Fuel Processing Technology 90 (2009) 1220–1225

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Fuel Processing Technology

j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / f u p r o c

Synthesis of ethylbenzene by alkylation of benzene with diethyl oxalate over HZSM-5

Yongxin Li ⁎, Bing Xue, Yantao Yang
College of Chemistry and Chemical Engineering, Jiangsu Polytechnic University, Changzhou, Jiangsu, 213164, China

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

Article history: Catalytic synthesis of ethylbenzene by alkylation of benzene with diethyl oxalate was carried out over HZSM-5
Received 2 September 2008 with Si/Al ratios from 50 to 250. The catalysts were characterized by X-ray diffraction (XRD), scanning electron
Received in revised form 18 March 2009 microscopy (SEM), ammonia temperature-programmed desorption (NH3-TPD) and pyridine IR techniques. As
Accepted 2 June 2009
revealed by the results of NH3-TPD and pyridine IR spectra, a significant decrease in acidic strength and the
number of acidic sites is observed with increasing Si/Al ratio from 50 to 250. The benzene conversion and
Keywords:
Ethylbenzene
ethylbenzene selectivity increases obviously with increasing Si/Al ratio from 50 to 200. With a further increase
Alkylation in Si/Al ratios, a slight decrease in the conversion of benzene and selectivity for ethylbenzene is detected,
Diethyl oxalate indicating that a proper acidic strength was required in this reaction. In addition, the effects of temperature and
HZSM-5 feed ratio on the catalytic activity and product distributions are also investigated in this study.
© 2009 Elsevier B.V. All rights reserved.

1. Introduction
Alkylation of benzene is an important reaction in the petrochem-
ical industry. As the most important alkylbenzene, ethylbenzene (EB)
is predominantly synthesized by alkylation of benzene with ethylene
over an acid catalyst [1,2]. Conventionally, to maintain a good catalyst
lifetime, a high molar ratio of benzene to ethylene is required in the
alkylation of benzene with ethylene. However, a high molar ratio of
benzene to ethylene results in a low conversion of benzene, which
may cause a great quantity of unconverted benzene to remain cir-
culating in the industrial process resulting in more energy consump-
tion [3]. In recent years, some investigations were conducted to
synthesize ethylbenzene by using other alkylating agents, such as
ethanol, as a substitute for ethylene [4,5]. A significant deactivation in
activity with time was also observed in the on-stream alkylation of
benzene with ethanol [5]. Diethyl oxalate (DEO) is a versatile com-
pound that represents an attractive alternative to both ethyl halides
and phosgene for ethylation and carbonylation processes, respectively
[6,7]. The replacement of ethylene with DEO as the alkylating agent
would lead to significant commercial and environmental benefits in
the EB production due to the higher availability of DEO and the energy
demanding processes of ethylene production [8]. To our knowledge,
there are no reports using DEO as the ethylating agent to synthesize
EB.
ZSM-5, a typical MFI-type zeolite, is a well-known crystalline mi-
croporous aluminosilicate that possesses a three-dimensional frame-
work and an acidity that is different from those of silicon dioxide
⁎ Corresponding author. Tel./fax: +86 519 86330135.
E-mail address: liyx@em.jpu.edu.cn (Y. Li).
and alumina [9]. ZSM-5 zeolites have attracted much attention as
alkylation catalysts due to their high acidity, their potential for
regeneration, their easy separation from reaction products and the
elimination of problems associated with the disposal of spent catalysts
such as AlCl3 [10]. The ZSM-5 zeolites are also of interest as they are
free from corrosive substances. Because of its special shape selectivity
and surface acidity, in recent years, ZSM-5 has been applied to com-
mercial processes for ethylbenzene and cumene production by
alkylation of benzene with ethylene and propylene, respectively [3].
The activity and selectivity of zeolites for acid-catalyzed alkylation
reactions, such as the alkylation of benzene with ethylene, is directly
related to the catalyst acidity. It is also well known that the acidity of
zeolites is invariant of the Si/Al ratio [11]. With a view to under-
standing the number of acidic sites and acidic strength distribution
of the catalyst, we have investigated HZSM-5 zeolites with different
Si/Al ratios and characterized the acid properties using ammonia
temperature-programmed desorption (NH3-TPD) and pyridine IR
techniques. The catalytic performance of HZSM-5 zeolites with
different Si/Al ratios in the synthesis of EB by alkylation of benzene
with DEO was also investigated in the present study.
2. Experimental
2.1. Catalyst preparation
ZSM-5 zeolites with Si/Al ratios of 50, 100, 150, 200 and 250 were
synthesized by hydrothermal crystallization according to the reported
procedure [12]. The NH4 form of the as-synthesized zeolites was
obtained by ion-exchange with a 0.5 mol/l NH4NO3 solution
performed in triplicate. After drying at 393 K for 12 h and calcining

0378-3820/$ – see front matter © 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.fuproc.2009.06.001
 Y. Li et al. / Fuel Processing Technology 90 (2009) 1220–1225
at 823 K for 4 h, the acidic form of the ZSM-5 zeolite catalyst was
obtained. The obtained samples are designated HZSM-5–50, HZSM-5–
100, HZSM-5–150, HZSM-5–200 and HZSM-5–250.
2.2. Catalyst characterization
X-ray diffraction (XRD) measurements were conducted using a
Rigaku D/max 2500PC diffractometer with CuKα (λ = 1.54 Å) radia-
tion. Diffractograms were recorded in the 2θ range of 5–50° in steps of
0.02° with a count time of 15 s. The crystal size and morphology of the
microscale HZSM-5 zeolites were determined by scanning electron
microscopy (SEM, JSM-6360LA, JEOL Ltd.).
Sample acidity was measured by NH3-TPD using a Quantachrome
CHEMBET-3000 instrument. A 200 mg sample was pre-treated at
823 K for 1 h in dry helium (50 ml/min) and cooled to 393 K. It was
then exposed to 10 vol.% NH3/He for 0.5 h. After purging the catalyst
with He for 0.5 h, a TPD plot was obtained at a heating rate of 10 K/min
from 393 K to 823 K.
IR spectroscopy with pyridine adsorption was carried out on a
Bruker FT-IR spectrometry (TENSOR 27) equipped with a high tem-
perature vacuum chamber. The scanning range was from 1700 to
1400 cm− 1 and the resolution was 4 cm− 1. Sample powder was
pressed into a self-supporting wafer. Before each experiment, the
catalysts were evacuated (1 Pa) at 653 K for 3 h. The samples were
then cooled to 303 K for 2 h. The material was exposed to pyridine at
30 Torr for 5 min, and finally evacuated for an additional 1 h at 303 K.
After adsorption, the samples were heated to 473 K and 673 K at a rate
of 10 K/min and the IR spectra were recorded.
2.3. Ethylation of benzene with DEO
Vapor phase alkylation of benzene with DEO was carried out in a
fixed bed continuous down-flow reactor. About 2 g of the catalyst
(as pellets of 20–40 mesh) was loaded into the middle of the reactor
(L = 45 cm, D = 8 mm). A reaction mixture consisting of benzene and
DEO was introduced at the top of the reactor by means of an infusion
pump. The products were collected in an ice-cooled condenser
attached to the end of the reactor and were analyzed using a gas
chromatograph (SP-6890) fitted with an OV-101 capillary column and
a flame ionization detector (FID). The products were identified using a
GC-MS (GC-MS-QP2010, Shimadzu, OV-101 capillary column,
30 m × 0.25 mm × 0.25 µm) with helium as a carrier gas at a flow
rate of 1 ml/min. The conversion was compared after the steady state
Fig. 1. X-ray diffraction pattern of HZSM-5 with different Si/Al ratios. a HZSM-5–50;
b HZSM-5–100; c HZSM-5–150; d HZSM-5–200; e HZSM-5–250.
1221
Fig. 2. SEM image of HZSM-5–200.
was reached during the experiment. The conversion percentage was
calculated based on the benzene.
3. Results and discussion
3.1. Characterizations
Fig. 1 shows the XRD patterns of the HZSM-5 zeolite with different
Si/Al ratios. The number and position of the peaks do not change
with increasing Si/Al ratio, corresponding to the specific peaks of the
ZSM-5 zeolite [13]. The high intensity of peaks in the XRD patterns
indicates that the zeolite samples are highly crystalline. It can be
found that the intensities of the peaks increase slightly with Si/Al
ratios from 50 to 250, indicating that the formation of the ZSM-5
zeolite becomes easier as the Si/Al ratios increase in the gel [13,14].
Fig. 2 shows the SEM images of the HZSM-5–200 zeolite. It can be
found that the crystal size of HZSM-5 was approximately 1–2 µm,
which was consistent with the character of the microscale crystal [9].
The NH3-TPD patterns of the investigated samples are shown in
Fig. 3. As shown in Fig. 3, the two peaks of NH3 desorption observed
around 525 and 725 K can be ascribed to desorption of adsorbed
ammonia from the weaker acidic sites and stronger acidic sites,
respectively. The number of weak acidic sites is greater than the
number of strong acidic sites over all the samples. It can be found that
the total number of acidic sites decreases remarkably with increasing
Si/Al ratio from 50 to 250. A significant shift to lower temperatures for
strong acidic sites is detected with increasing Si/Al ratio from 50 to
Fig. 3. NH3-TPD pattern of HZSM-5 with different Si/Al ratios. a HZSM-5–50; b HZSM-5–
100; c HZSM-5–150; d HZSM-5–200; e HZSM-5–250.
1222 Y. Li et al. / Fuel Processing Technology 90 (2009) 1220–1225

Fig. 4. Py-IR spectra of HZSM-5 with different Si/Al ratios at 473 K. a HZSM-5–50; Fig. 5. Conversion of benzene over HZSM-5 with different Si/Al ratios. Conditions:
b HZSM-5–100; c HZSM-5–150; d HZSM-5–200; e HZSM-5–250. temperature 653 K, feed ratio = 4:1(benzene:DEO), WHSV 1.5 h− 1.

250, corresponding to a decline in the strengths of the strong acidic the activation of carbocations [16]. As was reported [17], dialkyl
sites. oxalate was found to be easily decarbonylated and then dialkyl car-
The Py-IR spectra of the HZSM-5 zeolites with different Si/Al ratios bonate was obtained as the main product. However, dialkyl carbonate
are presented in Fig. 4. The IR adsorption peak at 1545 cm− 1 is can be further decomposed to produce dialkyl ether over acid cat-
assigned to the Brønsted acid sites, while the peak at 1455 cm− 1 is alysts, and the decomposition of dialkyl carbonate increased with
attributed to the Lewis acid sites according to the reported method increases in the acidity of the catalyst [18,19]. Therefore, there is a
[15]. As shown in Fig. 4, the number of Brønsted acid sites is much competition between the decomposition of DEO and alkylation of
greater than the number of Lewis acid sites over all the investigated benzene with DEO in this process. The low conversion of benzene over
catalysts. The number of Lewis acid sites decreases markedly with HZSM-5–50 in the alkylation of benzene with DEO may be ascribed
increasing Si/Al ratio from 50 to 250. In addition, the obvious Brønsted to the decomposition of DEO over acid catalysts, which leads to
acid sites still survives even on the HZSM-5–250 catalyst. The results a decrease in the concentration of ethyl cations. With decrease in
calculated according to the Py-IR at different temperatures are listed strength and number of acidic sites, the decomposition of DEO is
in Table 1. The number of Brønsted acid sites and Lewis acid sites suppressed, resulting in the increase in conversion of benzene with
decreases as the Si/Al ratio increased significantly. An increase in the increasing Si/Al ratios from 50 to 200. With a further increase in Si/Al
B/L ratio is apparent with an increase in the Si/Al ratio from 50 to 100, ratios, a slight decrease in benzene conversion is detected over HZSM-
while a decrease is noted as the Si/Al ratios increased. 5–250. It has been considered that the alkylation of benzene was a
typical acid catalyzed process. As the alkylation of benzene with DEO
3.2. Catalysts performances requires prior formation of ethyl cation on the catalyst, the presence of
Brønsted acid sites on the catalyst is essential [9]. As shown in the
3.2.1. Effect of Si/Al ratios results of the NH3-TPD and Py-IR studies, the number and strength of
Fig. 5 shows the on-stream benzene conversion over HZSM-5 the acidic sites of HZSM-5–250 decreases sharply compared with
catalysts with Si/Al ratios ranging from 50 to 250 as a function of time. HZSM-5–200. It can be concluded that the HZSM-5–250 acidity was
As shown in Fig. 5, the conversion of benzene increases significantly too weak to catalyze the alkylation of benzene with DEO. Therefore,
with Si/Al ratios from 50 to 200, and achieves a maximum over the HZSM-5–200, with a proper strength of acidity, is the appropriate
HZSM-5–200 catalyst. According to the acid properties and strength catalyst in this reaction. Conversion of DEO detected by GC is over 99%
characterization (shown in Figs. 2 and 3), HZSM-5–50 exhibits the in all cases, which is similar to the conversion of ethylene in the
strongest acidity among the investigated catalysts, but it demonstrates alkylation of benzene with ethylene.
the lowest benzene conversion, indicating that the strong acidity was Table 2 shows the product distributions of HZSM-5 catalysts
not favored for the alkylation of benzene with DEO. Interestingly, the with Si/Al ratios ranging from 50 to 250 in the alkylation of ben-
effect of acidity on the conversion of benzene in this reaction is zene with DEO. The products as identified by GC-MS are found to
different from that of benzene with ethylene or ethanol. In the be EB, toluene, para-diethylbenzene (p-DEB), ortho-diethylbenzene
conventional alkylation of benzene with ethylene or ethanol, the (o-DEB), meta-diethylbenzene (m-DEB), triethyl benzene (TEB) and
conversion of benzene increased markedly with improvement in the other substituted benzenes such as, polyalkyl benzene. The alkylation
acidity of the catalysts because the strong acid sites were required for
Table 2
Table 1 Effect of Si/Al ratios of HZSM-5 on products selectivity.a
Brønsted acid sites and Lewis acid sites of catalysts obtained by Py-IR.a
Catalysts WHSV Con.% Sel.%
Samples Brønsted acid sites Lewis acid sites B/L h− 1 EB Toluene m-DEB o-DEB p-DEB TEB Other
473 K 673 K 473 K 673 K 473 K 673 K HZSM-5–50 1.5 33.2 74.5 10.8 2.0 1.0 4.8 1.5 5.4
HZSM-5–50 1.34 0.55 0.38 0.26 3.53 2.12 HZSM-5–100 1.5 34.1 77.6 10.7 1.6 0.9 6.0 1.2 2.0
HZSM-5–100 1.20 0.42 0.29 0.21 4.13 2.00 HZSM-5–150 1.5 37.3 79.9 7.9 1.5 1.0 6.7 1.0 2.0
HZSM-5–150 0.87 0.29 0.22 0.13 3.95 2.23 HZSM-5–200 1.5 38.8 84.2 4.5 0.9 0.9 7.5 0.6 1.4
HZSM-5–200 0.36 0.14 0.15 0.08 2.40 1.75 HZSM-5–250 1.5 37.8 82.5 1.8 1.1 0.9 12.8 0.4 0.5
HZSM-5–250 0.15 0.05 0.11 0.06 1.36 0.83 HZSM-5–100 1.0 34.4 77.1 10.8 1.6 0.8 6.3 1.2 2.2
a HZSM-5–100 0.5 34.9 76.7 11.0 1.8 1.0 6.3 1.1 2.1
The number of acid sites is a relative value of Brønsted acid sites and Lewis acid
sites, as estimated by the corresponding calibrated peak area. a
Temperature 653 K, feed ratio= 4:1(benzene:DEO), WHSV 1.5 h–1, time on stream 10 h.
 Y. Li et al. / Fuel Processing Technology 90 (2009) 1220–1225 1223

Scheme 1. A possible mechanism for the reaction of benzene with DEO over HZSM-5.

of benzene is an electrophilic substitution reaction on the aromatic
ring. According to the product distributions, the reaction of benzene
with DEO over HZSM-5 catalysts is given in Scheme 1. It can be found
that benzene alkylation (including mono-alkylation and multi-
alkylation), EB disproportionation and cracking, DEB isomerization
reactions co-exists during the alkylation process of benzene with DEO
over HZSM-5. As shown in Table 2, EB is obtained as the most
predominant product over all the catalysts. The formation of EB with
high selectivity might be due to its free diffusion without steric
hindrance through the pores of HZSM-5. The selectivity for EB
increases with increasing Si/Al ratio from 50 to 200 and the highest
EB selectivity of 84.2% is achieved over HZSM-5–200. With decreasing
acidity, a slight decrease in EB selectivity is observed over HZSM-5–
250, which may be due to the improvement in subsequent alkylation
of EB. Among the products of DEB isomers, p-DEB shows the highest
selectivity. The low selectivity for o-DEB might be due to the steric
hindrance to diffusion. The selectivity for m-DEB is less because this
position is not activated for electrophilic reaction. Therefore, electro-
philic reactions occur predominantly at the para position as it is free
from steric hindrance [20]. As the Si/Al ratio increases, the selectivi-
ty for p-DEB increases obviously, while the selectivity for m-DEB and
o-DEB decreased slightly. It has been reported by Park et al. [21] that
the para-isomer of DEB was formed as the primary product and this
was subsequently isomerized into o- and m-isomers mainly on the
external acid sites of the zeolites. According to Guan et al. [22],
the reduction of acidity could be responsible for the improvement
of the para-selectivity because the isomerization of para-DEB was
suppressed due to the absence of strong acidic sites. As was reported
[23], the isomerization of the para-isomer was generally considered to
take place on Brønsted acid sites, but not on Lewis acid sites. As shown
in Table 1, the B/L ratio decreases significantly over HZSM-5–250
compared with HZSM-5–50. The decrease in the number of Brønsted
acid sites suppresses the isomerization of para-DEB effectively, which
led to the improvement in the selectivity for para-DEB. As shown in
Table 2, toluene is obtained in considerable amounts over HZSM-5–50
and HZSM-5–100, which can be attributed to EB cracking on the
strong acidic sites. The selectivity for toluene decreases sharply with
increasing Si/Al ratio from 50 to 250, suggesting that the acidic sites
catalyzing the EB cracking reaction are relatively stronger than the
acidic sites catalyzing the benzene alkylation reaction. The formation
of TEB and multi-alkylated products with high selectivity can be
ascribed to the poor diffusion of the primary products facilitating
polyalkylation.

Table 3
Effect of temperature on products selectivity over HZSM-5–200.a

Entry T Sel.%
(K) EB Toluene m-DEB o-DEB p-DEB TEB Other
1 593 73.1 1.8 5.1 3.5 13.6 0.6 2.3
2 613 77.4 2.6 4.4 2.5 10.4 0.7 2.0
3 633 82.5 3.9 1.3 1.0 7.9 0.6 2.8
4 653 84.2 4.5 0.9 0.9 7.5 0.6 1.4
5 673 78.9 8.0 1.1 1.1 6.6 1.3 3.0
Fig. 6. Effect of temperature on conversion of benzene over HZSM-5–200. Conditions:
feed ratio = 4:1 (benzene:DEO), WHSV 1.5 h− 1. a
Feed ratio = 4:1 (benzene:DEO), WHSV 1.5 h− 1, time on stream 10 h.
1224 Y. Li et al. / Fuel Processing Technology 90 (2009) 1220–1225

diffusion of EB can suppress the subsequent alkylation reactions

effectively, which may lead to a significant decrease in the selectivity
for DEB isomers. It can also be found that among the DEB isomers, the
selectivity for p-DEB is much higher than that of o-DEB and m-DEB. As
discussed above, when EB in the vapor phase approaches the layer of
ethyl cations on the channel surface, it can better use its para position
for electrophilic attack to produce p-DEB, as its ortho position offers
little steric hindrance and the meta position demands a high activation
energy for electrophilic attack. Hence, the selectivity for p-DEB is
higher than for the other isomers. As illustrated in Table 3, the for-
mation of toluene increases significantly with increasing temperature
from 593 to 673 K, indicating that the high temperature is in favor of
the EB cracking reaction. A slight increase in the high selectivity for
TEB and polyalkylbenzene is observed at higher temperatures, which
may be ascribed to the poor diffusion of the DEB [20].

Fig. 7. Effect of feed ratios (benzene:DEO) on conversion of benzene over HZSM-5–200. 3.2.3. Effect of feed ratio
Conditions: temperature 653 K, WHSV 1.5 h− 1. The effect of feed ratio on benzene conversion and product
selectivity has been studied over HZSM-5–200. Fig. 7 shows the effect
of feed ratios on the conversion of benzene in the on-stream alkylation
Table 2 also shows the effect of weight hourly space velocity of benzene with DEO as a function of time. The conversion of benzene
(WHSV) on conversion of benzene and selectivity for EB over HZSM- shows a significant decline with increasing feed ratio of benzene to
5–100. It appears that the conversion of benzene and selectivity for DEO from 2:1 to 6:1. This is because of the increased dilution of DEO by
EB have no significant changes with varying the WHSV from 1.5 to benzene. With increasing feed ratios of benzene to DEO, the
0.5 h− 1, indicating that the influence of contact time on EB selectivity opportunity of benzene attacked by ethyl cations are reduced, and
can be neglected compared with the change in acidic strength. As then a lower benzene conversion is obtained. Table 4 presents the
shown in Table 2, a similar conversion levels between 37% and 39% is results of product selectivity over HZSM-5–200 in the alkylation of
obtained over HZSM-5 with Si/Al ratio of 150 and 200, but the benzene with DEO. The selectivity for EB is improved obviously with
selectivity for EB obviously increases with increasing Si/Al ratio from an increase in the ratio of benzene to DEO. However, the selectivity for
150 to 200, indicating that the selectivity for EB is mainly influenced all the by-products decreases simultaneously with an increase in the
by the acidic strength and the number of acidic sites of the catalysts. ratio of benzene to DEO. The increase in selectivity for EB may
therefore be due to the dilution of benzene, thus reducing its
3.2.2. Effect of temperature accessibility to yield subsequent alkylated products.
The alkylation of benzene with DEO was carried out at 593, 613,
633, 653 and 673 K over HZSM-5–200. Fig. 6 shows the effect of
temperature on the conversion of benzene in the on-stream alkylation 4. Conclusions
of benzene with DEO as a function of time. It can be seen that the
conversion of benzene increases from 593 to 653 K and attains a This study reveals that the alkylation of benzene with DEO over
maximum at 653 K. As the temperature of the system increased, the HZSM-5 is a convenient route for the synthesis of EB. Of the catalysts,
number of activated molecules also increased, resulting in an increase HZSM-5 with a Si/Al ratio of 200 exhibits the highest benzene
in the conversion of benzene. Beyond this temperature, the con- conversion and EB selectivity due to the proper strength of acidity.
version of benzene decreases as a result of coke deposition, which can Side reactions, such as EB cracking and DEB isomerization, can be
lead to the partial blocking of active sites and the formation of suppressed with decreases in the strength and number of acidic sites.
polyalkylated products at higher temperature [20].
Table 3 presents the results of product selectivity over HZSM-5– Acknowledgments
200 in the alkylation of benzene with DEO at different temperatures. It
is observed that the selectivity for EB increases obviously with We deeply appreciate the financial support from the High
increasing temperatures from 593 to 653 K, and the highest selectivity Technology Research and Development Program of Jiangsu Province
for EB of 84.2% is achieved at 653 K. With further increases in tem- (BG2006015) and the Foundational Research Project of the Depart-
perature, a clear decline in EB selectivity is observed, which can be ment of Education of Jiangsu Province (06KJA5013).
ascribed to the subsequent side reactions of EB. A high selectivity for
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