China Petroleum Processing and Petrochemical Technology
Scientific Research
2013, Vol. 15, No. 1, pp 54-60
March 30, 2013
Et3NHCl-AlCl3 Ionic Liquids as Catalyst for Alkylation of
Toluene with 2-Chloro-2-methylpropane
Chen Han1; Luo Guohua1; Xu Xin1; Wang Yanli2; Xia Jiajia2
(1. Department of Chemical Engineering, Beijing Institute of Petrochemical Technology, Beijing 1026172;
2. College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029)
Abstract: Alkylation of toluene with 2-chloro-2-methylpropane (t-Bu-Cl) to synthesize para-tert-butyltoluene (PTBT) was
carried out in the presence of triethylamine hydrochloride-aluminum chloride ionic liquids used as the catalyst. The ionic
liquids were prepared with different molar ratios of Et3NHCl to AlCl3, and the effect of the molar ratio between AlCl3 and
Et3NHCl, the reaction time, the reaction temperature, the ionic liquid dosage, as well as the molar ratio of toluene to chloro2-methylpropane on the alkylation reaction of toluene with chloro-2-methyl-propane was investigated. The test results
showed that the acidic ionic liquids prepared with Et3NHCl and AlCl3 had good activity and selectivity for the alkylation
reaction of toluene with alkyl chloride to produce PTBT. The optimal reaction conditions were specified at an AlCl3 to Et3NHCl ratio of 1.6, a reaction temperature of 20 ℃, a mass fraction of toluene to ionic liquid of 10%, and a chloro-2-methylpropane to toluene molar ratio of 0.5. Under the suitable reaction conditions, a 98% conversion of chloro-2-methylpropane
and an 82.5% selectivity of PTBT were obtained. Ionic liquids could be reused 5 times with its catalytic activity unchanged,
and the regenerated ionic liquids can be recycled.
Key words: alkylation; ionic liquid; toluene; 2-chloro-2-methylpropane; Et3NHCl-AlCl3
1　Introduction
Para-tert-butyltoluene (PTBT) is a valuable raw material
in spice industry and an important intermediate for manufacture of pharmaceutics and insecticides[1-2]. PTBT has
been synthesized via the Friedel-Crafts alkylation of toluene and isobutylene in the presence of catalysts consisting of homogeneous acid such as AlCl3, H2SO4, HF and
other Lewis acid catalysts used in the spice industry[3].
However, almost all of the processes have encountered
some common problems, such as heavy environmental
pollution, and tough problems associated with product recovery and purification[4]. Therefore, the investigation and
development of environmentally friendly catalytic technology have become the focus of a t t e n t i o n i n chemical industry.
Recently, the ionic liquids that are known as environmentally benign catalysts and solvents have been extensively
used in the alkylation reaction[5-9]. Ionic liquids uniquely
integrate many valuable properties including high polarity, low viscosity, high liquid temperature range, high thermal stability, wide tunability, immiscibility with certain
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54 ·
organic solvents, and absence of effective vapor pressure.
The main advantages of ionic liquid catalysis are its ability to greatly enhance reaction rates, along with higher activity at low temperature and higher selectivity[10-15]. Lowmelting ionic liquids composed of an organic chloride
and aluminum chloride are used as solvents and catalysts
for the Friedel–Crafts reactions as referred to in literature
reports[16-17]. The alkylation of toluene with 2-chloro-2methylpropane (t-Bu-Cl) to synthesize PTBT was carried out in the presence of triethylamine hydrochloridealuminum chloride ionic liquids used as the catalyst under
optimal reaction conditions. The effect of process parameters like the reaction time, the reaction temperature,
and the reactants ratio was investigated. Furthermore, the
recyclability and regeneration of ionic liquids were also
studied. As a result, some useful basic data for industrial
production can be provided.
Recieved date: 2012-10-17; Accepted date: 2012-12-01.
Corresponding Author: Professor Luo Guohua, E-mail:
[email protected].
Chen Han, et al. Et3NHCl-AlCl3 Ionic Liquids as Catalyst for Alkylation of Toluene with 2-Chloro-2-methylpropane
2　Experimental
2.1　Synthesis of ionic liquid
Ionic liquid prepared from triethylamine hydrochloride
and anhydrous AlCl3 was selected as the catalyst from a
series of ionic liquids for the alkylation of toluene with
t-Bu-Cl. Et3NHCl-AlCl3 (Al-IL) was prepared by slow
addition of a desired amount of anhydrous AlCl3 to the reagent triethylamine hydrochloride[18-19]. The reaction was
carried out under stirring for 3 hours at room temperature,
in order to yield a perfect compound of triethylamine
hydrochloride with AlCl3 (Al-IL)[20-24]. The whole process
was kept under blanketing with a dry nitrogen atmosphere
to avoid the hydrolysis of AlCl3. The Al-IL, once prepared, could be stored for a long time in a dry inert atmosphere.
The ionic liquid used in this work had an AlCl3 to triethylamine hydrochloride (Et3NHCl) molar ratio of 2.0.
The ratio (XAlCl3) is defined as:
X AlCl3 =
nAlCl3
nAlCl3 + nEt3 NHCl
The reaction for synthesis of ionic liquid was carried out
under an inert gas atmosphere, owing to the hydrophilicity of the catalyst towards moisture. The solvents were
dried according to the procedure referred to in the literature[25-26].
2.2　Alkylation reaction
The liquid-phase alkylation reaction of toluene and t-Bu-Cl
in the presence of ionic liquids used as the catalyst was
performed in a glass reactor, fitted with a reflux condenser
and magnetic stirrer. In a typical run, toluene after being
dehydrated with anhydrous calcium chloride together
with an appropriate amount of newly-made catalyst, were
added in the reactor prior to slow addition of a specified
amount of t-Bu-Cl in the reactor under constant stirring.
The reactor was then heated in a water bath by an electric
heater to the desired temperature, at which the reaction
was initiated in the specified temperature range. After
several minutes, the reaction mixture was cooled down to
room temperature with the catalyst being separated from
the reaction mixture.
The liquid samples were analyzed by GC equipped with
a flame ionization detector (FID) provided with a 5%
phenyl methylsilicone capillary column (measuring 30
m×0.25 mm) using nitrogen as the carrier gas. Reference
substances and GC–MS (GC 6890–MS 5973N) were used
for identification of the products. Ortho-tert-butyltoluene
did not appear as product due to the orientation effect and
space steric effect of methyl group which could be verified by chromatographic analysis.
3　Results and Discussion
3.1　Influence of the acidity of ionic liquids on
reaction
Et3NHCl−nAlCl3 was synthesized at the Et3NHCl/AlCl3
molar ratios varying in the range of 1:n. The molar fraction of AlCl3 had a significant influence on the acidity of
ionic liquids, which could decide the catalytic activity.
When the molar ratio between Et3NHCl and AlCl3 was
more than one, the molten salt remained in a state of viscous glassy material at room temperature and atmospheric
pressure, which would reduce the catalytic activity of the
ionic liquid itself. Furthermore, the reaction cannot be
observed as long as the Et3NHCl/AlCl3 molar ratio is 1:1
according to the data collected from experiments. It is
reported that the acidity of ionic liquids should be present
as long as the molar ratio of Et3NHCl and AlCl3 is under
1:1. The acidity of the ionic liquids showed an upward
trend with the increase of XAlCl3. As it can be seen from the
data collected from experimental results, when the molar
ratio of Et3NHCl and AlCl3 reached 1:1.1, the alkylation
reaction could be catalyzed effectively since the formation of carbocation could greatly contribute to alkylation
reaction of toluene, denoting that the increasing Lewis
acidity of catalyst was responsible for its activity. Furthermore, the molar fraction of AlCl3 had a decisive influence
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China Petroleum Processing and Petrochemical Technology
on the product selectivity. The influence of the acidity of
ionic liquids on the alkylation reaction is shown in Figure 1.
It can be seen from the data that the conversion of t-Bu-Cl
and selectivity of PTBT reached 98% and 83.3%, respectively, when the molar ratio of Et3NHCl to AlCl3 was 1:1.6,
indicating that the acidity, which is determined by anions
in the ionic liquid, should be treated as the essential factor
that can affect the selectivity of catalyst. In conclusion,
the selectivity of the catalyst could be regulated through
adjusting the molar ratio of AlCl3.
2013,15(1):54-60
tween toluene and poly-butylated toluene to transform the
byproducts into PTBT and MTBT(m-tert-butyltoluene),
so that the selectivity of target product would increase.
However, an excessive molar ratio between chloro-2methylpropane and toluene would reduce the efficiency
of reaction unit and increase the load of separation unit.
According to the experimental results, the selectivity of
PTBT accounted for 82.5% when the molar ratio between
chloro-2-methylpropane and toluene was 0.5:1, and the
selectivity would be affected if this molar ratio increased
excessively. In conclusion, the appropriate molar ratio
between chloro-2-methylpropane and toluene should be
0.5:1.
Figure 1　Influence of molar ratio of AlCl3 to Et3NHCl on
alkylation reaction
■—Selectivity of MTBT; ●—Selectivity of PTBT
(Reaction conditions: molar ratio of toluene to t-Bu-Cl=2:1,
dosage of catalysts=10% by weight of toluene, reaction
temperature=293 K, reaction time=10 min.)
3.2　Influence of t-Bu-Cl to toluene molar ratio
on the alkylation reaction
The influence of the molar ratio on the alkylation reaction is shown in Figure 2. It was observed that with an
increasing amount of t-Bu-Cl, the conversion of toluene
increased and the selectivity of PTBT also increased provided that the t-Bu-Cl /toluene molar ratio was less than
0.5. The selectivity was determined by the molar ratio
between chloro-2-methylpropane and toluene when other
conditions were fixed and this effect was made up of two
factors. On the one hand, not only did the probability of
reaction between toluene and chloro-2-methylpropane
rise, but also the opportunity for formation of deep alkylate of chloro-2-methylpropane with MTBT and PTBT
declined due to the dilution effect caused by toluene. On
the other hand, the increasing concentration of toluene
would be beneficial to the disproportionation reaction be·
56 ·
Figure 2　Influence of t-Bu-Cl to toluene molar ratio on
target product selectivity of alkylation reaction
■—Selectivity of PTBT; ●—Conversion of toluene
(Reaction conditions: n(AlCl3)/n(Et3NHCl)=1.6 in ionic liquids,
dosage of catalysts=10% by weight of toluene, reaction
temperature=293 K, reaction time=10 min.)
3.3　Influence of catalyst amount on alkylation
reaction
The influence of the amount of ionic liquids on the alkylation reaction is shown in Figure 3, when alkylation
of t-Bu-Cl with toluene was carried out with various
percentage of aluminum chloride radicals in ionic liquid
ranging from 2% to 20% (based on the total weight of
toluene). When the amount of ionic liquid increased under
the same reaction conditions, the conversion of t-Bu-Cl
increased. When the catalyst dosage was 10%, the conversion of t-Bu-Cl reached 98.2%. The reason why the
catalytic activity did not perform perfectly during the
alkylation reaction might be attributed to the insufficient
amount of the catalyst to provide a necessary amount of
Chen Han, et al. Et3NHCl-AlCl3 Ionic Liquids as Catalyst for Alkylation of Toluene with 2-Chloro-2-methylpropane
acid sites. The trend of increase in conversion of chloro2-methylpropane could be explained by the fact that the
quantity of acid sites increased with an increasing dosage
of catalyst.
However, the conversion of t-Bu-Cl still remained stable
at 98% even though the amount of catalyst increased
to 20% (Figure 3), which indicated that the ionic liquid
could be treated as a solvent so that once the reactant was
diluted by a redundant amount of solvent, the catalytic activity did not perform perfectly in the reaction. This trend
also illustrated that 10% of catalyst in the catalytic system
would have enough acid strength and concentration to effectively catalyze the alkylation reaction, leading to a 98.2%
conversion of t-Bu-Cl and also an 83% selectivity to PTBT.
Figure 3　Influence of amount of ionic liquid on alkylation
was obtained at a temperature of about 20 ℃ (293K). Meanwhile, the selectivity of MTBT saw an upward trend with
the increase of reaction temperature, while the selectivity
of PTBT witnessed a downward trend simultaneously.
The reason why this phenomenon might occur was that
the isomerization reaction played a significant role at high
temperature, because there was a trend on converting
PTBT to MTBT, which could be treated as an important
factor causing a sliding selectivity of PTBT. However, the
reaction kinetics must be taken into account in order to
guarantee an unrestricted flowability of ionic liquid and
also an appropriate reaction velocity, even though the selectivity of PTBT was higher at lower temperature. Therefore, a temperature of 20 ℃ (293K) would be an adequate
compromise between thermodynamic and kinetic factors.
reaction
Figure 4　Influence of temperature on alkylation reaction
■—Conversition of t-Bu-Cl; ●—Selectivity of PTBT
■—Selectivity of MTBT; ●—Selectivity of PTBT
(Reaction conditions: n(AlCl3)/n(Et3NHCl)=1.6 in ionic liquids,
(Reaction conditions: n(AlCl3)/n(Et3NHCl)=1.6 in ionic liquids,
molar ratio of toluene to t-Bu-Cl=2:1, reaction temperature=293 K,
molar ratio of toluene to t-Bu-Cl=2:1, dosage of catalysts=10% by
reaction time=10 min.)
weight of toluene, reaction time=10 min.)
3.4　Influence of temperature on the alkylation
reaction
3.5　Influence of reaction time on alkylation
reaction
Reaction temperature is regarded as one of the essential
factors to the activity of catalyst, because the reaction
temperature not only can influence both the activity of
catalyst and the reaction rate during alkylation, but also
can affect the diffusion rate of both reactants and products. Alkylation reaction between toluene and chloro-2methylpropane is an exothermic reaction with remarkable
reaction heat release, which implies that a lower temperature is more suitable to the reaction.
The influence of the reaction temperature on toluene
alkylation reaction was also investigated and the results
are shown in Figure 4. The maximum selectivity of PTBT
The influence of reaction time on the conversion of
t-Bu-Cl and the PTBT selectivity of ionic liquids is given
in Figure 5. It can be readily seen from Figure 5 that the
reaction time had only a slight influence on the outcome
of alkylation reaction. Within 5 min, the catalytic activity
and product selectivity reached an equilibrium (which is
clearly shown in Figure 5); an 83% selectivity of desired
product (PTBT) was achieved and no decomposition of
PTBT and secondary alkylation reaction were detected
when the alkylation reaction terminated. So, this is a
quick reaction to achieve kinetic and thermodynamic
equilibrium.
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China Petroleum Processing and Petrochemical Technology
2013,15(1):54-60
ing from 1 446.4 cm-1 to 1 448.5 cm-1), indicating that the
Lewis acidity saw an upward trend once the amount of
AlCl3 increased.
3.7　Reusability of the catalyst
Figure 5　Selectivity of products obtained at different
reaction time
■—Selectivity of PTBT; ●—Selectivity of MTBT
(Reaction conditions: n(AlCl3)/n(Et3NHCl)=1.6 in ionic liquids,
molar ratio of toluene to t-Bu-Cl=2:1, dosage of catalysts=10% by
weight of toluene, reaction temperature=293 K.)
MTBT=m-tert-butyltoluene; PTBT=p-tert-butyltoluene
3.6　Characterization of catalysts
FT-IR spectral analysis was performed because the acidity of ionic liquid could be regarded as a prominent factor
that could have influence on the selectivity of alkylate. In
this experiment, pyridine was used as the probe molecule
and the related spectrograms are shown in Figure 6. It can
be seen from Figure 6 that there were two characteristic
peaks (near 1 450 cm-1 and 1 540 cm-1 simultaneously),
which implied that both Lewis acid sites and Brønsted acid
sites were contained in the ionic liquid Et3NHCl-AlCl3.
With an increasing molar fraction of AlCl 3, the wave
number shifted to 1 448.5 cm-1 after the occurrence of
reaction between pyridine and ionic liquid (with different
Lewis acidity). It was a kind of hypsochromic shift (mov-
The reusability of the ionic liquids was investigated and
the related results are presented in Table 1. Both the
amount of reactants and catalyst was increased in order to
investigate the reusability of the catalyst and to examine
the sensitivity of the chloroaluminate ionic liquid catalyst
to moisture and its loss in the separation process. The
catalyst was separated out through a separatory funnel
after the alkylation reaction and then reused for the next
experiment under the same experimental conditions.
The data (as shown in Table 1) which were collected
from the cycle No.1 to the cycle No.5 suggested that the
Et3NHCl-AlCl3 ionic liquids could be reused thanks to its
favourable stability, and a high conversion of t-Bu-Cl and
a good selectivity of PTBT could still be observed even
though the ionic liquid was reused for 5 times. However,
the data which were acquired from the cycle No. 6 to the
cycle No. 7 of operation on reused catalyst implied that
the conversion of chloro-2-methylpropane had dropped
to 81.1% steeply, which demonstrated that the activity of
ionic liquids tumbled drastically since AlCl3 had dissolved
in the system. It was the AlCl3 solution that had broken
down the ionization equilibrium: [AlxCly]- [Alx-1Cly-3]+AlCl3, which could impair the Lewis acidity, resulting in
a weakened activity of catalyst.
Table 1　Results on recycle of Et3NHCl-1.6AlCl3 ionic
liquid used in alkylation reaction
No. of cycles
Conversion of
t-Bu-Cl, %
Selectivity of
MTBT, %
Selectivity of
PTBT, %
1
98.3
16.8
83.2
2
97.4
17.2
82.8
3
97.0
17.6
82.4
4
96.5
18.0
82.0
96.3
18.3
81.7
5
Regenerated ionic liquid (with addition of fresh AlCl3)
1
Figure 6　FT-IR spectra of ionic liquids with different mole
ratios of AlCl3/Et3NHCl
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58 ·
97.9
17.3
82.7
2
97.2
17.5
82.5
3
96.8
18.1
81.9
(Reaction conditions: n(AlCl3)/n(Et3NHCl)=1.6 in ionic liquids, molar
ratio of toluene to t-Bu-Cl=2:1, dosage of catalysts=10% by weight of
toluene, reaction temperature=293 K, reaction time=10 min)
Chen Han, et al. Et3NHCl-AlCl3 Ionic Liquids as Catalyst for Alkylation of Toluene with 2-Chloro-2-methylpropane
Furthermore, the regeneration of inactivated ionic liquid
must be taken into account in order to abide by the environmental protection regulations, since the active component of this catalyst system is consumed in the course
of alkylation reaction, leading to a decline of both acidity
and activity of the catalyst. The recovery and reuse of the
catalyst can be realized when a certain amount of fresh
AlCl3 was added to the inactive ionic liquids, which is a
topic that needs to be further investigated. This finding
implies that the ionic liquid catalyst can be recovered and
recycled efficiently.
[2]　Perego C, Amarilli S, Carati A, et al. Mesoporous silicaaluminas as catalysts for the alkylation of aromatic hydrocarbons with olefins[J]. Microporous Mater, 1999, 27(2/3):
345-354
[3]　Tang A S, Shen D L, Zhou C F, et al. Studies on p-tertbutyltoluene synthesis[J]. Zhejiang Chem, 1993, 4(1): 6-8
(in Chinese)
[4] Xu L X, Yin J H, Chen X X. Progress in environmentally
friendly chemical process of heterogeneous catalysts[J].
Petrochemical Technology & Application, 2003, 2l(6): 444447 (in Chinese)
[5] Shen H Y, Judeh Z M A, Ching C B, et al. Comparative
4　Conclusions
studies on alkylation of phenol with tert-butyl alcohol in the
Alkylation of toluene with t-Bu-Cl was performed in
an attempt to optimize the process regime and study the
influence of process parameters, including the reaction
time, the reaction temperature, the reactants mole ratio,
and the catalyst (ionic liquid) to toluene mass ratio, on the
conversion of t-Bu-Cl and selectivity of PTBT. A series
of comparative experiments were used in order to acquire
the optimum data. The optimum parameters for conducting the batch alkylation of toluene with t-Bu-Cl using
Et3NHCl-AlCl3 ionic liquid as the catalyst include: a reaction temperature of 293 K, a t-Bu-Cl to toluene ratio of
0.5:1, a catalyst (IL) to toluene mass ratio of 1:10 and a
reaction time of 10 min. This set of optimum parameters
can result in a maximum of 98.2% conversion of t-Bu-Cl
and a maximum of 83.5% selectivity of PTBT. The initial
catalytic activity can be maintained even though the Et3NHCl-AlCl3 ionic liquid has been utilized for 5 times. The
Et3NHCl-AlCl3 ionic liquid has demonstrated a stably reusable performance and it can be regenerated for repeated
use when it becomes inactivated.
Acknowledgments: The authors are grateful for the financial
support from the Beijing University of Chemical Technology.
We also thank the Key Laboratory of Advanced Chemical Engineering and Technology, Beijing Institute of Petrochemical
Technology, for the analysis of samples.
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SINOPEC Successfully Implemented Testing of Unit for
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·
60 ·
Chinese invention patents along with its own proprietary
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