J. Chem. Chem. Eng.

5 (2011) 1179-1182

Hydrochlorination of Glycerol--The Role of the Water on

the Process

Georgy Dmitriev Sergeevich* and Leonid Zanaveskin Nikolaevich

Karpov Institute of Physical Chemistry, Federation State Unitary Organization, row Obuha, 3-1/12, building 6, Moscow 105064,
Russia

Received: August 01, 2011 / Accepted: September 06, 2011 / Published: December 10, 2011.

Abstract: In the present study the investigation of the glycerol hydrochlorination process has been presented. It is shown that water
concentration strongly affects the reaction rates. It deals with the phenomenon of hydration. The kinetic parameters of the reactions
have been determined.

Key words: Glycerol, hydrochlorination, dichlorohydrin, kinetics, hydration.

1. Introduction alternative rout. It is more environmental-friendly and

economically feasible. Gl is a by-product of the
The hydrochlorination of glycerol is the first step of
large-scale biodiesel production. Gl is cheap and
the epichlorohydrin production from glycerol.
available; above all, it is produced from natural
Epichlorohydrin (EPCH) is a valuable and important
renewable resource.
chemical for industry and national economy. The
The estimated production of EPCH proceeds in two
production of EPCH in the world exceeds 1.5 million
main steps. In the first step, Gl is hydrochlorinated to
ton per year. About 85 percent of EPCH are converted
the mixture of ,- and ,-dichlorohydrins. In the
into epoxy resins. They are used in the production of
second step, this mixture is dehydrochlorinated to
vanishes, paints, powder coatings, adhesives and so on.
EPCH (Scheme 2).
Besides, EPCH and its derivatives are used in the
It is known that hydrochlorination of glycerol should
production of ion exchange resins, surface active
be carried out at atmospheric pressure and temperature
agents, plasticizers, insecticides and a lot of other
range 100-140 C. Gaseous hydrogen chloride or its
goods [1-2].
aqueous solution can be used as chlorination agent.
The production of EPCH has been practiced since
Carboxylic acids are used as catalysts, for example,
1947 and it is based on propylene (Scheme 1) [3]. This
acetic acid.
process has some undesirable features, for example,
There are a number of articles and patents which
raw dependence on oil, low selectivity of reactions and
deal with this process [4-12]. And all of them state that
consequently significant amount of organic withdrawal
water has a negative effect on the process by means of
(up to 0.5 t/t EPCH) and large amount of polluted
equilibrium. But it contradicts with some
sewage (up to 54 t/t EPCH).
investigations where it is proved that hydrochlorination
The synthesis of EPCH from glycerol (Gl) is an
of glycerol is irreversible process [6]. Water can be part
of raw glycerol or hydrogen chloride. And it is also a
*
Corresponding author: Georgy Dmitriev Sergeevich, product of reactions. The role of the water on the
postgraduate student, research fields: organic products, kinetics
and technology. E-mail: dmitriev.gs@mail.ru. process is a very important question but there is no
1180 Hydrochlorination of Glycerol-The Role of the Water on the Process
Scheme 1 Synthesis of epichlorohydrin from propylene.
Scheme 2 Synthesis of epichlorohydrin from glycerol.
definite answer in the literature. The understanding of
the water role can help us to realize the mechanism of
the process and the ways to control the reaction rates.
2. Equipment, Analyses and Operating
Conditions
The experiments were carried out in continuous
mode in glass reactor, equipped with stirrer, electric
heater and reflux condenser. The concentration of
water in the feed mixture with glycerol had variations
from 1.6% to 40% by weight. Acetic acid was used as
catalyst. Organic products were analyzed by the gas
chromatograph. Determination of hydrochloric acid
and acetic acid was carried out with the help of
conductivity measurement device.
3. Results and Discussion
It is commonly known that hydrochlorination of
alcohols is a reversible process described by
bimolecular nucleophilic substitution (SN2)
mechanism. It was found that hydrochlorination of
glycerol is irreversible process [13].
Therefore, the hydrochlorination of glycerol is to be
described by the second order equation:
r k CGl HCl (1)
We used this equation in our investigation of
non-catalytic reaction. But it was found that kinetic
constant decreases with the increase of water
concentration, namely, with the increase of molar ratio
between water and hydrogen chloride. Obtained data
are presented in Fig. 1.
The obtained results may be explained by the
phenomenon of hydration [14-15].
There are polar organic compounds in the reaction
mixture such as glycerol and chlorohydrins. They may
orientationaly interact and form hydrogen bonds both
with each other and with molecules of water. But there
are chlorine anions in the same mixture. They bring
negative charge and have small radius. Molecules of
water may hydrate both glycerol (chlorohydrins) and
chlorine anions. But it is clear that chlorine anions are
hydrated most strongly. Redistribution of negative
charge takes place in such hydrated chlorine anions.
The more molecules of water are in such complexes,
the less the density of surface charge is.
Anions, hydrated with one, two, three and more
molecules of water, are different reagents and each of
them has its own kinetic constant.
So, the experimental curves represent the
dependence of kinetic constant on the degree of
chlorine anion hydration and they are described by the
following kinetic equation:
 Hydrochlorination of Glycerol-The Role of the Water on the Process 1181

4,5

4,0

3,5

3,0
117
k 105, l/(mols)

2,5

2,0
110
1,5
110
1,0
90
0,5
80
0,0
0,4 0,6 0,8 1,0 1,2 1,4 1,6 1,8 2,0 2,2 2,4 2,6 2,8 3,0
2/HCl
Fig. 1 Dependence of kinetic constant on the molar ratio between water and hydrogen chloride for the reaction of -MCH
formation at temperatures 80-117 C.

HCl ( a bT ) HCl ( a bT )
r k 0 e ( E / RT ) ( ) Gl HCl (2) r k0 e( E / RT ) ( ) Gl HCl AcA (3)
H 2O H 2O
where a and b are empiric coefficients. Catalytic rates were calculated as difference between
There is the factor of molar ratio between hydrogen observed rates and non-catalytic rates. It was found that
chloride and water in the empiric power. It non-catalytic rates are less than 3% of the observed
characterizes the effect of hydration. This factor rates. That is why the investigation of ,-DCH and
depends on the temperature and reduces with its ,-DCH formation was carried out only in the
increase. So the influence of the hydration on the presence of catalyst. The formation of ,-DCH and
reaction rates decreases at higher temperatures. And it ,-DCH is described by the following kinetic
is logical because of increase of system entropy and equation:
loosening of intermolecular bonds. HCl ( a b T )
r k0 e ( E / RT ) ( ) - MCH HCl AcA (4)
The values of pre-exponential factor, activation H 2O
energy and empirical coefficients for the reactions The values of pre-exponential factor, activation
of -MCH and -MCH formation are presented in energy and empirical coefficients for the catalytic
Table 1. reactions of -MCH, -MCH, ,-DCH and ,-DCH
Investigation of glycerol hydrochlorination in the formation are presented in Table 2.
presence of catalyst results in the similar kinetic
Table 2 The values of pre-exponential factor, activation
equation for the -MCH and -MCH formation:
energy and empirical coefficients for the catalytic reactions
Table 1 The values of pre-exponential factor, activation of -MCH, -MCH, ,-DCH and ,-DCH formation.
energy and empirical coefficients for the reactions of Reaction number corresponds to the one in the Scheme 2.
-MCH and -MCH formation. Reaction number Reaction No k0, l2/(mol2s2) , J/mol b
corresponds to the one in the Scheme 2. 1 1.24 1011 86000 25.63 0.056
Reaction No k0, l/(mols) , J/mol b 2 1.38 1010 91500 13.36 0.026
1 2.1 109 102000 10.5 0.023 3 2.51 104 47000 35.74 0.084
2 2.2 1012 132000 14.7 0.034 4 1.62 108 92000 16.85 0.038
1182 Hydrochlorination of Glycerol-The Role of the Water on the Process
The presented equations are empiric and are true at
molar ratio between water and hydrogen chloride:
from 0.5 (half) to 3 for non-catalytic reactions and
from 1 to 6 for catalytic reactions.
The above mentioned range of molar ratio between
water and hydrogen chloride for the catalytic reactions
was used in our investigation because the
hydrochlorination of glycerol proceeds in these
conditions.
4. Conclusion
The hydrochlorination of glycerol to isomeric
monochlorohydrins and dichlorohydrins were
investigated. It was determined that these reactions are
irreversible. But water has a negative effect on the
reaction rates. We suppose that it deals with the
phenomenon of hydration.
Small chlorine anions are in the reaction mixture in
the hydrated state. And the hydration degree very
strongly affects the reaction rates.
We obtained the kinetic equations for the studied
reactions. They include the factor of molar ratio
between hydrogen chloride and water which
characterizes the phenomenon of hydration.
So an appropriate solution was found. The reactions
are irreversible but water content strongly affects the
reaction rates by hydration. And we found out its
interconnection with kinetics.
References
[1] Oschin, L. A. Chemistry: Industrial Chlororganic
Products; Moscow, 1978.
[2] Product Stewardship Manual, Safe Handling and Storage;
Dow: Epichlorohydrin, May 2007.
[3] Oschin, L. A. Chemistry: Production of Synthetic
Glycerol; Moscow, 1974.
[4] Tesser, R.; Santacesaria, E.; Serio, M. Di; Nuzzi, G. Di;
Fiandra, V. Kinetics of Glycerol Chlorination with
Hydrochlorid Acid: A New Route to ,-dichlorohydrin.
Ind. Eng. Chem. Res. 2007, 46, 6456-6465.
[5] Bell, B. M.; Brigs, J. R. Glycerin as a Renewable
Feedstock for Epichlorohydrin Production. The GTE
Process: Clean 2008, 36(8), 657-661.
[6] Luo, Z. H.; You, X. Z.; Li, H. R. A Kinetic Model for
Glycerol Chlorination in the Presence of Acetic Acid
Catalyst. Korean J. Chem. Eng. 2010, 27(1), 66-72.
[7] Lim, J. H.; Song, W. S.; Woo, S. Y.; Lee, D. H. Kinetic
Model of Glycerol Chlorination with Hydrochloric Acid.
Korean J. Chem. Eng. 2010, 27(3), 785-790.
[8] Zhao, Z.; Qiao, X.; Tang, J. H.; Cui, M. F. Discrimination
of by-Products and Analysis of Reaction Mechanism in
Preparation of Dichloropropanol from Glycerol. The
Chinese Journal of Process Engineering 2008, 8(6),
1098-1102.
[9] Method for Converting Polyhydroxylated Aliphatic
Hydrocarbons into Chlorohydrins. Patent US2008194848,
Solvay, 2008.
[10] Process for Producing Dichloropropanol from Glycerol,
the Glycerol Coming Eventually from the Conversion of
Animal Fats in the Manufacture of Biodiesel. Patent
WO2005054167, Solvay, 2005.
[11] Method of Producing Dichloropropanols from Glycerol.
Patent RU2356878, 2009.
[12] Conversion of a Multihydroxylated-Aliphatic
Hydrocarbon or Ester Thereof to a Chlorohydrin. Patent
WO2006020234, 2006.
[13] Lebedev, N. N. Chemistry: Chemistry and Technology of
Basic Organic and Petrochemical Synthesis; Moscow,
1988.
[14] Reichardt, C. Solvents and Solvent Effects in Organic
Chemistry; Mir: Moscow, 1991.
[15] Schmid, R.; Sapunov, V. N. Non-Formal Kinetics; Mir:
Moscow, 1985.