Chinese Journal of Chemical Engineering, 16(1) 151154 (2008)

RESEARCH NOTES

Preparation of Butyl Chloride from Butanol and Hydrochloric Acid

Using Ionic Liquids as Catalyst*
SUN Aijun (), NIE Yi (), LI Chunxi ()** and WANG Zihao ()
College of Chemical Engineering, Beijing University of Chemical Technology, Beijing 100029, China

Abstract The catalytic performance of some quaternary ammonium salts for the liquid phase reaction of butanol
and hydrochloric acid at different conditions was studied experimentally and compared with the traditional catalyst
(ZnCl2). The organic ammonium catalysts investigated include ionic liquids N-butyl-N-methyl imidazolium fluoborate ([BMIM][BF4]) and N-butyl-N-methylimidazolium chloride ([BMIM]Cl) as well as hydrochloric salts of
N-methylimidazol ([HMIM]Cl), pyridine ([HPy]Cl) and triethylamine ([HEt3N]Cl). It is shown that the intrinsic
catalytic performance of all organic ammonium salts except [HEt3N]Cl is slightly superior to ZnCl2, while the selectivity of butyl chloride is nearly at the same level around 96%. The conversion of butanol increases slightly with
temperature and the catalyst amount added while the variation of selectivity is not obvious. Based on the recycle
experiments, the ionic liquids as catalyst for the reaction of butanol and hydrochloric acid can be used more than 5
times, which suggests great potential of using ionic liquids as novel catalyst for such reactions.
Keywords ionic liquid, butyl chloride, butanol, hydrochloric acid, catalyst

INTRODUCTION

Butyl chloride is an important chemical which is

widely used as solvent and chemical reagent for preparing butyl lithium, a catalyst for preparing synthetic
rubbers, cationic surfactants, pesticides and pharmaceutical products. Alkyl chloride is generally prepared
by the corresponding alcohol and a chlorinating agent
such as hydrochloric acid, thionyl chloride, phosgene
or phosphorus chloride, or by reacting the corresponding alkene with hydrogen chloride in the presence of catalysts. Typical catalysts include zinc chloride, pyridine or ammonium halides [1-5]. In addition,
the catalyst can be used directly or supported on such
carriers as silica gel, activated carbon or alumina depending on the reacting conditions adopted, and the later
is usually used for vapor phase reaction systems [6-8].
Hydrochloric acid is a widely used chemical,
which is produced as a byproduct in producing chlorinated products, for example, high chlorinated polyethylene (HCPE), chlorinated polypropylene (CPP),
chlorinated paraffin (CP), chlorinated rubber (CR),
and chlorobenzene etc. The industrial grade hydrochloric acid containing 20%-35% HCl by mass is
abundant. Hence, it is of practical significance to
convert the by-produced hydrochloric acid to high
valued chemicals, e.g. alkyl chlorides.
For the preparation of alkyl chloride with the corresponding alcohol and hydrochloric acid, it is imperative to develop some high performance catalysts.
Ionic liquids used as catalysts for some reactions have
been reported [9-14]. But to our knowledge, reaction
of butanol with hydrochloric acid catalyzed by imidazolium hydrochloric ([HMIM]Cl), N-butyl-Nmethylimidazolium chloride ([BMIM]Cl) and N-butylN-methyl imidazolium fluoborate ([BMIM][BF4]) is
not reported. The objective of this work is to investigate the possibility of using ionic liquids (ILs) as a
new kind of catalyst. Toward this end, the catalytic

performance of a series of imidiazolium based ionic

liquids such as imidazolium chloride ([HMIM]Cl),
N-butyl-N-methylimidazolium chloride ([BMIM]Cl)
and N-butyl-N-methyl imidazolium fluoborate
([BMIM][BF4]) were evaluated for the first time and
compared with the traditional catalysts, e.g. zinc chloride (ZnCl2), pyridine chloride ([HPy]Cl) and
triethylammonium chloride ([HEt3N]Cl).
2

EXPERIMENTAL

Analytical grade ZnCl2, n-butanol, triethylamine

(Et3N), pyridine, N-methyimidiazole and hydrochloric
acid containing 36.5% of HCl by mass were used.
Catalysts [HPy]Cl, [HEt3N]Cl, and [HMIM]Cl were
prepared by neutralization of the corresponding bases
with equal moles of hydrochloric acid. The reaction
and purification process was simple and straightforward, and thus not illustrated here [15]. Ionic liquids
[BMIM]Cl and [BMIM][BF4] were prepared and purified following the procedures described elsewhere [16].
The purity of the ILs prepared was about 98% in terms
of H nuclear magnetic resonance (HNMR) analysis.
The experimental set-up is shown in Fig. 1,
which in fact is a total reflux reactor with magnetic
stirring and heated in a thermostatic oil bath. The reactor used is a 50 ml pyrex glass tube with 25 cm in
height and 2 cm in inner diameter.
The experiment was performed as follows. First,
an admixture with known amount of butanol, hydrochloric acid (36.5%, by mass) and catalyst was added
to the reactor, which was then heated to a setting temperature under magnetic stirring and totally refluxed.
As the reaction proceeded, two liquid phases, i.e. a
water-rich and a butyl chloride-rich phase were
formed gradually. After a definite period of time, the
reaction was terminated by cooling the reactor to room
temperature and adding sodium hydroxide aqueous
solution dropwise into the reactor to neutralize the

Received 2007-03-26, accepted 2007-12-24.

* Supported by the National Natural Science Foundation of China (No.20376004).
** To whom correspondence should be addressed. E-mail: licx@mail.buct.edu.cn

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Chin. J. Chem. Eng., Vol. 16, No. 1, February 2008

Figure 1 Experimental set-up

1reactants; 2reaction tube; 3condenser;
4thermostatic bath with magnetic stirring; 5water

residual HCl. The upper phase containing butyl chloride and butanol was weighed by a precision electronic balance and its composition analyzed by a gas
chromatography, while the amount of butyl chloride
dissolved in concentrated NaCl aqueous phase was
deemed as negligible. On this basis, the conversion of
butanol and yield of butyl chloride were calculated.
In order to evaluate the performance of catalysts,
batch reaction was carried out for two reactions,
namely reaction of t-butanol or n-butanol with hydrochloric acid at different conditions. For the reaction of
butanol (BuOH) with hydrochloric acid, the reaction
rate of t-butanol is much faster than that of n-butanol.
Hence, the reaction of t-butanol with hydrochloric
acid was conducted at room temperature, while the reaction of n-butanol was at reflux temperature, ca. 353
K. For both reactions, the molar ratios of the feedstock
were BuOHHCl = 11 and BuOHcat. = 10.15.
The gas chromatography used was Shimadzu
GC2010 equipped with FFAP column, 30 m0.53
mm1 m and a hydrogen flame ionization detector
(FID) and analyzed by the software GC solution. Carrier gas was N2. The temperature program started from
80C remained for 1 min, then increased to 140C by

10Cmin 1 and remained at 140C for 2 min. The

liquid composition was determined using the calibration curve method. For each sample, GC analysis was
repeated three times to obtain the average values.
3
3.1

RESULTS AND DISCUSSION

Reaction of t-butanol and hydrochloric acid

Experimental results concerning the evolution of

conversion of t-butanol and selectivity of t-butyl chloride over different catalysts were plotted in Figs. 2 and
3, respectively.
As seen from Fig. 2, the conversion of t-butanol
increases rapidly in first 5 h and then levels off, which
is common for all reversible reactions. Also it is noted
that the activity of the catalysts at the first 2 h follows
the order of [HPy]Cl [HMIM]Cl [BMIM]Cl
[BMIM][BF4]ZnCl2[HEt3N]Cl, implying that the
intrinsic catalytic activity of all organic ammonium
salts except [HEt3N]Cl is superior to the inorganic salt
ZnCl2, while for the long term performance, ZnCl2 is

Figure 2 Conversion of t-butanol vs. time with different

catalysts (reaction temperature 298 K, with molar ratio of
t-BuOHHCl11, t-BuOHcat.10.15 and t-BuOH
0.2 mol)
[MIM]Cl; [BMIM]Cl; [BMIM][BF4]; + [HPy]Cl;
[HEt3N]Cl; ZnCl2

Figure 3 Selectivity of t-butyl chloride vs. time with different catalysts (reaction temperature 298 K, with molar ratio
of t-BuOHHCl11, t-BuOHcat.10.15 and t-BuOH
0.2 mol)
[MIM]Cl; [BMIM]Cl; [BMIM][BF4]; + [HPy]Cl;
[HEt3N]Cl; ZnCl2

the best followed by [BMIM][BF4], [HMIM]Cl,

[HPy]Cl, [BMIM]Cl and [HEt3N]Cl. The latter trend
is likely attributed to the much lower activity of water
in ZnCl2 solution than in other ammonium solutions at
the same concentration, which favors the reaction
equilibrium toward the formation of BuCl and hence a
high conversion of butanol. The overall catalytic performance of [BMIM][BF4], [HMIM]Cl and [HPy]Cl
is comparable to that of traditional catalyst, ZnCl2.
Figure 3 indicates that the selectivity of t-butyl
chloride is basically a constant for all catalysts except
[HEt3N]Cl, for which the selectivity decreases gradually with time.
3.2

Influence of temperature

To investigate the influence of temperature on the

reaction of t-butanol and hydrochloric acid, some experiments were performed at 298 K, 313 K and 333 K,
respectively for 2 h. The experimental results were
shown in Figs. 4 and 5. It is shown that the conversion
of t-butanol increases with temperature, while the selectivity of t-butyl chloride is virtually independent of
temperature for all catalysts studied except [HEt3N]Cl.
In addition, the intrinsic catalytic performance of all
organic ammonium salts seems superior to the traditional catalyst, ZnCl2.

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Chin. J. Chem. Eng., Vol. 16, No. 1, February 2008

one. For both reactions studied, the overall catalytic

activity of organic ammonium salts is comparable to
that of ZnCl2, which suggests that the catalytic effect
is likely due to the ammonium cation while the influence of anion is of secondary importance.
3.4

Figure 4 Conversion of t-butanol vs. temperature for different catalysts (reaction time 2 h, molar ratio of t-BuOHHCl
11, t-BuOHcat.10.15 and t-BuOH0.2 mol)
[MIM]Cl; [BMIM]Cl; [BMIM][BF4]; + [HPy]Cl;
[HEt3N]Cl; ZnCl2

Influence of molar ratio of HCl/n-butanol

The influence of the relative amount of HCl on

the conversion of n-butanol was investigated by conducting the reaction for 10 h at reflux temperature and
varying molar ratio of HCl/n-BuOH with catalyst
[HMIM]Cl being 15% of the moles of n-BuOH. The
results were listed in Table 2. It was seen that the
highest conversion of n-butanol was achieved for the
stoichiometric molar ratio of HCl/n-BuOH, and other
ratios all gave rise to a reduction of conversion of butanol, because for the homogeneous reaction system,
excessive amount of any component could lead to a
dilution of other reactants and catalyst. The selectivity
of n-butyl chloride was irrespective of the ratio of
HCl/n-BuOH.
Table 2 Conversion of n-butanol (Cn-BuOH) and
selectivity of n-butyl chloride (Sn-BuCl) with
different molar ratio of HCl/n-BuOH

Figure 5 Selectivity of t-butyl chloride vs. temperature for

different catalysts (reaction time 2 h, molar ratio of t-BuOH
HCl11, t-BuOHcat.10.15 and t-BuOH0.2 mol)
[MIM]Cl; [BMIM]Cl; [BMIM][BF4]; + [HPy]Cl;
[HEt3N]Cl; ZnCl2

3.3

Comparison between n-butanol and t-butanol

The experiment results for the reaction of

n-butanol and hydrochloric acid as well as t-butanol
and hydrochloric acid under similar conditions were
listed in Table 1 for comparison. It is shown that the
conversion of t-butanol is about triple of that of
n-butanol, meanwhile the selectivity of t-butyl chloride is slightly better than that of n-butyl chloride,
which is closely related to the much higher stability of
the tertiary carbonic cation over that of the primary
Table 1 Conversion of butanol (CBuOH) and selectivity of
butyl chloride (SBuCl) with different catalysts
(36.5% hydrochloric acid)
Catalyst

n-Butanol reaction

t-Butanol reaction

Cn-BuOH

Sn-BuCl

0.63

0.153

0.955

0.80

0.156

0.954

1.00

0.157

0.954

1.20

0.146

0.956

1.50

0.139

0.958

2.00

0.137

0.96

Note: Molar ratio of n-BuOHcat.10.15, temperature 353 K,

reaction time 10 h, n-BuOH0.2 mol.

3.5

Influence of catalyst amount

Table 3 showed the influence of the amount of

catalyst, [HMIM]Cl, on the reaction. The experiments
were performed at reflux temperature for 10 h with the
stoichiometric amount of hydrochloric acid/n-butanol
and different molar ratios of catalyst to n-butanol. As
shown in Table 3, both conversion of n-butanol and
selectivity of n-butyl chloride increased slightly with
the increase of molar ratio of catalyst/n-BuOH.

Cn-BuOH

SBuCl

Ct-BuOH

SBuCl

ZnCl2

0.141

0.918

0.507

0.991

[HPy]Cl

0.145

0.948

0.49

0.982

[HEt3N]Cl

0.142

0.92

0.416

0.937

[HMIM]Cl

0.157

0.951

0.493

0.983

[BMIM]Cl

0.149

0.952

0.438

0.978

[BMIM]BF4

0.149

0.948

0.504

0.984

At 353 K for 10 h, n-BuOH0.2 mol, molar ratio of

n-BuOHcat.10.15 and n-BuOHHCl11.
At 298 K for 10 h, t-BuOH0.2 mol, molar ratio of
t-BuOHcat.10.15 and t-BuOHHCl11.

n(HCl/n-BuOH)

Table 3 Conversion of n-butanol (Cn-BuOH) and selectivity

of n-butyl chloride (Sn-BuCl) with different molar ratio of
catalyst/n-BuOH
n(cat./n-BuOH)

Cn-BuOH

Sn-BuCl

0.15

0.157

0.954

0.30

0.163

0.959

0.45

0.174

0.964

0.60

0.177

0.967

1.00

0.193

0.972

Note: Molar ratio of n-BuOHHCl11, temperature 353 K,

reaction time 10 h, n-BuOH0.2 mol.

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Table 4
Times

[HPy]Cl

Reusage of catalysts for the reaction of hydrochloric acid and n-butanol

[HEt3N]Cl

[HMIM]Cl

[BMIM]Cl

[BMIM][BF4]
Sn-BuCl

Cn-BuOH

Sn-BuCl

Cn-BuOH

Sn-BuCl

Cn-BuOH

Sn-BuCl

Cn-BuOH

Sn-BuCl

Cn-BuOH

1st

0.145

0.948

0.142

0.92

0.157

0.951

0.149

0.952

0.149

0.948

2nd

0.145

0.947

0.143

0.924

0.159

0.959

0.149

0.955

0.147

0.947

3rd

0.141

0.951

0.157

0.931

0.161

0.948

0.153

0.950

0.151

0.952

4th

0.146

0.943

0.139

0.916

0.157

0.961

0.152

0.948

0.148

0.957

5th

0.146

0.946

0.145

0.918

0.153

0.952

0.151

0.956

0.149

0.953

Note: molar ratio of n-BuOHHCl11, and n-BuOHcat.10.15, temperature 353 K, reaction time 10 h, n-BuOH0.2 mol.

3.6

Reuse of catalyst

Reuse of catalyst for reaction of n-butanol with

hydrochloric acid was carried out under the same conditions. That was, molar ratio of n-BuOHcat. = 0.15
1, molar ratio of n-BuOHHCl = 11, reflux temperature of n-butyl chloride at 351 K for 10 h. After
the first time reaction completed, the mixture were
dried in vacuum at 383 K for 10 h before next time
usage. The catalyst was reused for 5 times, and the
results of the reaction were listed in Table 4.
From the table, we can see that conversion of
n-butanol and selectivity of n-butyl chloride showed
no evident fluctuation, suggesting that all the ionic
liquid catalyst investigated can be reused in reaction
of butanol and hydrochloric acid. The general excellent stability of ionic liquids and the present results
suggest that ionic liquids investigated can be reused
for much more times.

12

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