ISSN 00231584, Kinetics and Catalysis, 2013, Vol. 54, No. 6, pp. 667670. Pleiades Publishing, Ltd., 2013.

Original Russian Text M.N. Makhin, L.N. Zanaveskin, G.S. Dmitriev, 2013, published in Kinetika i Kataliz, 2013, Vol. 54, No. 6, pp. 707710.

Kinetics of Propylene Glycol Hydrochlorination

M. N. Makhin*, L. N. Zanaveskin, and G. S. Dmitriev
Karpov Institute of Physical Chemistry, Moscow, 105064 Russia
*email: Makhin.Maxim@gmail.com
Received January 25, 2013

AbstractThe kinetics of hydrochlorination of propylene glycol with hydrogen chloride, both noncatalytic
and catalyzed by acetic acid, has been investigated. The type of kinetic equation, preexponential factor, acti
vation energy, and empirical coefficients characterizing the chloride ion hydration effect on the rate of pro
pylene glycol hydrochlorination have been determined.
DOI: 10.1134/S0023158413060074

The production of chemicals from renewable
resources is a promising trend in the chemical industry.
These technologies include the synthesis of propylene
oxide, which is widely used in the production of poly
urethanes, glycols, solvents, cosmetics, and medicines
[1, 2]. Propylene glycol, an agro waste recycling prod
uct [3], undergoes hydrochlorination to form  and
propylene chlorohydrins, which, in turn, are used in
the synthesis of propylene oxide:
C3H8O 2 + HCl
(I)
C3H 7OCl + C3H 7OCl + H 2O.
In process design for obtaining chemical products,
one of the most important problems is to optimize the
process by studying the kinetics of the reactions taking
place. Here, we report the kinetics of propylene glycol
hydrochlorinationdata that have been hitherto
lacking in the literature.
EXPERIMENTAL
The kinetics of propylene glycol hydrochlorination
was studied in a continuous mode in a 45mL glass
reactor equipped with a magnetic stir bar, a bubbler, a
reflux condenser, a thermocouple, and an electric
heater. The rotational speed of the stirrer was no less
than 1500 rpm, which ensured the absence of reagent
concentration and temperature gradients throughout
the reaction volume. The temperature inside the reac
tor was controlled and measured with, a TRM101 sin
glechannel microprocessorbased programmable
temperature controller and an external relay. The tem
perature measurement accuracy of the thermocouple
was 0.1. Propylene glycol (or a propylene glycol +
water or propylene glycol + catalyst mixture) was con
tinuously pumped into the reactor at a rate of 10
15 g/h. The water concentration in propylene glycol
was varied between 5 and 50 wt %; the acetic acid con
centration, between 0.5 and 9 wt %. Hydrogen chlo
ride was continuously introduced into the reactor
through the bubbler at a rate of 712 g/h. The HCl
flow rate was adjusted and maintained using a flow
meter and a manostat. The reaction products were dis
charged from the reactor through a side outlet having
a liquid seal. Only those experiments in which the
temperature variation was less than 1C and the mass
imbalance was no greater than 5% were taken into
consideration.
Organic products were analyzed on a gasliquid
chromatograph with a flameionization detector.
Hydrochloric and acetic acids were quantified by con
ductometric titration or acidbase titration in the
presence of phenolphthalein.
RESULTS AND DISCUSSION
It is known from the literature that the hydrochlo
rination of glycols proceeds via a bimolecular nucleo
philic substitution mechanism (S N2 ) [4] and can be
described by the rate equation
E
w = k0e RT CC3H8O2 CHCl, (1)
where C382 and HCl are the propylene glycol and
hydrogen chloride concentrations, respectively.
The experimental results obtained at 100 in a
wide reactant concentration range are given in the
table. Note that the product formation rate constants
depend on the water concentration in the reaction
mixture.
The slowdown of the reaction by water was noted in
many works dedicated to the hydrochlorination of
alcohols [511]. A kinetic study of glycerol hydro
chlorination [11] showed that the adverse effect of an
increase in the water concentration on the reaction
rate is due to its high solvating power.
In the hydrochlorination of propylene glycol, the
main species undergoing solvation is the chloride
anion resulting from HCl dissociation. This is
explained by the fact that the chloride anion is much

667
668 MAKHIN et al.

Selected parameters of propylene glycol hydrochlorination at 100C

Concentration, mol/L wi 105, mol L1 s1 ki 105, L mol1 s1
Entry
C3H8O2 HCl H2O C3H7OCl C3H7OCl C3H7OCl C3H7OCl C3H7OCl C3H7OCl
1 9.564 3.071 1.651 0.689 1.041 8.091 11.448 0.275 0.390
2 9.783 3.385 3.491 0.291 0.751 3.674 9.490 0.111 0.287
3 8.380 4.299 9.923 0.118 0.701 1.145 6.783 0.032 0.188
4 8.006 4.503 12.498 0.059 0.470 0.978 6.089 0.024 0.169
5 4.916 6.414 24.901 0.039 0.340 0.483 4.302 0.015 0.136

smaller than organic molecules and is fully charged.
According to the S N 2 mechanism, the ratelimiting
step in the hydrochlorination of propylene glycol is the
attack of a chloride anion hydrated according to reac
tion (II) on the propylene glycol molecule (III):
HCl nH 2O + H 2O H3O + Cl nH 2O, +
(II)
CH 3CH(OH)CH 2OH 2+ + Cl nH 2O
(III)
C 3H 7OCl + ( n + 1)H 2O.
The presence of a solvation shell around the chlo
ride anion and the number of water molecules in this
shell have the determining effect on the process rate.
The higher the concentration of water in the reaction
mixture, the larger the number of its molecules reacting
with the chloride anion and the stronger the hydration
shell of the anion and, as a consequence, the higher the
activation energy and the lower the reaction rate.
To describe the process, we introduced the coeffi
cient characterizing the degree of hydration of the
chloride anion, defined as the ratio of the water con
centration to the HCl concentration. Based on the
assumptions made, we considered the dependences of
the propylene chlorohydrin formation rate constant
calculated via Eq. (1) on the coefficient (Fig. 1). This
allowed determination of the reaction rate constants at
different temperatures at any = 04, the interval in
which propylene glycol hydrochlorination occurs. The
rate constants obtained in this way at a constant value
obey the Arrhenius equation. A typical example for = 2
is presented in Fig. 2.
Mathematical processing of the data plotted in
Fig. 2 allowed determination of the apparent activa
tion energy and preexponential factor. The rate equa
tion for the formation of propylene chlorohydrin at
= 2 is
166400 100
w = 7.89 1016 e RT
CC3H8O2 CHCl mol L1 s 1. (2)
The same processing of the experimental data in the
range from 1 to 3.5 showed that, with an increasing
degree of hydration of hydrogen chloride, there were
both a decrease in the rate constant and a noticeable
increase in the apparent activation energy (Fig. 3). The
plot shown in Fig. 3 is described by the equation
E = (140200 + 37760ln) 100 J/mol, (3)
and the preexponential factor is described by the equation
k0 = 4.76 1013 10.70 L mol1 s1. (4)
Thus, the formation of propylene chlorohydrin
in the temperature and concentration ranges exam
ined can be described in terms of the rate equation
wC3H7OCl = 4.76 10
13 10.70
(140200 +37760 ln ) 100 (5)
e RT
CC3H8O2 CHCl mol L1 s 1.

k 105, L mol1 s1 lnk [L mol1 s1]

0.5 13
0.4 5
14
0.3 4
3 15
0.2 2
1 16
0.1
17
2.60 2.64 2.68 2.72 2.76
0 1 2 3 4 5 1000/T, K1

Fig. 1. Propylene chlorohydrin formation rate constant

as a function of the degree of hydration of HCl at (1) 90, Fig. 2. Linearization of the Arrhenius equation for the for
(2) 95, (3) 100, (4) 105, and (5) 110C. mation of propylene chlorohydrin at = 2.

KINETICS AND CATALYSIS Vol. 54 No. 6 2013

 KINETICS OF PROPYLENE GLYCOL HYDROCHLORINATION 669

E, kJ/mol k 10 4, L mol1 s1
190 6
180
170 5
160 4
150
5
140 3
1.0 1.5 2.0 2.5 3.0 3.5 4
2 3
2
Fig. 3. Activation energy of the formation of propylene 1 1
chlorohydrin as a function of the degree of hydration of HCl.
0
0.5 1.0 1.5 2.0
The rate equation for the formation of propylene
chlorohydrin was Obtained in the same way:
Fig. 4. Rate constant of the formation of propylene
wC3H7OCl = 1.27 10 6 2.67 chlorohydrin as a function of the degree of hydration of

(83160 +9880ln ) 100 (6) HCl in the presence of the catalyst (acetic acid) at (1) 80,
1 1 (2) 85, (3) 90, (4) 95, and (5) 100C.
e RT
CC3H9O2 CHCl mol L s .
The study of the kinetics of propylene glycol hydro
chlorination showed that, in the absence of the cata Note that the catalyst changes the selectivity, mak
lyst, the reaction is too slow to be industrially imple ing the isomer dominant. The catalytic action of
mented. Acetic acid is known to be the best catalyst for acetic acid consists in the formation of propylene gly
hydrochlorination of glycols [1, 1216], and, in the col acetates whose aceto group is more readily
general case, the reaction rate is described by the replaceable by a chlorine atom than the initial
equation hydroxyl group. In accordance with the known mech
E anism of esterification [17], the process mainly yields
w = k0e RT
CC3H8O2 CHClCCH3COOH. (7) the ester and, consequently, propylene chlorohy
Taking into account the effect of hydration on the drin. Its formation selectivity in the catalytic hydro
reaction rate (see above), we found that the rate con chlorination of propylene glycol increases as is
stant of the catalytic formation of propylene chlorohy increased and does not depend on the temperature.
drins also depends on the degree of hydration of HCl Thus, the kinetics of noncatalytic and catalytic
(Fig. 4). hydrochlorination of propylene glycol was elucidated.
Mathematical processing of experimental data sug Its specific feature is that the reaction rate decreases
gests that the formation rates of  and propylene with an increasing water concentration in the reaction
chlorohydrins in the temperature and concentration mixture due to the hydration of the chloride anion.
ranges examined can be described by the equations This is the reason why, in the industrial implementa
(61360 +2940ln) 100 tion of the process, water should be removed from the

wC3H7OCl = 1.98 10 5 0.18
e RT reaction zone to accelerate the reaction.
(8)
1 1
CC3H8O2 CHClCCH3COOH mol L s ,
(65280 +16150ln ) 100
ACKNOWLEDGMENTS

wC3H7OCl = 1.35 10 5 4.62
e RT
(9)
This work was supported by State Contract
1 1
No. N.4b.45.90.11.1133 of April 12, 2011.
CC3H9O2 CHClCH3COOH mol L s .
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Translated by K. Utegenov
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