Applied Catalysis A: General 286 (2005) 44–51

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A novel route to produce 4-t-butyltoluene by t-butylation of toluene

with t-butylalcohol over mesoporous Al-MCM-41 molecular sieves
M. Selvaraj a,*, S.H. Jeon a, J. Han b, P.K. Sinha c, T.G. Lee a,**
a
Research Institute of New Energy and Environmental System, Yonsei University, Seoul 120-749, South Korea
b
Environment & Process Technology Division, KIST, Seoul 136-791, South Korea
c
CWMF, BARC Facilities, Govt. of India, Kalpakkam 603102, India
Received 16 August 2004; received in revised form 16 February 2005; accepted 23 February 2005
Available online 8 April 2005

Abstract

t-Butylation of toluene with t-butylalcohol (t-BuOH) as alkylating agent was conducted under liquid phase reaction conditions over Al-
MCM-41 with different Si/Al ratios for highly selective synthesis of 4-t-butyltoluene. For the reactions, the influences of various reaction
parameters such as reaction temperature, time and t-BuOH to toluene ratio are discussed. With increasing the Si/Al ratios of Al-MCM-41
catalysts from 21 to 104, the conversion of toluene, and the yield and selectivity of 4-t-butyltoluene decreased because the number of Brønsted
acid sites in Al-MCM-41catalysts is found to decrease almost linearly with increasing ratios of Si/Al. The conversion and selectivity is
increased in Al-MCM-41(21) with each cycling of reaction. The Si/Al ratio of 21 is found to be more suitable for the t-butylation of toluene to
highly selective synthesis of 4-t-butyltoluene. Thus the selectivity of 4-t-butyltoluene is higher in Al-MCM-41(21) than that in other Al-
MCM-41 samples.
# 2005 Elsevier B.V. All rights reserved.

Keywords: Al-MCM-41; Catalytic activity; Brønsted acidity; Conversion of toluene; Selectivity of 4-t-butyltoluene

1. Introduction Ioffe et al. [9] studied different catalytic systems such as

The alkylations of aromatic hydrocarbons with olefins/
different types of alcohols are applied on a large scale in the
chemical industry [1]. Among para-dialkylated aromatics,
p-xylene, p-diisopropylbenzene, p-ethyltoluene, p-dietyl-
benzene, p- and m-cymenes and 4-tert-butyltoluene are very
important in fine chemical and petrochemical industries [2–
6]. The above products are alkylated-aromatic products. 4-t-
Butyltoluene is produced by alkylation of toluene with
anyone alkylating agent such as isobutylene, diisobutylene,
MTBE or t-BuOH. The product has been used as an
intermediate product to produce 4-t-butylbenzoic acid and
4-t-butylbenzaldehyde; they are especially used in perfum-
ery and in the fields of plastics and resins [7,8].
* Corresponding author. Tel.: +82 2 2123 5751; fax: +82 2 312 6401.
** Co-corresponding author.
E-mail addresses: selvarajman25@yahoo.com (M. Selvaraj),
teddy.lee@yonsei.ac.kr (T.G. Lee).
AlCl3, AlCl3–CH3NO2, sulfuric acid and polyphosphoric
acid in the liquid phase for alkylation of toluene by C4-
alcohols. By the above reaction, low yield and selectivity
of para isomer was obtained. These alkylations are still
performed with catalysts in chemical industries. Often
such catalysts are strong mineral acids or Lewis acids (e.g.
HF, H2SO4, and AlCl3), which are highly toxic and
corrosive. They are dangerous to handle and to transport as
they corrode storage and disposal containers. Often the
products need to be separated from the acid with a difficult
and energy consuming process. Finally, it occurs fre-
quently that these acids are neutralized at the end of the
reaction and, therefore, the correspondent salts have to be
disposed. Similar problems arise when free bases are used
as catalysts.
In order to avoid these problems many efforts have been
devoted to the search of solid acid catalysts that are more
selective, safe, environmentally friendly, regenerable, and
reusable and which do not have to be destroyed after reaction.

0926-860X/$ – see front matter # 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.apcata.2005.02.027
 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51
Thus, some solid acid catalysts are used for t-butylation of
toluene.
t-Butylation of toluene reaction was carried out using
toluene with MTBE, t-BuOH and t-butyl chloride in the
presence of activated clay, silica-alumina and iron sulphate
catalysts under liquid phase reaction conditions [10,11].
The 4-t-butyltoluene was synthesized over NiY zeolite as
catalyst, but, by the above reactions, the yield and
selectivity of the products ( p, m and o-isomers) were
very low because the activity of the catalysts is very low
[12]. From the above solid acid catalysts, low yield and
selectivity of para isomer was obtained, because all the
catalysts have small surface areas along with different
structures. The performance of the zeolite is also limited
by diffusional constraints associated with smaller pores.
These materials suffer from limited thermal stability as
well as negligible catalytic activity due to framework
neutrality. Moreover, the need for present day hetero-
geneous catalysts in processing hydrocarbons with high
molecular weights has made researchers search for better
systems. These limitations were overcome after the
discovery of mesoporous materials [13,14].
Incorporation of aluminum [15] and other metals [16,17]
into their mesoporous structure has therefore been inves-
tigated in order to introduce solid-state acidity and thereby
catalytic function. The typical characteristics of Al-MCM-
41, viz. highly ordered mesoporosity, large surface area,
high thermal stability and mild acidity, give the possibility of
applying these materials as catalysts in the synthesis and
conversion of large molecules.
Corma et al. [15] first reported the details of synthesis
and characterization of aluminum incorporating mesopor-
ous materials. However, the catalytic activity of the
material was low in comparison to the usual silica-alumina
catalyst and also the thermal stability was poor. Busio et al.
[18] also reported synthesis and characterization of the Al-
MCM-41, wherein incorporation of an excess of aluminum
(Si/Al = 10) formed an impure crystal-phase tridimite, and
the Lewis acid site prevailed because of the octahedral
non-framework aluminum, accompanied with the collapse
of the structure. Selvaraj et al. [2,3,19–23] reported the
details of synthesis and characterization of some meso-
porous solid acid catalysts. These have been used for
isopropylation of toluene, ethoxylation of b-naphthol, self-
condensation of acetophenone and intermolecular cycliza-
tion of ethanolamine; from those reactions, good conver-
sion and product selectivity are obtained. Particularly,
alkylation of toluene was carried out over mesoporous
solid acid catalysts by the best candidates [3,5,6]. We have
applied the mesoporous catalysts for highly selective
synthesis of 4-t-butyltoluene.
In the present study, Al-MCM-41 with Si/Al ratios
equal to 21, 42, 62, 83 and 104 were synthesized and
characterized according to the published method [22–24]
using cetyltrimethylammonium bromide as template under
hydrothermal conditions. The materials have been used as
45
catalysts for the higher selectivity of 4-t-butyltoluene
produced by the alkylation of toluene using t-BuOH as the
alkylating reagent. Owing to its low cost and extensive use
in industries, t-BuOH was chosen instead of isobutene. The
effects of reaction temperature, time and t-BuOH to
toluene ratio on the selectivity of 4-t-butyltoluene were
investigated.
2. Experimental
2.1. Materials
The syntheses of Al-MCM-41 materials were carried out
by hydrothermal method using sodium metasilicate (Na2
SiO3
5H2O), cetyltrimethylammonium bromide (C16H33
(CH3)3N+Br), aluminum sulphate (Al2(SO4)3
18H2O), sul-
furic acid (H2SO4). In order to study the formation of 4-t-
butyltoluene by t-butylation of toluene, the reagents t-BuOH
((CH3)3–C–OH), toluene (C7H8O) and decane were used.
All chemicals (AR grade) were purchased from Aldrich &
Co., USA.
2.2. Synthesis and characterization of Al-MCM-41
Al-MCM-41 with Si/Al ratios equal to 21, 42, 62, 83 and
104 were synthesized and characterized; acidity measure-
ments were done according to the published method [22–
24].
2.3. t-Butylation of toluene—experimental procedure for
liquid phase catalytic reaction
The Al-MCM-41 catalyst (0.2 g freshly calcined
catalyst kept at 400 8C was used) was added into a
mixture of t-BuOH/toluene (various mmol ratios) with
100 ml of decane as solvent. Each reaction was carried out
in a stirred batch autoclave reactor (100 ml, Autoclave
Engineers) at reaction temperatures between 125–200 8C
for different times (h). The reactor was flushed twice with
nitrogen to replace air. Alkylation reactions were carried
out at the autogeneous pressure. The reactor was cooled
down to 0 8C and the reaction products were recovered
from the reactor.
The samples of the reaction mixture were withdrawn
periodically from the closed reactor and analysed on a
CHROMPACK 9002 gas chromatograph equipped with a
CP Sil 5 CB column (25 m  0.53 mm) and an FID detector.
The temperature program was held at 60 8C (5 min),
increased from 60 to 220 8C with a slope of 5 8C/min and
held at 220 8C during 5 min isothermally.
The products of the reaction were identified on a GC/MS
QP5000 (Shimadzu) with EI and capillary column (HP-1,
50 m  0.2 mm  0.33 mm); carrier gas was helium (1 ml/
min). Temperature program: from 50 8C with a gradient of
5 8C/min to 240 8C was used.
46 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51

3. Results and discussion protonated by the catalyst to form t-butyl carbocation

The synthesized Al-MCM-41 catalysts have been used
for t-butylation of reaction with t-BuOH to highly selective
synthesis of t-butyltoluene. The reaction mechanism is
discussed.
3.1. Mechanism of t-butylation of toluene
The t-butylation of toluene with t-BuOH is an electro-
philic substitution reaction on the aromatic ring. t-
Butylation reactions catalyzed by acids or solid acid zeolites
are commonly considered to proceed via carbenium ion
mechanisms [3].
t-BuOH reacts with solid acid catalyst to form isobutene,
along with removal of water (Eq. (1)). Isobutene is
(Eq. (2)). The carbocation further reacts with toluene in
the presence of the catalyst to form 4-t-butyltoluene and
3-t-butyltoluene Eq. (3). Either 4-t-butyltoluene or 3-t-
butyltoluene reacts with the carobocation over the catalyst
to form 3,5-di-t-butyltoluene (Eq. (4)). Excess isobutylene
further reacts with each molecule over the catalyst to
form oligomers (Eq. (5)) while the oligomers (R-alkyl
groups) react with excess toluene in the presence of the
catalyst to form alkyltoluenes with longer alkyl chains
(Eq. (6)). The remaining oligomers further react with
water over the catalyst to form alcohols (Eq. (7)). All the
above products (all equations) are obtained with respect to
the catalytic properties along with optimal reaction
conditions. The reaction of toluene with t-BuOH is given
in Fig. 1.

Fig. 1. Reaction scheme of t-butylation of toluene.

 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51 47

In all cases, the main reaction products have been
identified as 4-t-butyltoluene and 3-t-butyltoluene. 2-t-
Butyltoluene was present in the reaction products only in
trace amounts. The main product is logically 4-t-butylto-
luene because para-position is favored by the influence of
the steric hindrance of the methyl group on one side and
voluminous t-Bu group due to the structure of mesoporous
Al-MCM-41 catalysts.
The formation of 2-t-butyltoluene is hindered by ortho-
position of methyl and voluminous t-Bu group. The same
steric effect allows only the formation of 3,5-di-t-
butyltoluene, where all alkyl groups are in the meta-
position. 3,5-Di-t-butyltoluene was also found in the
reaction products, but only in trace amounts obtained over
Al-MCM-41 catalysts. The other products have been
identified by GC–MS as alkyltoluenes with longer alkyl
chains. These products were formed by alkylation of toluene
with lower oligomers of isobutene (preferentially by
dimers). The effects of various parameters on the t-
butylation of toluene reaction are discussed.
3.2. Selectivity of 4-t-butyltoluene
The reaction of t-butylation of toluene was carried out in
the presence of various Si/Al ratios of Al-MCM-41 catalysts.
Maximum conversion of toluene to the extent of 86.2 and
92.3% 4-t-butyltoluene selectivity was obtained when the
reaction was carried out in the presence of Al-MCM-41(21).
The conversion of toluene and selectivity of 4-t-butyltoluene
in the presence of Al-MCM-41(21) are higher, due to the
high aluminum content, the high hydrothermal stability and
also the higher number of Brønsted acid sites from creation
of negative charges on the pore walls, which is attributed to
the incorporation of Al trivalent ions in place of tetrahedral
Si in the structure. The number of acid sites for the
different catalysts follow the order; Al-MCM-41(21) > Al-
MCM-41(42) > Al-MCM-41(62) > Al-MCM-41(83) >
Al-MCM-41(104), as obtained from TPD and FTIR-
pyridine treatment. This reaction is activated on the m-
and the p-positions by the presence of the methyl group. The
selectivity of 4-t-butyltoluene is higher than those of 3-t-
butyltoluene, 2-t-butyltoluene and 3,5-di-t-butyltoluene due
to steric hindrance of the methyl group at the para-position.
The 3-t-butyltoluene and 3,5-di-t-butyltoluene are thermo-
dynamically more stable [3]. Thus, the conversion of toluene
and selectivity of 4-t-butyltoluene are higher in Al-MCM-
41(21) than in the other Al-MCM-41 catalysts. The results
are shown in Table 1.
3.3. Variation of reaction time with different Si/Al
ratios of Al-MCM-41
The liquid phase reaction of t-butylation of toluene was
carried out at various reaction times with 2:1 mmol ratio of t-
BuOH to toluene and 100 ml of decane as solvent at 175 8C
reaction temperature, in the presence of Al-MCM-41 with
different Si/Al ratio catalysts. Lower reaction time (<1 h)
does not favor the formation of 4-t-butyltoluene because
surface activity of the catalysts is insufficient to react with
reactants. Then conversion of toluene, yield and selectivity

Table 1
t-Butylation of toluene: variation of reaction time with different Si/Al ratios of Al-MCM-41
Catalysts Time (h) Conversion of toluene (%) Yield of the products (%) 4-t-BT selectivity
4-t-BT 3-t-BT Others
Al-MCM-41(21) 1 74.3 65.3 5.1 3.9 87.88
2 86.2 79.6 5.3 1.3 92.34
4 93.4 56.7 30.4 6.3 60.70
8 96.2 52.4 37.0 6.8 54.46
Al-MCM-41(42) 1 69.2 59.8 5.0 4.4 86.41
2 81.0 74.1 5.1 1.8 91.48
4 88.7 51.2 29.6 7.9 57.72
8 90.8 46.9 35.3 8.6 51.65
Al-MCM-41(62) 1 63.1 53.3 4.8 5.0 84.46
2 74.8 66.6 4.9 3.3 89.03
4 81.8 45.7 28.4 7.7 55.86
8 84.4 41.4 34.8 8.2 49.05
Al-MCM-41(83) 1 56.0 44.8 4.6 6.6 80.00
2 67.6 57.1 4.7 5.8 84.46
4 74.5 40.2 28.1 6.2 53.95
8 77.0 35.9 33.4 7.7 46.62
Al-MCM-41(104) 1 47.9 36.3 4.4 7.2 75.78
2 59.4 45.8 4.5 9.1 77.10
4 66.2 34.7 27.7 3.8 52.41
8 68.6 30.4 31.1 7.1 44.31
Reaction conditions: 0.2 g of catalyst; reaction temperature (T) = 1758C; 1:2 mmol ratio of t-butylalcohol to toluene; 100 ml of n-decane; 4-t-BT, 4-t-
butyltoluene; 3-t-BT, 3-t-butyltoluene; others—2-t-butyltoluene, 2,5-di-t-butyltoluene and oligomers.
48 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51

Table 2
t-Butylation of toluene: variation of reaction temperature with different Si/Al ratios of Al-MCM-41
Catalysts Temperature (8C) Conversion of toluene (%) Yield of the products (%) 4-t-BT selectivity
4-t-BT 3-t-BT Others
Al-MCM-41(21) 125 66.7 55.4 4.8 6.5 83.05
150 75.3 65.3 5.2 4.8 86.71
175 86.2 79.6 5.3 1.3 92.34
200 90.3 58.4 23.5 8.4 64.67
Al-MCM-41(42) 125 61.4 49.7 4.5 7.2 80.94
150 70.1 59.7 4.7 5.7 85.16
175 81.0 74.1 5.1 1.8 91.48
200 84.9 52.6 22.1 10.2 61.95
Al-MCM-41(62) 125 54.9 42.0 4.4 8.5 76.50
150 63.8 52.1 4.6 7.1 81.66
175 74.8 66.6 4.9 3.3 89.03
200 78.3 44.8 21.5 12.0 57.21
Al-MCM-41(83) 125 47.5 32.3 4.2 11.0 68.0
150 56.5 42.5 4.3 9.7 75.22
175 67.6 57.1 4.7 5.8 84.46
200 70.8 35.2 20.8 14.8 49.71
Al-MCM-41(104) 125 40.1 22.9 3.9 13.3 57.10
150 49.2 32.9 4.1 12.2 66.86
175 59.4 45.8 4.5 9.1 77.10
200 63.0 25.5 19.7 17.8 40.47
Reaction conditions: 0.2 g of catalyst; reaction time = 2 h; 1:2 mmol ratio of t-butylalcohol to toluene; 100 ml of n-decane; 4-t-BT, 4-t-butyltoluene; 3-t-BT, 3-t-
butyltoluene; others—2-t-butyltoluene, 2,5-di-t-butyltoluene and oligomers.

of 4-t-butyltoluene increase with increasing reaction time up because the acid sites on the catalyst surface are decreased
to 2 h over different Al-MCM-41 (different Si/Al ratios) with decreasing aluminum content. The results are shown in
catalysts in the same reaction conditions. But the conversion, Table 1. When the reaction time is increased (>3 h), the
yield and selectivity decrease with increasing Si/Al ratios, conversion of toluene increased, but the yield and selectivity

Table 3
t-Butylation of toluene: variation of mmol ratio (t-butylalcohol/toluene) with different Si/Al ratios of Al-MCM-41
Catalysts t-BA/toluene mmol ratio Conversion of toluene (%) Yield of the products (%) 4-t-BT selectivity
4-t-BT 3-t-BT Others
Al-MCM-41(21) 1:1 40.4 29.4 8.4 2.6 72.77
2:1 86.2 79.6 5.3 1.3 92.34
1:2 89.9 63.3 18.4 8.2 70.41
1:4 72.3 49.5 10.4 12.4 68.46
Al-MCM-41(42) 1:1 35.1 25.5 7.2 2.4 72.64
2:1 81.0 74.1 5.1 1.8 91.48
1:2 84.8 59.7 17.2 7.9 70.40
1:4 67.1 44.8 10.2 12.1 66.76
Al-MCM-41(62) 1:1 28.9 19.9 6.8 2.2 68.85
2:1 74.8 66.6 4.9 3.3 89.03
1:2 78.7 55.0 16.2 7.5 69.88
1:4 60.9 39.5 9.6 11.8 64.86
Al-MCM-41(83) 1:1 21.6 13.2 6.5 1.9 61.11
2:1 67.6 57.1 4.7 5.8 84.46
1:2 71.5 49.5 14.7 7.3 69.23
1:4 53.6 33.0 9.1 11.5 61.56
Al-MCM-41(104) 1:1 13.4 7.3 4.4 1.7 54.47
2:1 59.4 45.8 4.5 9.1 77.10
1:2 63.2 42.3 13.8 7.1 66.93
1:4 45.3 24.6 9.5 11.2 54.30
Reaction conditions: 0.2 g of catalyst; reaction temperature (T) = 1758C; reaction time = 2 h; 100 ml of n-decane; 4-t-BT, 4-t-butyltoluene; 3-t-BT, 3-t-
butyltoluene; others—2-t-butyltoluene, 2,5-di-t-butyltoluene and oligomers.
 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51
Fig. 2. Variation of reaction time with (a) conversion of toluene (%) and (b)
selectivity of 4-t-butyltoluene (%) at different temperature over Al-MCM-
41(21) material.
of 4-t-butyltoluene decreased, because 4-t-butyltoluene is
gradually transformed to 3-t-butyltoluene, while the other
by-products, namely 2-t-butyltoluene, 3,5-di-t-butylto-
luene and oligomers slightly increased. The conversion
of toluene and selectivity of 4-t-butyltoluene are higher in
Al-MCM-41(21) than those of other Al-MCM-41 cata-
lysts due to the greater chemisorption of reactants on the
catalyst surface pores due to the higher number of
Brønsted acid sites at 175 8C for 2 h; the results are shown
in Table 1. So the optimum reaction time was found to be
2 h for the highly selective synthesis of 4-t-butyltoluene.
Such higher yield and selectivity of 4-t-butyltoluene
and conversion of toluene using Al-MCM-41(21) depict
its superiority in performance compared to other Al-
MCM-41.
49
Fig. 3. Variation of reaction time with (a) conversion of toluene (%) and (b)
selectivity of 4-t-butyltoluene (%) on different mmol ratio (t-butanol/
toluene) over Al-MCM-41(21) material.
3.4. Variation of reaction temperature with different
Si/Al ratios of Al-MCM-41
The t-butylation of toluene was carried out at various
reaction temperatures with 2:1 mmol ratio of t-BuOH to
toluene and 100 ml of decane as solvent for 2 h reaction time
in the presence Al-MCM-41 with different Si/Al ratio
catalysts. The results are shown in Table 2. When the
temperature was increased up to 175 8C at the same reaction
conditions, the conversion of toluene, yield and selectivity of
4-t-butyltoluene increased. After the reaction temperature of
175 8C, the conversion increases, but the yield and
selectivity of 4-t-butyltoluene decrease, because the
selectivity of 3-t-butyltoluene and of other by-products
namely 2-t-butyltoluene, 3,5-di-t-butyltoluene and oligo-
50 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51
Fig. 4. Variation with run of the catalysts with (a) conversion of toluene (%)
and (b) selectivity of 4-t-butyltoluene (%) in the presence of different Al-
MCM-41 materials.
mers increase by transalkylating of 4-t-butyltoluene, while
the 4-t-butyltoluene has low thermodynamical stability at
higher reaction temperature (>175 8C). The conversion of
toluene, yield and selectivity of 4-t-butyltoluene are higher
over Al-MCM-41(21) than that the values of other Al-
MCM-41 catalysts due to the increased catalytic activity
along with the higher number of Brønsted acid sites on the
surface of the catalyst while most of converted reactants are
favored into 4-t-butyltoluene at 175 8C for 2 h. So the
optimum reaction temperature was found to be 175 8C for
the highly selective synthesis of 4-t-butyltoluene. When the
reaction temperature is further increased to 200 8C, the
conversion of toluene and yield and selectivity of 4-t-
butyltoluene decreased. This may be due to the debutylation
of 4-t-butyltoluene with formation of toluene and isobuty-
lene.
The liquid phase reaction of t-butylation of toluene was
carried out at various reaction times with 2:1 mmol ratio of t-
BuOH to toluene and 100 ml of decane as solvent at different
reaction temperatures in the presence of Al-MCM-41(21).
When the reaction time was increased to 2 h at the
temperature from 125 to 175 8C in the same reaction
conditions, the conversion of toluene increases while the
yield and selectivity of 4-t-butyltoluene increases, but, after
2 h, the yield and selectivity decreased. The results are
shown in Fig. 2. When the reaction time (>4 h) along with
temperature (>175 8C) are increased, selectivity of 3-t-
butyltoluene increased and yields of other by-products as 2-
t-butyltoluene and 3,5-di-t-butyltoluene also increased,
because of debutylation of 4-t-butyltoluene with formation
of toluene and isobutylene.
3.5. Variation with t-butanol to toluene ratio
The t-butylation of toluene was carried out at 175 8C
reaction temperature with various mmol ratios of t-BuOH to
toluene and 100 ml of decane as solvent for 2 h reaction time
in the presence Al-MCM-41 with different Si/Al ratio
catalysts; the results are shown in Table 3. The conversion of
toluene, yield and selectivity of t-butyltoluene decreased at
1:1 mmol ratio of t-BuOH to toluene. This may be due to the
t-BuOH is insufficient to react with toluene. As the 2 mmol
of t-BuOH is increased to 1 mmol of toluene, the conversion
of toluene, yield and selectivity of 4-t-butyltoluene increase.
This may be due to equilibrating of the two reactants on the
Brønsted acid sites of the inner side surface of catalyst. As
the 2 mmol of toluene is increased to 1 mmol of t-BuOH, the
conversion increased, but the yield and selectivity of 4-t-
butyltoluene the 3-t-butyltoluene decreased, while other by-
products slightly increased. When 4 mmol of toluene was
combined with 1 mmol of t-BuOH, the conversion of
toluene, yield and selectivity of 4-t-butyltoluene and 3-t-
butyltoluene decreased, but the other products of oligomers
increased. In all the cases, 4-t-butyltoluene was obtained as
the major product along with small amounts of 3-t-
butyltoluene products. In addition, trace amounts of other
alkylated products like 3,5-di-t-butyltoluene, 2-t-butylto-
luene and oligomers were also observed. At a reaction
temperature of 175 8C for reaction time at 2 h over different
Si/Al ratios of Al-MCM-41 catalysts, the highest conversion
of toluene and highest selectivity of 4-t-butyltoluene were
obtained at t-BuOH to toluene ratio of 2:1, while the
conversion and yield and selectivity increased with high
aluminum content such results are shown in Table 3.
Generally, as the molar ratio of toluene is increased with t-
BuOH, the conversion of toluene decreased, and as the molar
ratio of t-BuOH is increased with toluene, the conversion of
toluene decreased. This may be due to coking of the catalyst
by unsaturation of reactant and catalyst pores; then there
would be fast diffusion without reaction from the catalyst
active sites. Hence the optimal molar ratio of t-BuOH to
toluene is 2:1. Thus, the optimum conditions for obtaining
 M. Selvaraj et al. / Applied Catalysis A: General 286 (2005) 44–51
maximum conversion of toluene (86.2%) and highest
selectivity of 4-t-butyltoluene (92.3%) can be summarized
as follows: Catalyst, Al-MCM-41 with Si/Al = 21; reaction
temperature = 175 8C, time = 2 h and t-BuOH to toluene
ratio = 2:1.
The liquid phase reaction of t-butylation of toluene was
carried out at various reaction times with different mmol
ratios of t-BuOH to toluene and 100 ml of decane as solvent
at 175 8C in the presence Al-MCM-41(21); the results are
given in Fig. 3. The conversion of toluene and selectivity of
4-t-butyltoluene increase but the yield and selectivity
decrease with different time in the series 1:1 <
1:4 < 1:2 < 2:1 mmol ratios of t-BuOH to toluene. The
conversion and selectivity are higher in 2:1 mmol ratios for
2 h than those of other mmol ratios due to equilibrium of the
reactants with the greater chemisorption on the Brønsted
acid sites of catalyst surfaces. The yields of other products
such as oligomers in 1:1 mmol ratio, 3-t-butyltoluene and
2,5-di-t-butyltoluene in 1:2 and 1:4 ratios are slightly higher
than those of 2:1 mmol ratio due to the favorable catalyst
surface and reaction conditions.
3.6. Recyclability
All Al-MCM-41 catalysts were reused for the t-
butylation of toluene at 175 8C with 2 h reaction time and
2:1 mmol ratio of t-BuOH to toluene for the highly selective
synthesis of t-butyltoluene; the results have been depicted in
Fig. 4. No loss of catalytic activity was observed after 4 runs.
Instead, its conversion of toluene, yield and selectivity of t-
butyltoluene increased with each cycling in Al-MCM-
41(21). But the conversion, yield and selectivity decreased
in other Al-MCM-41 catalysts at the same reaction
conditions. The results are shown in Fig. 4. This may be
due to decreasing of the catalytic activity along with
dehydration of Brønsted acid sites on the surface of the
catalyst because of the catalysts having less aluminum
content.
4. Conclusions
The selective synthesis of 4-t-butyltoluene was carried
out over Al-MCM-41 catalysts with different optimal
conditions. The Si/Al-molar ratios are increased, the
conversion of toluene, yield and selectivity of 4-t-
butyltoluene decreased. When the Al-MCM-41(21) was
reused for the t-butylation of toluene with 2:1 mmol ratio of
t-BuOH to toluene at 175 8C reaction temperature and at 2 h
reaction time, the conversion of toluene and selectivity of 4-
t-butyltoluene increased in only Al-MCM-41(21) with each
cycling. The conversion and selectivity of t-butyltoluene are
51
higher in recyclable Al-MCM-41(21) than the values of
other Al-MCM-41 catalysts due to no loss of catalytic
activity after the recycling process. Thus, a higher yield and
selectivity of 4-t-butyltoluene and conversion of toluene
using Al-MCM-41(21) depicts its superiority in perfor-
mance compared to other Al-MCM-41 catalysts.
Acknowledgement
The authors gratefully acknowledge the Korea Research
Foundation for sponsoring this work (KRF-2003-005-
D00002).
References
[1] H.G. Franck, J.W. Stadelhofer, Industrial Aromatic Chemistry,
Springer, Berlin, 1988.
[2] M. Selvaraj, A. Pandurangan, K.S. Seshadri, P.K. Sinha, V. Krishna-
samy, K.B. Lal, J. Mol. Catal. A: Chem. 186 (2002) 173.
[3] M. Selvaraj, A. Pandurangan, K.S. Seshadri, P.K. Sinha, K.B. Lal,
Appl. Catal. A: Gen. 242 (2003) 347.
[4] A.B. Halgeri, J. Das. Catal. Today 73 (2002) 65.
[5] C. Perego, S. Amarilli, A. Carati, C. Flego, G. Pazzuconi, C. Rizzo, G.
Bellussi, Micropor. Mesopor. Mater. 27 (1999) 345.
[6] J. Cejka, A. Krejei, N. Zilkova, J. Dedecek, J. Hanika. Micropor.
Mesopor. Mater. 44–45 (2001) 499.
[7] G.W. Hearne, T.W. Evans, V.W. Buls, C.G. Schwarzer, Ind. Eng.
Chem. 47 (11) (1995) 2311.
[8] N. Kusano, T. Kobayashi, H. Miyajima, JP 61145130 (1986).
[9] B.V. Ioffe, R. Lemann, B.V. Stoljarov, Neftekhimija 9 (3) (1969) 386.
[10] N. Kusano, T. Kobayashi, H. Miyajima, JP 61145130 (1986).
[11] M. Hino, K. Arata, Chem. Lett. (1977) 277.
[12] B. Coughlan, W.M. Carroll, J. Nunan. J. Chem. Soc. Faraday Trans. 79
(1) (1983) 327.
[13] C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vashuli, J.S. Beck,
Nature 359 (1992) 710.
[14] J.S. Beck, J.C. Vartuli, W.J. Roth, M.E. Lernowicz, C.T. Kresge, K.D.
Schmitt, C.T.W. Chu, D.H. Olson, E.W. Sheppard, S.B. Mccullen, J.B.
Higgins, J.C. Schlenker, J. Am. Chem. Soc. 144 (1992) 10834.
[15] A. Corma, V. Forance, M.T. Navarro, J. Perez-Parients, J. Catal. 148
(1994) 569.
[16] G. Bellussi, G. Pazzuconi, C. Perego, G. Girotti, G. Terzoni, J. Catal.
157 (1995) 227.
[17] K.A. Koyano, T. Tatsumi, J. Chem. Soc., Chem. Commun. (1996) 145.
[18] M. Busio, J. Janchen, J.H.C. van Hooff, Micropor. Mater. 5 (1995) 211.
[19] M. Selvaraj, A. Panurangan, K.S. Seshadri, P.K. Sinha, V. Krishna-
samy, K.B. Lal, J. Mol. Catal. 192 (2003) 153.
[20] M. Selvaraj, P.K. Sinha, K.S. Seshadri, A. Pandurangan, Appl. Catal.
A: Gen. 265 (2004) 75.
[21] M. Selvaraj, P.K. Sinha, A. Pandurangan, Micropor. Mesopor. Mater.
70 (2004) 81.
[22] M. Selvaraj, B.R. Min, Y.G. Shul, T.G. Lee, Micropor. Mesopor.
Mater. 74 (2004) 143.
[23] M. Selvaraj, B.R. Min, Y.G. Shul, T.G. Lee, Micropor. Mesopor.
Mater. 74 (2004) 157.
[24] M. Selvaraj, Ph.D. thesis, Anna University, Tamil Nadu, India (2003).