alkylation while acidic zeolites can catalyze to reported to have the following characteristics (1)
the ring of toluene [8]. Toluene/methanol side chain appropriate strength of base to dehydrogenate methanol to
alkylation is a well-known acid-base synergistic catalysis formaldehyde, (2) polarization and stabilization of methyl
process [9-11]. Usually, acidic sites can stabilize and group of adsorbed toluene, and (3) balanced reactant
adsorb toluene; however the function of base sites is to sorption stoichiometry [3,19]. From previous studies it was
trigger the carbon atom of the side chain of toluene found that the catalyst prepared by CsX modified by
followed by the methanol to formaldehyde K3PO4 could enhance the amount and strength of the

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International Journal of Advanced Engineering Research and Science (IJAERS) [Vol-7, Issue-6, Jun- 2020]
https://dx.doi.org/10.22161/ijaers.76.24 ISSN: 2349-6495(P) | 2456-1908(O)

middle base on the catalyst and reduce the number of acid Temperature-programmed desorption (TPD) of
sites leading to the improved catalytic effect in adsorbed CO2 was done on a TP-5080 to analyze the basic
toluene/methanol side chain alkylation [20]. Although this sites. The sample (0.1 g) was pretreated at 450°C for 103
system (CsX modified by K3PO4) was energy-efficient min in a He stream before taking measurements and cooled
however, the major drawback for using K3PO4 was the down to the required temperatures. The samples were
higher cost of the raw materials. exposed to pure CO2 at 100°C for 30 min. The samples
In order to solve the problem of raw materials cost we were heated to 810°C with a temperature ramp at 10 °C
supposed to use Na3PO4 modified NaX molecular sieve in min-1 after purging with helium.
our current study, which is cheaper than K3PO4 system and A Quanta-chrome Autosorb QDS-30 physical
investigated the effect of Na3PO4/NaX in the adsorption analyzer system at −196°C was used to attain
toluene/methanol side chain alkylation for the production N2 adsorption-desorption isotherms. The samples were
of styrene. The results of our study showed that as the degassed under vacuum at 200°C for 4 hours prior to
concentration of Na3PO4 increased, the amount of middle taking a measurement. Pore volumes and Specific surface
base sites also increased leading to the higher yield of areas were determined by BJH method and Brunauer-
ethylbenzene and styrene signifying that the strength and Emmett-Teller (BET) method separately.
amount of middle base sites is a crucial factor for the Scanning electron microscopy SEM images of catalysts
toluene/methanol side chain alkylation. were obtained by a JESOL JSM-6010PLUS/LV scanning
microscope. The samples were loaded onto the sample
II. EXPERIMENTAL SECTION holder, seized with conductive aluminum tape and vacuum
2.1 Materials: coated gold film with Cressington sputter ion coater prior
Zeolite NaX (Si/Al = 1.25) was attained from Nankai to taking SEM photographs. Magnification was 5000, with
University's Catalyst Plant. Methanol, and Toluene, with a an acceleration voltage of 20kV.
purity of 99%, were obtained from Tianjin Kemio 2.4 Catalytic Tests:
Chemical Reagent Co., Ltd. For the toluene/methanol side chain alkylation,
2.2 Catalyst Preparation: Na3PO4/NaX powder was crushed, pressed, and sieved (40-
A series of Na3PO4 catalysts were produced by loading 60 mesh). A fix bed reactor was used to carry out the
different concentrations of Na3PO4 on NaX zeolite reaction, and 1.2 g of the catalyst was positioned in the
(SiO2/Al2O3 = 2.4) at 80°C. Procedures followed are center of a stainless-steel tube having 7 mm inner diameter,
described below: and the catalyst was supported by quartz sands at the outlet
of the reaction tube, and separated by quartz cotton at both
Different concentrations of Na3PO4 solution (solid/liqui ends to prevent catalyst from blowing into GC columns.
d ratio, 10g/100ml) were loaded three times on 10g of Nitrogen was the carrier gas and the flow rate was 10.0
NaX at 80°C for 2 h. The Buchner funnel was used to filter mL/min, the molar ratio of toluene to methanol was 5:1,
the slurry. The cake obtained as a result of filtration was and the mass space velocity was 1.0 h-1. The catalyst was
absorbed again in an aqueous solution of Na3PO4 (100 ml, activated at 450°C for 2 h under an atmospheric nitrogen
0.5M) and agitated for 2 h at the same temperature. atmosphere and then lowered to 425°C for evaluation. The
Filtration and absorption processes were repeated further reaction products were quantitively examined online by
two times. The resulting residue was filtered. The mixture Haixin GC950 gas chromatograph equipped with an HP-
was dehydrated at 80°C for 12 h followed by the FFAP column (0.53 mm × 50 m), and the products were
calcination at 3 K/min. After 3 hours of calcination at detected by a hydrogen flame ionization detector (FID).
500°C, the resulting powder was crushed, pelletized and Since the access of toluene in the reaction system was
sieved to obtain the zeolite catalyst with a size between 40 used, the conversion rate, product selectivity, and yield
mesh and 60 mesh. The powder obtained was ready for were calculated based on methanol given in the equation
reaction and referred to as Cat-n, where n is the below.
concentration of Na3PO4 in the catalyst.
2.3 Characterization of Catalysts:
The X-ray diffraction (XRD) of catalysts were recorded
on a Rigaku D/max 2500 X-ray diffractometer using Ni-
filtered Cu Kα radiation (λ = 0.15406 nm), activated at 100
mA and 40 kV. A 10°/min scanning rate was used for
Bragg’s angles 2θ = 5-80°.

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International Journal of Advanced Engineering Research and Science (IJAERS) [Vol-7, Issue-6, Jun- 2020]
https://dx.doi.org/10.22161/ijaers.76.24 ISSN: 2349-6495(P) | 2456-1908(O)

3.4 BET
The pore volume, pore diameter, and total surface area
of all the catalysts are given in Table 1. It can be perceived
III. RESULTS AND DISCUSSION
3.1 TPD-CO2 from these results that pore volume and catalyst surface
To examine the base properties of the catalysts, we area was considerably reduced with an increase in the
conducted Temperature-programmed desorption (TPD) concentration of Na3PO4 as displayed in Fig 4. It might be
experiments of CO2, and TPD-CO2 spectra of all catalysts because Na3PO4 occupied some parts of the zeolite pores.
such as NaX, cat-0.01, cat-0.05, cat-0.075, cat-0.1 were Combined these results with the catalytic performance,
shown in Fig.1. Three kinds of desorption peaks were seen catalyst with concentration 0.1 mol/L showed best ability
for all catalysts. The first region was at a low-temperature to catalyze the reaction indicating that small pore volume
range between 50°C-250°C correspond to the weak base having microporous structure might be suitable for the
site; the second region ranges between 250°C-500°C toluene/methanol side chain alkylation
indicates a middle base site while the third region is the
strong base site at around 500°C-800°C. As the loading of IV. FIGURES AND TABLES
Na3PO4 enhanced, the CO2 desorption peak area of the
middle base site increased and shifted towards higher Cat-0.1
temperature while the desorption peak area decreased at
low temperatures indicating that during the impregnation
process, the amount of base sites of support enhanced. It
Intensity(a.u.)
Cat-0.075
can be elucidated from these results that a suitable amount
of Na3PO4 may considerably increase the amount and the
strength of middle base sites on the surface of the catalysts.
3.2 XRD Diffraction Cat-0.05
Fig. 2 depicts the XRD patterns of different catalysts
(NaX, cat-0.01, cat-0.05, cat-0.075, cat-0.1). It could be
perceived from our results that all the catalysts showed Cat-0.01
diffraction peaks of the faujasite framework signifying a
typical arrangement of X-zeolite. However, in comparison 100 200 300 400 500 600 700 800
Temperature(0C)
with NaX zeolite, the relative diffraction peak intensity of
cat-0.05, and cat-0.1 slightly decreased at 26.7°. This
Fig 1. TPD-CO2 profile of catalysts cat-0.01, cat-0.05, cat-
might happen because the zeolite structure was slightly
0.075 and cat-0.1
damaged in the process of impregnation. Except for zeolite
X, there were no other noticeable peaks seen in all XRD 26.70
patterns, suggesting that the assembly of NaX was not
destroyed during the catalyst preparation process, and
Na3PO4 has well dispersed on the surface of NaX zeolite. NaX
3.3 SEM
Fig 3 shows SEM images cat-0.01, cat-0.05, cat-0.075, Cat-0.01
Intensity/(a.u)

cat-0.1. All the catalysts had same size distribution and

irregular octahedron structures. The catalysts were mainly Cat-0.05
made up of crystallites having size about 2 to 3 µm and
small particles. SEM images of cat-0.01 (a) and cat-0.075 Cat-0.075
(c) are similar. Fig. 3.4(d) represents that there were a huge
number of white particles which showed the loading of Cat-0.1
Na3PO4 on NaX zeolite surface and also represented a
uniform mixing which might be the reason of stability and 20 40 60 80
high catalyst performances. Based on the results we 2/degree
elucidated that more the dispersion of the particles on the
surface, higher the performance of the toluene/methanol Fig 2. XRD patterns of catalysts NaX, cat-0.01, cat-0.05, cat-
side chain alkylation. 0.075, and cat-0.1

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International Journal of Advanced Engineering Research and Science (IJAERS) [Vol-7, Issue-6, Jun- 2020]
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Table.2: Performance of Catalyst

Reaction Selectivity
Temp(°C) MET of products Yield of products (%)
Catalyst
conv% (%)
SEB SSTY YEB YSTY Y(EB+STY)
0.01M 425 96.9 18 2.2 17.9 2.1 20
0.05M 425 100 23 3.8 23.5 3.8 27.3
0.075M 425 100 15 2.6 15.3 2.6 17.9
0.1M 425 100 31 7.5 31.9 7.5 39.4
Where: M= mol/L, cat-0.01=0.01M, cat-0.05=0.05M, cat-
0.075=0.075M, cat-0.1=0.1M

V. CATALYTIC REACTION
The reaction performance for the toluene/methanol side
Fig 3. SEM images of catalysts (a) cat-0.01, (b) cat-0.05,
chain alkylation over a series of catalyst Cat-n (n
(c) cat-0.075, and (d) cat-0.1
represents loading of Na3PO4) is shown in Table 2.
Ethylbenzene and styrene were regarded as the main
products for the toluene/methanol side chain alkylation
while there exist some byproducts such as methane and
Cat-0.01
xylene. With the loading of Na3PO4 by impregnation
dv(d) cc/nm/g

Cat-0.05

Cat-0.075
method, methanol conversion reached up to 99%, and the
Cat-0.1
selectivity and yield of styrene and ethylbenzene were also
Intensity (a.u.)

0 5 10 15 20 25 30 35
Pore Diameter (mm)
expressively increased. The activity of the catalyst and the
yield of styrene and ethylbenzene were enhanced
0.01
considerably when the concentration of Na3PO4 was 0.1
0.05 mol/L, i.e., yield (Ethylbenzene + Styrene) 39.4%. At this
concentration of Na3PO4, the conversion of methanol was
0.075 100%.
0.1 The catalytic activity data in Table 2 and TPD-CO2
(Fig. 1) showed that selectivity (ethylbenzene + styrene)
0.0 0.2 0.4 0.6 0.8 1.0
and the activity of the catalyst has improved with an
Temperature 0C
appropriate amount and strength of middle base sites,
which suggested the middle base sites were advantageous
Fig 4. BET images of catalysts cat-0.01, cat-0.05, cat- for the toluene/methanol side chain alkylation reaction.
0.075, and cat-0.1
VI. CONCLUSION
Table.1: Textural properties of different catalysts In this work, a cheap and new zeolite catalyst
Pore Pore Total containing different concentrations of Na3PO4 supported
Catalysts Volume Diameter surface area on NaX has successfully synthesized and characterized by
cm3/g nm m2/g TPD-CO2, XRD, SEM, and BET. The TPD-CO2 results
0.01M 0.032 3.408 595.85 revealed that as the loading of Na3PO4 on NaX zeolite
0.05M 0.029 3.819 553.79 emhanced, the amount of middle base sites also increased
0.075M 0.033 3.825 610.66 which led to the higher yield of ethylbenzene and styrene
0.1M 0.025 3.820 541.14 i.e, the yield of ethylbenzene and styrene, and conversion
of methanol reached 39.4% and 100% signifying that the
Where: M= mol/L, cat-0.01=0.01M, cat-0.05=0.05M, cat- presence of amount of middle base sites on the surface of
0.075=0.075M, cat-0.1=0.1M the catalyst was crucial factor for the toluene/methanol side
chain alkylation.

ACKNOWLEDGEMENTS
The authors are thankful to the financial support from
the National Key Technology Research & Development

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International Journal of Advanced Engineering Research and Science (IJAERS) [Vol-7, Issue-6, Jun- 2020]
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