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Synthesis of Epichlorohydrin (Kinetic)
Synthesis of Epichlorohydrin (Kinetic)
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;
EPCH NaOH H2 O
catalyst
C3 H8 O3 HCl ! C3 H6 Cl2 O
H2 O
! C3 H8 O3 NaCl
(1)
C3 H6 Cl2 O NaOH
! C3 H5 ClO NaCl H2 O
(3)
(2)
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
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)
1
(b a)
h
1
ai
ln
(k0 k/ ) (k0 kt )
b
kt k/
(5)
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
Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A12): 15801585
(7)
1582
MA et al.
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.
(9)
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)
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
Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A12): 15801585
1583
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
(10)
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:
(11)
Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A12): 15801585
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.
363.15
458.80
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)
353.15
280.65
(13)
NOMENCLATURE
a
b
A
CNaOH
E
Ea
k1
k2
Ke
Ke0
mm
[OH-]
[DCP]
[EPCH]
r1
r2
rdehy
rhydr
R
t
T
Greek symbols
kt
k0
Trans IChemE, Part A, Chemical Engineering Research and Design, 2007, 85(A12): 15801585
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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