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

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
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. rate constants obtained in this way at a constant value
According to the S N 2 mechanism, the ratelimiting obey the Arrhenius equation. A typical example for = 2
step in the hydrochlorination of propylene glycol is the is presented in Fig. 2.
attack of a chloride anion hydrated according to reac Mathematical processing of the data plotted in
tion (II) on the propylene glycol molecule (III): Fig. 2 allowed determination of the apparent activa
tion energy and preexponential factor. The rate equa

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

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

0.5 13
0.4 5
0.3 4
3 15
0.2 2
1 16
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.



E, kJ/mol k 10 4, L mol1 s1
190 6
170 5
160 4
140 3
1.0 1.5 2.0 2.5 3.0 3.5 4
2 3
Fig. 3. Activation energy of the formation of propylene 1 1
chlorohydrin as a function of the degree of hydration of HCl.
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.
1 1
CC3H8O2 CHClCCH3COOH mol L s ,
(65280 +16150ln ) 100

wC3H7OCl = 1.35 10 5 4.62
e RT
This work was supported by State Contract
1 1
No. N.4b. of April 12, 2011.
CC3H9O2 CHClCH3COOH mol L s .
The hydrochlorination of propylene glycol in the
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