I n d . Eng. Chem. Res.

1994,33, 259-264 259

Kinetics of 1,2-Dichloroethane Formation from Ethylene and Cupric

Chloride
Shun Wachi' and Yousuke Asai
Kaneka Corporation, Takasago, Hyogo 676, Japan

The catalytic process of ethylene oxychlorination can be split into two steps, uiz.ethylene chlorination
with the reduction of cupric chloride and reoxidation of the cuprous chloride by hydrogen chloride
and oxygen. The transient process of 1,2-dichloroethaneformation was observed by selected ion
chromatography using a mass spectrometer. While the reaction exhibited first-order kinetics in
regard to the concentration of cupric chloride, the dependency on ethylene concentration was
interpreted by a Langmuir-Hinshelwood mechanism. Optimal performance was achieved by
impregnating ea. 5 w t 76 of copper into y-alumina powder, and 64% of the copper contained in the
alumina powder contributed to the formation of 1,2-dichloroethane,

Introduction
Oxychlorination of ethylene has been widely applied to
the industrial process of vinyl chloride manufacturing,
where the intermediate product of 1,2-dichloroethane is
prepared from ethylene, hydrogen chloride, and oxygen
as
C,H4 + 2HC1+ -
'/,O, C,H4C1, + H,O.
Since the chemical reaction is catalyzed by the Deacon
catalyst, Le., cupric chloride on an aluminasupport, it was
once assumed that the reaction proceeds with the pro-
duction of chlorine uia the Deacon reaction and the
subsequent addition of chlorine to ethylene (Allen, 1962):
2HC1+ '/,02 C1, - + H,O
2CuC1+ 2HC1+ '/,O, - 2CuC1, + H,O. (5)
Advantages of this dual-step reaction process over the
conventional one would include efficient separation of
waste effluenb from the product stream, prevention of
the flammable mixture of ethylene and oxygen, and
improvement of the reaction yield. The first advantage
(1)
would certainly contribute to cleaner production tech-
nology in terms of environmental protection, otherwise
extensive treatment of chlorinated hydrocarbon in effluent
air would be required. The dual-step reaction should be,
then, practically performed in the two-vessel reactor with
the circulation of catalyst particles such as fast fluidized
bed or moving bed. While the flow dynamics of catalyst
particles in the reactor system is another point to be
addressed, a detailed study of the reaction kinetics in eqs

-
(2)
C,H, + C1, C2H4C1,. (3)
The chlorinating agent is, however, thought not to be
chlorine but to be copper chloride, where the adsorption
of ethylene is the rate-controlling step (Arganbright and
Yates, 1962). The formation of 1,2-dichloroethane was
observed by the impulse injection of ethylene into a packed
bed of cupric chloride (Kominami et al., 1965; Hall et al.,
1984). The catalyst used for the oxychlorination reaction
contained chlorides of Cu(1) and Cu(II), as detected by
X-ray studies (Todo et al., 1966). The formation of 1,2-
dichloroethane was attributed to the valency change of
the copper as
C2H4 + 2CuC12 -.t C2H4C12 + 2CuC1. (4)
A rather different interpretation was reported by Carrubba
and Spencer (1970) who stated that the chemical reaction
proceeded via an intermediate complex of ethylene oxide.
As the mixture of reactant gas was contacted with large
catalyst pellets, ca. 5 mm, the rate-controlling mechanism
could be different from the elemental step of eq 4. The
majority of the kinetic studies on this system has been
dedicated toward the investigation of oxychlorination with
the mixed supply of ethylene, hydrogen chloride, and
oxygen (Kominami et al., 1966;Todo et al., 1966;Miyauchi
et al., 1968; Arcoya et al., 1982).
Essential improvement in the process performance,
however, could be achieved by the introduction of a two-
step reaction system, where the regeneration of cuprous
chloride is conducted separately:
* Address correspondence to this author.
0888-5885/94/2633-0259$04.50/0
4 and 5 should be essential for process-engineering
purposes. To measure kinetics of individual reaction steps,
impulse reactor methods have been employed (Kominami
et al., 1965; Allen and Clark, 1971; Hall et al., 1984), but
the concentration of gaseous reactant is hardly clarified
in these types of experiments. Much information on the
kinetics, then, would be obtained by applying an alter-
native dynamic method with stepwise supply of reactant,
where each component of the reactor effluent is contin-
uously analyzed by means of a mass spectrometer (Muller
and Hofman, 1987).
The present work investigated the kinetics of 1,2-
dichloroethane formation from ethylene and cupric chlo-
ride. The effect of ethylene concentration was observed
quantitatively by the continuous supply of the gaseous
reactants to the bed of cupric chloride. Transient response
of 1,Bdichloroethane concentration was directly measured
by a mass spectrometer with a selected ion-chromatograph
mode.
Experimental Section
The experimental apparatus is schematically described
in Figure 1. The reactor tube was made of stainless steel
(SUS 316 L), 4 mm in inside diameter and 50 mm in length.
Approximately 0.57 g of catalyst was packed in the reactor
with glass wool at both ends. The reactor was placed in
an oven to maintain the temperature between 423 and 523
K. Streams of gaseous reactants were fed through mass-
flow controllers (SEC400, Stec Inc.) at flow rates up to
1.33STPcm3/seach, and the streams of hydrogen chloride
and oxygen were then combined. Using a 4-port valve,
the gaseous supply to the reactor was switched from the
mixture of hydrogen chloride and oxygen to ethylene or
0 1994 American Chemical Society
260 Ind. Eng. Chem. Res., Vol. 33, No. 2, 1994

02

HC I

C2H4

He

He

VP
Figure 1. Experimental apparatus: FC, flow controller; 4PV, 4-port valve; RE,reactor; OV, oven; SP, separator; CGT, capillary glass tube;
MS, mass spectrometer; PC, personal computer: and VP,vacuum pump.

vice versa. The concentration of the gaseous reactants

was controlled by dilution with helium at the feeding rate
up to 2.67 STPcm3/s. Further amounts of helium, 6.67 /0' (m.n.42)
STPcm3/s, were added to the reactor effluent to reduce
the delay in the chromatograph due to tubing volume and
to dilute the gases. A part of the mixture was continuously
introduced into a mass spectrometer (QP-2000,Shimadzu
Co.) through a capillary glass tube, 0.25 mm in inside
diameter and 500 mm in length. This apparatus, together
with a further separation system (WIF-30, Shimadzu Co.),
supplied an appropriate rate of gas to the detector, and
the pressure of the vacuum chamber was maintained at 0 100 200 300 400
0.00133 Pa. Each component of the reactor effluent was Is1
independently analyzed by a specific ion-chromatography Figure 2. Transient profiles of selected ion chromatographs: (I)
mode at the corresponding mass number: 62 for 1,2- production of 1,2-dichloroethane (mn = 62) by the stepwise intro-
dichloroethane, 28 for ethylene, 36 for hydrogen chloride, duction of ethylene (mn = 28) and (11) production of water (mn =
18) by the stepwise introduction of an oxygen (mn = 32)-hydrogen
32 for oxygen, and 18 for water. The intensity of each chloride (mn = 36) mixture.
chromatograph was converted to the molar flow rate, which
is calibrated by the injection of standard sample. The
rest of the reactor effluent was fed into an absorber,
maintaining the reactor at atmospheric pressure.
The catalyst was prepared by immersing y-alumina
powder (MSC-lA, Mizusawa Chemical Co.) into an
aqueous solution of cupric chloride. Particle density of
the y-alumina powder was 1369 kg/m3, while the solid
density was 3075 kg/m3. The particles had a median
diameter of 51.9 pm and an internal surface area of 221 000
m2/kg determined by a Coulter counter (Coulter Elec-
tronics, Model TA 11)and the BET method, respectively.
The amount of copper loaded into the alumina carrier was
4.23 wt %, i.e., 993 mol/m3, determined by an atomic t [SI
spectrometer. Different amounts of copper impregnation Figure 3. Transient profiles of 1,2-dichloroethane formation fol-
were also prepared by altering the concentration of the lowing the stepwiseintroduction of ethylene at various temperatures.
copper chloride solution. Fresh catalysts thus prepared
were pretreated in the reactor tube, maintained at 473 K, The formation of water detected at a mass number of 18
for around 20 h with a helium atmosphere. indicates the oxidative chlorination of cuprous chloride
to produce cupric chloride. The formation of 1,Bdichlo-
Results and Discussion roethane and water are reproduced in turn by switching
the supply of gaseous reactants. The present observation
Typical ion chromatographs observed by the step supports the chemical reaction scheme of eqs 4 and 5 rather
injection of reactants over the packed catalyst reactor are than the mechanisms via an intermediate of ethylene oxide.
illustrated in Figure 2. The stepwise supply of ethylene Figure 3 shows chromatographs of 1,2-dichloroethane
was monitored at mass number 28, and the resulting formation started by the stepwise introduction of ethylene
production of 1,2-dichloroethane was detected as the peak at various temperatures. The higher the temperature, the
at mass number 62. Eventually, the chemical reaction faster the reduction of cupric chloride was completed. The
ceases because of the complete reduction of the cupric amount of 1,Zdichloroethane produced was obtained by
chloride. Afterwards, the mixture of hydrogen chloride integration of the chromatograph data and plotted in
and oxygen was supplied to the reactor instead of ethylene. Figure 4. Regardless of the reaction temperature or the
 Ind. Eng. Chem. Res., Vol. 33, No. 2, 1994 261
, ,

w
C,H,CI, / CUCI, = 0.32 .
-14
1
-13 F '

.
" " ' " ' ' ' ' " " ' ' ' ' " ' " "1

A
L j;
11
0

11- C, 0.427[ mol / m 3 ]

1.227
4.294
J -15 :

-16 4.29 mol / m3

0
450 500 550
T [Kl
Figure 4. Amount of 1,2-dichloroethaneproducedper mole of copper
loaded on catalyst.

concentration of ethylene, approximately 0.32 mol of 1,2- 0 523 K

dichloroethane was produced per mole of cupric chloride
supported in the alumina. The relationship of eq 4
corresponds to the formation of 0.5 mol of 1,2-dichloro-
ethane/mol of cupric chloride, and 64% of the copper
effectively participated in the chemical reaction. It is
presumable, then, that among the total copper loaded on
the y-alumina powder, the chemical reaction is limited to
some extent of mixed cuprous-cupric chloride or, alter-
natively, some fraction of copper is geometrically inac-
cessible to ethylene.
The gradual decay of 1,2-dichloroethane formation,
shown in Figures 2 and 3, may suggest that the reaction
rate is dependent on the amount of unreacted cupric
chloride, while the concentration of ethylene is maintained
constant through out the reaction. The assumption of
first-order kinetics to the concentration of cupric chloride
leads to the rate equation as
r = - -dCc
-
dt
-
kCc
where Cc represents the concentration of cupric chloride
effective to the chemical reaction. Given the initial value,
ie., Cc = Co at t = 0, eq 6 can be integrated. According
to eq 4, a mole of 1,2-dichloroethane should be produced
by the consumption of 2 mol of cupric chloride. Neglecting
the accumulation in the reactor, the entire amount of
reaction product should be detected at the effluent of the
reactor as
Vr = 2FC,.
Then, combination of eqs 6 and 7 leads to:
VkC,
c, =-2F exp(-kt).
Experimental chromatographs of 1,2-dichloroethane for-
mation are shown in semilogarithmic scale in Figure 5.
Except for a slight delay in the response signal at the very
beginning of the ethylene supply, the linear curve can be
represented by the relationship of eq 8, while the latter
part of the curve is less accurate due to the increased ratio
of noise to signal. Thus, the assumption is justified that
the reaction rate is first order with respect to the
concentration of cupric chloride. According to eq 8, the
value of the reaction rate constant k can then be deter-
mined from the slope of the straight line at the range of
the chromatograph peak ratio of 0.2 to 0.8.
Values of the reaction rate constant were plotted as a
function of ethylene concentration in Figure 6: the higher
the reaction temperature, the greater the value of the rate
constant. The rate constant also increases with an increase
'1 473 K
C A 453 K
0 423 K
-. 0.031 ,f
0 5 10 15
C, [ mol / m3 ]
Figure 6. Effect of ethylene concentration on the reaction rate
constant; solid lines represent Langmuir-Hinshelwood kinetics by
eq 10.
in the ethylene concentration, approaching an asymptotic
value. Although the kinetic analysis of the pulse injection
method assumes first-order dependency on the concen-
tration of ethylene (Kominami et al., 1965;Allen and Clark,
1971; Hall et al., 1984), linear dependency seems to hold
at low concentrations only. The concentration dependency
observed in this experiment suggests that the reaction is
closer to Langmuir-Hinshelwood kinetics, where the
chemical reaction proceeds between cupric chloride and
molecules of ethylene adsorbed onto the catalyst. Given
the adsorption equilibrium of Langmuir type, the chemical
reaction rate can be described as:
(7)
k$aCECC
r=
+ KaCE
Combination of eqs 6 and 9 leads to the following
(8) relationship:
To examine this relationship, the data points appearing
in Figure 6 were transformed to the Langmuir plot in Figure
7. At eachtemperature,the plot of l/k against 1/CE could
be represented by a linear curve drawn in the figure. Solid
lines in Figure 6 were also drawn to represent the
corresponding curves in Figure 7.
Before drawing conclusions about the kinetic mecha-
nism, the rate-controlling step of 1,Zdichloroethane
formation must be considered. Figure 8 shows values of
the reaction rate constant k determined by eq 8 on the
basis of trials at various retention times of reactant gas,
VIF. Data points measured in a longer reactor tube, Le.,
180mm, are also plotted in the figure. At fixed conditions
262 Ind. Eng. Chem. Res., Vol. 33, No. 2, 1994
/:
-
" !
400 F
05 1 15
1 c, [ rn3 m o l ]
Figure 7. Langmuir plot of the reaction rate constant; solid lines
represent Langmuir-Hinshelwood kinetics by eq 10.
0 01 I
c: reactor length =180mm
- 0 reactor length = 50mm
01 I I
0.1 1 10
V/ F [SI
Figure 8. Effect of the retention time of the reactant gas on the
determination of the reaction rate constant (T= 453 K, CE = 2.58
moi/m3).
of reaction temperature and ethylene concentration at the
reactor inlet, the determined value of the rate constant
decreases with increasing retention time. This result can
be explained by the fact that the apparent value of the
rate constant decreases due to consumption of ethylene
used in the formation of 1,2-dichloroethane. The reaction
rate should now be evaluated as a function of ethylene
concentration in the reactor instead of that at the reactor
inlet as
Combining this equation with eqs 6 and 7 allows the
transient profile of 1,2-dichloroethane concentration to
be numerically predicted. Thus, the predicted value of k
can then be calculated from eq 8 and plotted in the figure
as a solid line. It is indicated both by the data points and
by the calculated line that the effect of ethylene con-
sumption is negligible for shorter retention times of less
than 1 s. The accumulation term is also negligible in eq
7 because the rate constant exhibits almost a constant
value at the retention times of less than 1s. The simplified
analysis employed in the present study is useful to discuss
the concentration dependency shown in Figure 6, while
the comprehensive analysis (Muller and Hofman, 1987)is
required for the general conditions.
The mass-transfer resistance of the gas film layer at the
outer surface of the y-alumina particle is most likely
negligible, since the change of gas flow rate hardly affects
the rate cosntant. The role of intraparticle diffusion of
ethylene can be evaluated by calculating the ratio of the
observed rate of 1,2-dichloroethane formation to the
maximum flux of ethylene diffusion into the porous particle
as
/
k, = 269 exp(-37.8/RT)
-6
2
0.0019 0.002 0.0021 0.0022 0.0023 0.0024
l / T [liK]
Figure 9. Arrhenius plot of the chemical reaction rate constant.
1
m
Y n 1
42 = akCc - (2.59 X 105)(0.04)(993)(0.64) -
(D$a)C, [(O.22 x 10-5)/(2.59x 106)](10)
7.75 x 104, (12)
where the value of effective diffusivity is estimated by
Since the value of q5 is far smaller than unity, Le., 0.027,
the intraparticle diffusion is rapid compared to the reaction
rate. However,the kinetic rate measured for larger catalyst
pellets, Le., around 5 mm (e.g., Carrubba and Spencer,
19701, might be limited by the diffusion of ethylene but
shoud not be used for data when estimating the chemical
reaction mechanism.
The reaction rate constant shown in Figure 7 would
then represent the chemical reaction between ethylene
and cupric chloride without being limited by diffusion
resistance. According to the relationship of eq 10, then,
the values of kr and K, are determined from the intercept
Ilk, and the slope l/krKa of the line, respectively. Values
of the chemicalreaction rate constant k,and the absorption
equilibrium constant K, are plotted against temperature
in Figures 9 and 10, respectively. The rate constants of
1,2-dichloroethane formation in eq 8 are correlated as
k, = 269 exp - -
( E,
K, = 0.63. (15)
The slope of the Arrhenius plot gives the activation energy
of the chemical reaction as 37.8 kJ/mol. While the
equilibrium constant of ethylene adsorption K, is inde-
pendent of temperature, the activity of the adsorption
site seems to be enhanced by an increase in temperature
(Hall et al., 1983; Baker and Holstein, 1983). In the rate

0.4 , . . , , . , . . , . . . . , . . . . 0.02
T = 473 K
c, = 2.34 mol / m3
-] 0015
t to the formation of 1,2-dichloroethane.
0 - 0
0 5 10 15 20
copper concentration [ wt % ]
Figure 11. Effect of copper concentration on the formation of 1,2-
dichloroethane.
expression of eq 9, however, the contribution of the
adsorption capacity should reflect to the chemical reaction
rate constant k,. The present value of activation energy
is in good agreement to those reported by Hallet al. (1984)
and Kitamura (1986),whereas Miyauchi et al. (1967) and
Allen and Clark (1971) obtained much larger values of
activation energy, 63 and 79 kJ/mol, respectively. Since
Miyauchi et al. (1967) prepared the catalyst by the
coprecipitation of copper and alumina, the large activation
energy value could be due to a different orientation of the
cupric chloride. Since the precipitates of cupric chloride
employed by Hall et al. (1984) had relatively small surface
area, i.e., 3200 m2/kg, compared to that supported on
alumina, the value of the reaction rate constant was also
accordingly small. The reaction rate could be limited by
the migration of chlorine or ethylene, as the cupric chloride
impregnated on y-alumina could not disperse in mono-
layers but in the form of solid blocks of crystals.
Finally, the reaction kinetics were examined for various
catalysts containing different amounts of cupric chloride.
In Figure 11,the reaction rate constant k and the amount
of 1,2-dichloroethane produced are plotted against the
copper concentration in the catalyst. The optimal per-
formance in terms of both the rate constant and the amount
of 1,2-dichloroethane formed was achieved at the copper
concentration of 993 moi/m3, or ca. 5 wt % of copper
impregnated in y-alumina. Coincidentally, the ethylene
oxychlorination catalyst exhibited maximum activity at
6 wt % of copper supported on a-alumina together with
potassium chloride (Arcoya et al., 1982). If the reduction
of copper is chemically limited to some extent of mixed
cuprous-cupric chloride, the ratio of cuprous-cupric might
remain constant irrespective of copper concentration. It
is presumable, then, that the fraction of effective copper
is determined by some sort of geometrical factor rather
than the chemical nature. Since the aqueous solution of
copper chloride was accordinglydiluted for the preparation
of the lower concentration catalyst, the slow nucleation of
copper precipitation onto the surface of y-alumina would
eventually form crystals of large size. The decrease of
1,2-dichloroethane production might be due to the inac-
cessibility of the reactant molecules into the inside of the
large crystal of copper. On the other hand, a large increase
in copper loading again reduced the rate constant of the
chemical reaction. It could be due to either the blockage
of the y-alumina micropores or the multilayer orientation
of the copper.
Conclusions
The oxidation and reduction processes in the oxychlo-
rination of ethylene can occur independently. While
cuprous chloride is oxidized by hydrogen chloride and
oxygen in the former step, the reaction between cupric
Ind. Eng. Chem. Res., Vol. 33, No. 2, 1994 263
chloride and ethylene produces 1,2-dichloroethane in the
latter step. The present experiment toward the latter step
of the chemical reaction, Le., the formation of 1,2-
dichloroethane, indicated that the reaction rate is first
order on the concentration of unreacted cupric chloride
and that the dependency on ethylene concentration obeys
Langmuir-Hinshelwood kinetics. Optimal performance
was achieved by copper impregnation of ca. 5 wt % into
y-alumina, where 64% of the supported copper contributed
Acknowledgment
The authors are indebted to Mr. C. Witjes on leave from
the Chemical Engineering Department, Dortmund Uni-
versity, for undertaking the preliminary experiment during
the student-training program at Kaneka Corporation.
Nomenclature
a = particle radius, m
CC = effective concentration of cupric chloride in catalyst,
m01/m3
CD = concentration of 1,2-dichloroethanein gas phase, mol/
m3
CE = concentration of ethylene in gas phase, mol/m3
Ci, = CE at reactor inlet, m0l/m3
CO = initial value of CC, m0l/m3
De = effective diffusivity, m2/s
D, = molecular diffusivity of gas, m2/s
F = flow rate of gas, m3/s
k = first-order reaction rate constant, l / s
k , = chemical reaction rate constant, l/s
K , = adsorption equilibrium constant, m3/m0l
r = chemical reaction rate based on the volume of catalyst
particle, mol/s/m3
R = gas constant, kJ/mol/K
t = time, s
T = temperature, K
V = volume of catalyst, m3
Greek Letters
t = porosity
T = tortuosity factor
6 = Thiele modulus
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