SYNTHESIS OF EPICHLOROHYDRIN

FROM DICHLOROPROPANOLS
Kinetic Aspects of the Process
L. Ma, J. W. Zhu
, X. Q. Yuan and Q. Yue
Institution of Chemical Engineering, East China University of Science and Technology, Shanghai,
200237, China.

Abstract: The reactions involved in the industrial production of epichlorohydrin from dichloropropanols (DCP, including 1,3-dichloro-2-propanol and 2-3-dichloro-1-propanlol) have been kinetically investigated. The kinetics of dehydrochlorination of DCP has been studied in the presence
of caustic soda, by potentiometric techniques. The kinetic parameters of the reactions have been
determined. The epichlorohydrin hydrolysis has been studied by measuring the decrease of the
reagents during the time using titration. The whole study indicate that both dehydrochlorination
and hydrolysis reaction can be considered as second order kinetic reaction. It is also indicated
that the kinetic constant for dehydrochlorination reaction is far bigger than that for hydrolysis
reaction in the same conditions.
Keywords: dichloropropanol;
activation energy.

epichlorohydrin;

INTRODUCTION

Correspondence to:
Professor J.W. Zhu,
Institution of Chemical
Engineering, East China
University of Science and
Technology, Shanghai,
200237, China.
E-mail: jwzhu@ecust.edu.cn

DOI: 10.1205/cherd07061
02638762/07/
$30.00 0.00
Chemical Engineering
Research and Design
Trans IChemE,
Part A, December 2007
# 2007 Institution
of Chemical Engineers

kinetics;

dehydrochlorination;

hydrolysis;

equations (1) and (2) (Braun, 1932, 1943;

Fairbourne et al., 1930; Horsley, 1965):
The basic medium necessary for the
second reaction can be obtained by using a
caustic soda solution, afforded by Huayi
Group, Shanghai. Together with the dehydrochlorination reaction, hydrolysis always
occurs, according to the scheme:

Originally, epichlorohydrin(EPCH; IUPAC

name:1-chloro-2,3-epoypropane) was formed
by Berthelot in 1854 (Berthelot and Luca,
1856), and by Clarke and Hartman (1941),
using caustic soda for hydrolysis with the
product of the reaction happened between
hydrogen chloride and crude glycerol.

EPCH NaOH H2 O
catalyst

C3 H8 O3 HCl ! C3 H6 Cl2 O
H2 O

! C3 H8 O3 NaCl
(1)

But the hydrolysis reaction lowers the yields;

EPCH must be removed as quickly as possible from the reaction environment. The dehydrochlorination reaction is performed in a
distillation column, and EPCH is ashed out
with stream to shorten the contact time to
prevent hydrolysis.
Designing suitable reactors for dehydrochlorination reaction and the distillation
column and choosing the optimal operating
conditions require the determination of
kinetic parameters for the reactions involved
in the process and the evaluation of
vapourliquid equilibrium data. But both the
kinetics of dehydrochlorination and hydrolysis
in this process are also poorly described in
literatures.
In the present paper, the kinetics of dehydrochlorination of DCP and the hydrolysis of

C3 H6 Cl2 O NaOH
! C3 H5 ClO NaCl H2 O

(3)

(2)

At present, energy source shortages caused

obtaining chemical materials from biomass,
and it was successful. Because of the high
price of the petroleum, the glycerol process
of producing EPCH has lower cost than the
synthesis from petroleum products. And
now, the process of producing EPCH from
glycerol was considered by many big chemical groups, such as SOLVAY, DOW,
DUPONT, SHANG HAI HUAYI GROUP, and
so on. Then, EPCH will be mainly prepared
in industry from the DCP, followed by
dehydrochlorination of DCP, according to
1580

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SYNTHESIS OF EPICHLOROHYDRIN FROM DICHLOROPROPANOLS

EPCH have been studied, both in the presence of caustic
soda.

EXPERIMENTAL
Equipment, Reagents and Operating Conditions
Both the kinetics of dehydrolorination and hydrolysis reactions was studied in presence of caustic soda. Dehydrochlorination of DCP in aqueous basic solution is a fast reaction
occurring with the elimination of hydrogen chloride. In a
dilute caustic soda solution, the reaction rate has been determined by using a glass complex electrode to measure the
decrease of conductivity of the solution with time according
to the method described by Jin et al. (2005). The conductivity
varies with concentration of ions in the dilute electrolyte solution, and was recorded by the conductivity recorder with
the measure accuracy of 0.01 mS cm21 and the response
time of 0.01 s, which make sure that the conductivity
measurement system has high control accuracy. The temperature control device shown in Figure 1 makes sure of the
temperature-control with the measure accuracy of 0.01 K.
The dehydrochlorination reaction took place in a thermo
stated stirred batch reactor. Fifty millilitres of basic solution
containing about 0.01 mol L21 of NaOH was put into the reactor. When the reaction temperature was reached, 0.25 ml of
the organic reagent was injected into the solution using a
glass syringe, and the potentiometric response was
recorded. Runs made with the two pure dichloropropanols
isomers (1,3-DCP and 2,3-DCP) have shown identical reactivity. The kinetic data collected in this paper refer to an industrial mixture of the two isomers mentioned. The main
component of these mixtures is 1,3-DCP, with little 2,3-DCP
only (Krafft et al., 2005).
Hydrolysis reaction was studied in a different procedure.
The reactor for hydrolysis reaction study is almost the
same as the reactor shown in Figure 1 but with different
dimensions: diameter of 100 mm, height of 100 mm, and
the diameter of the anchor-like agitator is 45 mm. The

temperature control device is also the same as the one

used in dehydrochlorination reaction study. Since this is a
very slow reaction, the reaction rate was determined by
using titration to measure the decrease of the hydroxyl ion
concentration as a consequence of the reaction, and the
reaction took place in a thermo stated stirred batch reactor.
Three hundred millilitres of basic solution containing about
0.2 mol L21 of NaOH was put into the reactor. When the reaction temperature was reached, one equivalent of EPCH per
equivalent of base was used. Runs were made in the temperature range of 322.85 K344.25 K and in the rotation rate
range of 270 410 r min21.

RESULTS
Dehydrochlorination Reaction
In the dehydrochlorination reaction, the hydroxyl ion concentration decreases rapidly during the reaction, and
caused the conductivity decrease rapidly, which was
recorded by the conductivity recorder. The experimental
results, in fact, can be well represented by assuming a
second order kinetic model, of the type:
r1 k1 OH  DCP

(4)

The whole data processing was taken according to the

method mentioned by Li (2004).
Let
M

1
(b  a)



h
1
ai
 ln
 (k0  k/ )  (k0  kt ) 
b
kt  k/

(5)

The experimental data were obtained for runs made in

different operating conditions and the kinetic constants
have been calculated on the basis of the second order kinetic
model.
Figure 2 shows the values of M versus time for the dehydrochlorination reactions made at different temperatures.
The linearity of the curves justies the assumption of the
second order for dehydrochlorination reaction, and we determined the constant k by the slope of the straight line.
Figure 3 shows the exponential-like variation of the kinetic
constant with the temperature, compared with Figures 712
in literature (Hu, 1999), we can conclude that the dehydrochlorination reaction obeys the general reaction kinetics.
In Figure 4, an Arrhenius plot for this reaction is also
reported. From Figure 4, one can compare the kinetic constants of the reaction in different temperature range:
293 K  313 K and 313 K  333 K. According to the Arrhenius equation (Laidler, 1987a; Kooij, 1893)
k AeEa=RT

Figure 1. Conductivity measurement device: (1) conductivity recorder; (2) temperature recorder; (3) thermocouple in the reactor near
the wall; (4) glass complex electrode; (5) thermocouple for the tin
bath; (6) glass syringe; (7) oil; (8) anchor-like agitator with the diameter of 20 mm; (9) agitator to churn up the oil; (10) cylinder reactor
with the diameter of 50 mm, the height of 50 mm and four bafes to
strengthen the mixing effect; (11) temperature control device.

1581

(6)

One can calculate the values of Ea and A for each temperature range, respectively. We can then conclude that the dehydrochlorination reaction rate in the presence of caustic soda
in different temperature ranges can be expressed as:
293 K  313 K:
r1 1:77  107 e41,000=RT DCPOH  

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(7)

1582

MA et al.

Figure 2. A plot of M versus time for the dehydrochlorination reaction

performed in the temperature range of 293 K 333 K: reaction made
in caustic soda solutions with [OH-] 0.01 mol L21, [DCP] 0.05
mol L21; the kinetic constants have been calculated assuming a
second order kinetic model.

313 K  333 K:
r1 8:97  1020 e123,200=RT DCPOH  

(8)

Hydrolysis Reaction
Hydrolysis of EPCH lowers the yields of the process. It is
important to know the kinetic parameters of this reaction.
At rst, the inuence of rotation rate on hydrolysis reaction
in the reactor was studied, and the kinetic data of the hydrolysis reaction obtained at different rotation rate at 333.55 K
were shown in Table 1. The rotation rate was measured by
the digital infrared tachometer.
In Table 1, the value of the kinetic constant did not vary with
the value of the rotation rate. This indicates that the inuence
of rotation rate on hydrolysis reaction in the reactor could be

Figure 4. The Arrhenius plot for the kinetic constants of the dehydrochlorination reaction: reaction made in caustic soda solutions with
[OH-] 0.01 mol L21, [DCP] 0.05 mol L21.

neglected, and the reactor could be considered as a well

stirred batch reactor.
Runs were then made in the temperature range of
322.85 K  345.25 K at the rotation rate of 271 r min21. The
kinetic constant for the hydrolysis reaction can be calculated
by the determination of the decrease of the hydroxyl ion concentration. Both of the initial concentration of NaOH and
EPCH are 0.2314 mol L21.
The kinetic constants have been calculated on the basis of
the second order kinetic model. The experimental results can
be well represented by assuming a second order kinetic
model, of the type:
r2 k2 OH  EPCH

(9)

Figure 5 shows the values of 1/CNaOH versus time for runs

made at different temperatures. The linearity of the curves
justies the assumption of the second order for the hydrolysis

Table 1. Kinetic data of the hydrolysis reaction obtained at different

rotation rate at 333.55 K: the kinetic constants have been calculated
assuming a second order kinetic model; both of the initial concentration of NaOH and EPCH are 0.2314 mol L21.
N(r min21)
170

271

408
Figure 3. A plot of k versus time for the dehydrochlorination reaction
performed in the temperature range of 293 K 333 K: reaction
made in caustic soda solutions with [OH-] 0.01 mol L21,
[DCP] 0.05 mol L21.

Time (min)

[OH-] (mol L21)

k (L mol21min21)

0.00
2.00
6.00
10.00
14.00
18.00
0.00
2.750
7.30
11.00
15.00
20.60
0.00
3.50
8.30
15.00
22.00

0.2314
0.1871
0.1393
0.1089
0.09114
0.07565
0.2314
0.1747
0.1261
0.1026
0.08350
0.06539
0.2314
0.1630
0.1172
0.08450
0.06589

0.4944

0.5054

0.4929

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SYNTHESIS OF EPICHLOROHYDRIN FROM DICHLOROPROPANOLS

1583

Table 2. Kinetic data obtained for hydrolysis reaction at 318.3 K: with

the rotation rate at 271 r min21.
T (K)
318.3

Time
(min)

[OH-]
(mol L21)

[EPCH]
(mol L21)

k (L mol21
min21)

0
1.00
6.00
11.33
17.30
22.00

0.1097
0.1088
0.09929
0.09074
0.08400
0.07797

0.1316
0.13078
0.12122
0.11267
0.10593
0.09990

0.1379

DISCUSSION

Figure 5. A plot of 1/CNaOH versus time for the EPCH hydrolysis

reaction with the rotation rate at 271 r min21: the kinetic constants
have been calculated assuming a second order kinetic model; both
of the initial concentration of NaOH and EPCH are 0.2314 mol L21.

reaction. In Figure 6, an Arrhenius plot for the kinetic constant

of hydrolysis reaction is also drawn. The kinetic parameters,
including Ea and A, for hydrolysis reaction are also calculated
from the data shown in Figure 6. Then, the kinetic expression
of EPCH hydrolysis reaction can be simplied as follows:
r2 5:66  1010 e70 790=RT EPCHOH  

(10)

To prove that equation (10) could be well applied for the

description of hydrolysis reaction, another run was also conducted at different conditions (both for temperature and the
initial concentration of NaOH and EPCH) from the runs
shown in Figure 5. The reaction results show in Table 2.
The hydrolysis reaction kinetic constant at 318.3 K was calculated according to equation (10). And the calculated value
of k is 0.1354, which is almost the same as the experimental
value in Table 2, with the relative error of 1.81%, which is less
than 5%. This means equation (10) could be well applied for
the description of hydrolysis reaction.

The experiments described in this paper, allowed the determination of the kinetic parameters of the reactions involved in
the EPCH production process. The rates of reactions
involved in the progress are identical, as has been seen
experimentally.
The Boltzmann factor Ea/RT is considered as the statistical distribution of energies among the reacting molecules.
And the pre-exponential factor A represents the rate of
activated molecules converting into the product molecules
(Laidler, 1987b). Both the activation energy and preexponential factor are temperature dependent. In fact, the
activation could vary with the temperature, but could be considered as changeless at a certain temperature range, and it
was also shown in Figure 4. Apparently, the rate of activated
molecules converting into product molecules at temperature
range 313 K  333 K is big than that at the temperature
range 293 K  313 K. But in the hydrolysis reaction,
the Arrhenius plot is linear; the activation energy was a
constant at the experimental temperature range.
For the EPCH formation, the ring closure reaction, occurs
according to an internal nucleophilic substitution (SN2) mechanism preceded by a base catalyzed dissociation equilibrium.
It is belong to the Williamson reaction (Williamson, 1852;
Ullmann and Sponagel, 1905; Dermer, 1934; Allen and
Gates, 1945; Baker and Martin, 1960; Fieser and Fieser,
1961), and is similar to the reaction happens between propylene chlorohydrins and caustic soda, as described by Patai
(1967), Weissberger (1964) and Eldereld et al. (1950).
The reaction mechanism can be represented as follows:

Protonation of the hydroxyl makes a better C O HO C

group. This step is very slow and reversible. This is the rate
determining step. The lone pairs on the oxygen make it a
Lewis base. Simultaneous formation of C OC bond and
cleavage of the CCl bond allows the loss of the good leaving group, a neutral water molecule.
The reaction rate, in this case is
rdehy k  Ke  OH  R

Figure 6. An Arrhenius type plot for the kinetic constant k2.

(11)

where k is the kinetic constant and Ke is the equilibrium

constant for the formation of the intermediate ion. [R] is the
reagent concentration. The reaction strongly depends on
this equilibrium constant and therefore depends also on the
enthalpy change for the intermediate ion formation. The two

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1584

MA et al.
Table 3. The ratio between the dehydrochloriantion reaction rates and the hydrolysis reaction rates.

Temperature/K
Ratio

293.15
63.55

313.15
29.14

333.15
96.13

DCP isomers which can give EPCH, have the different reactivity. Apparently, in the reaction mentioned in progress, the
reactivity of 1,3-DCP is much higher than the reactivity of
2,3-DCP. This is due to the inductive effects (Clarki et al.,
1989) and space effect. In the structure gure, both halogenoalkyls in 1,3-DCP increased the chlorine mobility or the
negative charge on the oxygen, and the hydroxyl could
attack 1-C, and 3-C, but only one halogenoalkyl in 2,3-DCP
could increase the negative charge on the oxygen, and the
hydroxyl could only attack 2-C. At the same time, it is hard
for the hydroxyl to attack 2-C in 2,3-dicloropropanol due to
the space effect (Salaun, 2000), which is even not exist in
1,3-DCP.

So the probability of intermediate ion formation is evidently

not the same. And the activation energy value for the dehydrochlorination reaction in the presence of caustic soda is
equal to the true activation energy (E) plus the enthalpy
change (DHR ) in intermediate ion formation, that is:
Eapp E DHR

363.15
458.80

Although decreasing the temperature is also good for

improving dehydrochlorination reaction rate when the reaction temperature is below 313.15 K, the absolute reaction
rate is low; and such kind of low temperature is not practical
in industrial producing.

CONCLUSION
(1) Both of the dehydrocholorination reaction and hydrolysis
reaction were proved to be the second order kinetic
reaction, and could be well described by the second
kinetic model, which could be applied in reactor design
and reaction simulation, obtained in this paper.
(2) In the high temperature range (313.15 K 363.15 K),
enhancing temperature is good for dehydrocholorination
reaction, but it will also enhance the hydrolysis reaction
rate.
(3) If we consider the high temperature of 363.15 K, which is
the reaction temperature in industrial process, and for low
contact time, yields of EPCH could hardly be affected by
the hydrolysis reaction. Therefore, low contact time is one
of the important factors during designing the distillation
column and choosing the optimal operating conditions
for the process of synthesis of EPCH from DCP.

(12)

The hydrolysis or ring opening reaction is a base catalysed

reaction occurring according to the scheme suggested by
Patai (1967) and Sakakibara et al. (1992).

For this mechanism, kinetic law of the following type is

justied:
rhydr k 0  Ke0  OH  R

353.15
280.65

(13)

where k0 is the kinetic constant, K e0 is the equilibrium

constant, and [R] is the organic reagent concentration.
Finally, according to the kinetic model obtained, that is,
equations (8) and (10), assuming that the initial concentration
of DCP and EPCH were the same, the ratio between
the dehydrochloriantion reaction rates and the hydrolysis
reaction rates were calculated, as shown in Table 3.
In Table 3, apparently, it indicates that enhancing temperature is good for improving dehydrochlorination reaction rate
when the reaction temperature is above 313.15 K, but it will
also enhance the hydrolysis reaction rate, therefore a suitable reaction temperature should be considered in the industrial production. But for a low contact time, the problem could
be solved, because for a low contact time, the probability of
hydrolysis reaction was greatly reduced, which means that
the yields of EPCH could hardly be affected by the hydrolysis
reaction (Carra et al., 1979).

NOMENCLATURE
a
b
A
CNaOH
E
Ea
k1
k2
Ke
Ke0
mm
[OH-]
[DCP]
[EPCH]
r1
r2
rdehy
rhydr
R
t
T

the initial concentration of caustic soda in

dehydrochlorination reaction, mol L21
the initial concentration of DCP in dehydrochlorination
reaction, mol L21
preexponential factors of dehydrochlorination reaction, 1
concentration of caustic soda, mol L21
true activation energy for the EPCH synthesis, J mol21
apparent activation energy, J mol21
kinetic constant of dehydrochlorination reaction,
L mol21s21
kinetic constant of hydrolysis reaction, L mol21min21
equilibrium constant for the formation of the
intermediate ion during dehydrocholorination reaction, 1
equilibrium constant for the formation of the
intermediate ion during hydrolysis reaction, 1
millimeter, 1
hydroxyl ion concentration, mol L21
dichloropropanols concentration, mol L21
epichlorohydrin concertration, mol L21
reaction rate of dehydrochlorination reaction,
mol L21s21
reaction rate of hydrolysis reaction, mol L21min21
reaction rate of dehydrochlorination reaction,
mol L21s21
reaction rate of hydrolysis reaction, mol L21s21
general constant of gases, J mol21K21
time, min or s
absolute temperature, K

Greek symbols
kt
k0

the conductivity of solution in dehydrochlorination

reaction at any time, mS cm21
the initial conductivity of solution in dehydrochlorination
reaction, mS cm21

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SYNTHESIS OF EPICHLOROHYDRIN FROM DICHLOROPROPANOLS

k/
DHR

the innite conductivity of solution in

dehydrochlorination reaction, mS cm21
enthalpy change in intermediate ion formation during
the synthesis reaction, KJ mol21

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ACKNOWLEDGEMENT
The authors wish to acknowledge the nancial support by Shanghai
Huayi (Group) Company.
The manuscript was received 20 April 2007 and accepted for
publication after revision 16 August 2007.

Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A12): 15801585