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Model Evaluation for an Industrial Process of

Direct Chlorination of Ethylene in a Bubble-
Column Reactor with External...

Article in Chemical Engineering Science January 2001

DOI: 10.1016/S0009-2509(00)00255-4

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 Chemical Engineering Science 56 (2001) 513}522

Model evaluation for an industrial process of direct

chlorination of ethylene in a bubble-column reactor with external
recirculation loop
JoaqumH n A. Orejas*
Universidad Nacional de Rn& o Cuarto, Facultad de Ingeniern& a, Ruta Nac. 36, Km. 601 } 5800, Rn& o Cuarto, Argentina

Abstract

An industrial process for the direct chlorination of ethylene at low temperatures to yield 1,2-dichloroethane has been considered.
The reactor, whose con"guration corresponds to a bubble column with external recirculation loop, has a working capacity of 19 m
and a production capacity of 54 000 tons of 1,2-dichloroethane per year. In order to describe its operation, the predictions from
a model developed in a previous work were evaluated using a special analysis of experimental data. This enables to obtain both
a model and a numerical simulation program which not only predict various performance variables with satisfactory relative errors
but also have the capacity of representing the in#uence of changes in operating conditions adequately within the entire technically
feasible operating range.  2001 Elsevier Science Ltd. All rights reserved.

Keywords: Ethylene chlorination; 1, 2-Dichloroethane production; Bubble-column loop reactor; Airlift reactor; Chemical reactor

1. Introduction In a recent work (Orejas, 1999), a model and a numer-

Most of the technologies that have been developed to
obtain vinyl chloride monomer make use of a balanced
process starting from ethylene, chlorine and oxygen,
where the reaction of direct chlorination of ethylene is
employed to yield 1,2-dichloroethane (EDC). At present,
70% of the licences issued for this process are concerned
with technologies that perform the direct chlorination of
ethylene at low temperatures (Hydrocarbon Processing,
1997). Although there are various designs in use for the
reactor where this reaction takes place, the information
published in the open literature is scarce. The "rst models
proposed for this reaction were developed by Balasub-
ramanian, Rihani and Doraiswamy (1966) and Chua and
Ratcli!e (1971). SzeH pvoK lgyi and Ujhidy (1978) and Wachi
and Morikawa (1986) studied the kinetics of the chemical
reactions involved. Wachi and Morikawa (1987) ana-
lysed a process of direct chlorination at high temper-
atures in a pilot-scale bubble column with external loop
that operated at EDC's boiling point, its working capa-
city amounting to 0.9 m.
* Corresponding author. Tel./fax: #54-0-358-4676246.
E-mail address: jorejas@ing.unrc.edu.ar (J. A. Orejas).
ical simulation program that describe the operation of
a process for the direct chlorination of ethylene at low
temperatures were presented. The industrial reactor,
which is a bubble column with external recirculation
loop, has a working capacity of 19 m, yielding approx-
imately 54 000 ton/yr of EDC. Only with parameters
obtained from literature, without adjustments of any
kind, the simulation results satisfactorily approximate, in
terms of relative errors, the experimental values of di!er-
ent performance variables, obtained in trials accomp-
lished in a process plant for a wide range of operating
conditions.
In this work, the previously developed model and
numerical simulation program were evaluated, in order
to establish their capacity to represent adequately the
e!ects of the variations in the operating conditions, for
the di!erent variables that represent reactor perfor-
mance. It could be observed that even though in relative
error terms the predictions yielded by the program were
extremely satisfactory, there were di$culties when trying
to predict the conversion of one of the main reactants.
This made it necessary to carry out a parametric sensibil-
ity analysis followed by parameter adjustment. Further
consequences of parameter adjustment were analysed for
all the variables of interest and their in#uence in both the

0009-2509/01/$ - see front matter  2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 0 9 - 2 5 0 9 ( 0 0 ) 0 0 2 5 5 - 4
514 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522
model structure and the numerical simulation program
are described. In this way, an accurate model and a trust-
worthy numerical simulation program could "nally be
accomplished. In addition to predicting di!erent perfor-
mance variables with satisfactory relative errors, these
tools have the capacity of representing the in#uence of
the variations in the operating conditions adequately for
all the technically feasible operative range.
2. Process description
Fig. 1 shows the con"guration of the industrial reactor.
Ethylene and chlorine, both in gaseous state, are fed to the
reactor through di!erent distributors. These substances
are dissolved and di!used, reacting in liquid phase (EDC
'98% ww) to yield more EDC. The existing di!erence in
density between heterogeneous and thermal-exchange
zones enables the recirculation of the liquid phase in the
direction shown in the "gure, thus making it possible to
control the reaction temperature (50}703C) by means of
the heat exchanger located in the right branch. Under
industrial operating conditions, the main reaction is the
addition of chlorine to ethylene's double bond. The impor-
tant secondary products are 1,1,2-trichloroethane (ETC)
and hydrogen chloride (HCl). The presence of ferric chlor-
ide (FeCl ), which is soluble in the reaction medium,

favours the selectivity in EDC.
3. Model evaluation
Several experiments were carried out in order to assess
the capacity of the proposed model and the correspond-
Fig. 1. Diagram of the reactor.
ing numerical simulation program to represent how
changes in operating conditions a!ect the predictions
of the reactor's performance. The eight operating
conditions described in Table 1 were chosen for this
purpose.
The selected sets of conditions comprise the complete
variation range which is technically feasible for the vari-
ables that de"ne reactor's operation (Fig. 1). Experiment
6, in particular, was the one that had been considered in
detail in a previous paper (Orejas, 1999).
The numerical simulation program was employed for
each set of operating conditions so as to describe the
reactor's operation and the resulting predictions
were compared with the experimental data obtained
from the industrial reactor. The following performance
variables were considered in the analysis: EDC in the
liquid product, EDC and O in the gaseous e%uent, ETC

production, chlorine and ethylene conversions, amount
of heat exchanged and recirculation rate.
By way of illustration, the accuracy of the predictions
can be visualised in Figs. 2}4, where the estimated values
were plotted against experimental results for ETC pro-
duction, Cl and C H conversions, respectively. The
  
numbers 1}8 assigned to each estimated value refer to the
corresponding experiment in Table 1.
In terms of relative errors, it is clear from Figs. 2}4 that
the program's predictions are extremely satisfactory. Re-
sults of similar quality were obtained for all the other
performance variables that were analysed.
In Fig. 4, however, it can be observed that the simula-
tion program is unable to represent the in#uence of
changes in the operating conditions on the ethylene con-
version, because it predicts 100% conversion for all the
experiments, which is in total disagreement with the
corresponding experimental values.
In the next section it is described how this limitation
can be analysed in order to overcome it, thus improving
the proposed model.
4. Causes of the predicted errors in C H conversion
 
As mentioned above, the simulation program fails to
predict the right relationship between the sets of vari-
ables that de"ne reactor operation and the ethylene con-
versions. Since the experimental data were reliable, the
root of the problem must basically lie somewhere within
the model employed for the process representation,
which should, therefore, be reviewed in detail as the "rst
step of the analysis.
The model proposed to describe the reactor's opera-
tion (Orejas, 1999) consists of two main parts: the
heterogeneous zone (the left branch in Fig. 1) and the
thermal-exchange zone (the right branch in Fig. 1). The
models for these sections are complemented by a global
mechanical-energy balance that enables the prediction of
 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522 515

Table 1
Operating conditions employed in eight experiences

Experiment P (k Pa) (K) Chlorine (kg s\) Ethylene (kg s\) Inert (kg s\);10
-. -.
1 215.35 341.41 1.121 0.439 2.778
2 196.96 335.41 1.657 0.687 2.222
3 260.72 330.44 1.676 0.674 1.389
4 199.41 341.26 1.657 0.677 1.389
5 261.94 342.31 1.114 0.428 1.389
6 260.72 341.30 1.704 0.659 2.778
7 261.94 327.16 1.102 0.428 2.778
8 199.41 327.16 1.102 0.425 1.389

Fig. 4. Ethylene conversion.

Fig. 2. ETC production predictions.

perimental values for the recirculation rate, temperature

and composition of the liquid phase as boundary condi-
tions at the distributors zone (i.e., at z"0 in Fig. 1) were
carried out. The predictions thus obtained for ETC pro-
duction, C H and Cl conversions were highly similar
  
to those yielded by the complete model, thus showing the
lack of in#uence of the model for the thermal-exchange
zone on the conversions. So, in view of these results, it
could be stated that the estimated errors in ethylene
conversion were exclusively due to problems in the model
proposed to describe the heterogeneous zone.

4.1. Parametric sensitivity of the heterogeneous zone model

In order to determine the parameters which should be

Fig. 3. Chlorine conversion.
the recirculation rate for the liquid phase inside the
reactor.
The model for the thermal-exchange zone does not
a!ect the predictions of C H conversion because it has
 
experimentally been determined that the e!ects of chem-
ical reactions on this section are negligible (Orejas, 1999).
For further con"rmation, runs of the model for the het-
erogeneous zone (Orejas, 1999, Eqs. (1)}(28)) using ex-
adjusted to improve the ethylene conversion predictions,
a parametric sensibility analysis on the model that
represented the heterogeneous zone was carried out.
Experiment 4, where the model gave results with an
intermediate error for the ethylene conversion, was con-
sidered (see Fig. 4). Numerical simulations of the
behaviour in the heterogeneous zone were accomplished,
employing the experimental values for the recirculation
rate and for the corresponding liquid-phase composition
and temperature at the position z"0 (Fig. 1). The max-
imum and minimum errors reported in the literature for
516 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522
Fig. 5. E!ects of the model parameters on the ethylene conversion
prediction.
the selected expressions to evaluate the di!erent para-
meters of the model were introduced for these runs.
In Fig. 5, the experimental value is compared with the
estimations yielded by the model when supposing vari-
ous errors by excess (blank bars) or by defect (shaded
bars) for di!erent parameters of the model. The predic-
!X
 X
!X

tions were obtained for $50% deviations in the initial
X
bubble-size estimation (d );$30%, in the total gaseous
TQ
volumetric fraction (1e 2);$20%, in the liquid-phase
!P

% # 2!#
mass transfer coe$cient prediction (k );#130 and
* 2!#
#280%, in the gas-phase mass transfer coe$cient pre-
diction (k ) and $30%, in the mass axial dispersion
% above, supposing that the heterogeneous zone operates
coe$cient evaluation (D ). Finally, the results obtained
+X
by increasing the activation energy of the main reaction
(E ) in 5% (shaded column at the far right of the "gure)
 stants were obtained as a result of the adjustment:
and 7% (blank column at the far right of the "gure) have
been included in this "gure. The main conclusion of the
analysis is that the kinetic parameters are the only ones
that a!ect the predicted ethylene conversion signi"cantly.
At this point it is important to remark that the kinetics
employed in the simulation program was the one, deter-
mined by SzeH pvoK lgyi and Ujhidy (1978). It was chosen for
this work because it is the only one published up to now
that quanti"es the temperature, the secondary reaction
and the catalyst e!ects. However, the temperatures for
which it was developed range from 287 to 313 K, while
the industrial reactor of interest in this paper operates
between 327 and 342 K. Therefore, it is reasonable to
expect certain deviations when using those parameters
outside the original temperature range. Taking into
account the fact that they also proved to be sensitive
variables, i.e. those that most signi"cantly a!ected ethy-
lene-conversion predictions, the kinetic parameters were
selected as adjustment variables.
5. Adjustment of the kinetic parameters
Within the entire operating range, the di!erences in
temperature between the gas-phase distributors level and
the top of the reactor, respectively, corresponding to
z"0 and in Fig. 1, are only about 6 K. Therefore, the
possibility of simplifying the problem of adjusting the
kinetic parameters by employing a simpli"ed model for
the heterogeneous zone that considered that the whole
section operated isothermally at an average tempera-
ture which corresponded to the arithmetic mean between
the temperatures at z"0 and was evaluated. The
predictions from the simpli"ed model were compared
with those yielded by the original one for that zone. Since
similar results were obtained for ETC production as well
as for Cl and C H conversions, the simpli"ed model
  
was adopted and the parameter adjustment problem was
formulated as follows:
Given the kinetics:
C H #Cl PEDC, R "k C C ,
     ? @
C H #2Cl PETC#HCl, R "k C C,
     ? @
"nd values for k and k that minimise the following
 
objective function:



X
X(k , k )" ? ? # @ @
  X
? @


P
2!# (1)
P
for each one of the operating conditions considered
isothermally.
The following expressions for the reaction rate con-
k "11493.0 exp(!2156.58/) m kmol\ s\, (2)

k "8.517;10 exp(!7282.21/) m kmol\ s\. (3)

Figs. 6 and 7 show Arrhenius plots where the predic-
tions from Eqs. (2) and (3) (continuous lines) are com-
pared with the best values obtained for each operating
condition (squares). Apart from the results that corres-
pond to the experiments reported in Table 1, the estima-
tions for four additional operating conditions were also
included so as to have more information about the in#u-
ence of the temperature. The straight lines that corres-
pond to the extrapolation of the kinetics reported by
SzeH pvoK lgyi and Ujhidy (1978) were also plotted in these
"gures.
It can be noticed that globally, the dispersion of the
values of the adjusted constants around the regression
straight lines (Eqs. (2) and (3)) is somewhat important.
This is to be expected because in this interpretation the
errors from all sources, such as those introduced by the
other model parameters and even the experimental er-
rors, are being attributed solely to these two constants.
Nevertheless, the magnitude of these deviations is not
signi"cant when the straight lines given by Eqs. (2) and
(3) are compared with the extrapolation of the kinetics by
 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522
Fig. 6. Arrhenius plot for k .

Fig. 7. Arrhenius plot for k .
 adjusted kinetics can be employed to quantify the in#u-
SzeH pvoK lgyi and Ujhidy (1978). It is interesting to note
that, for example, in order to improve an error of less
than 0.9% in the prediction of the ethylene conversion,
the values of the kinetic constants had to be lowered
between 6 and 24 times for the main reaction and be-
tween 7 and 14 times for the secondary one, with respect
to the values given by the extrapolation of the kinetics
reported by SzeH pvoK lgyi and Ujhidy (1978).
In this work expressions (2) and (3) are proposed as
representations of the kinetics of the reactions involved
in this process because they provide the best approxima-
tion to the experimental results. Although they are no-
toriously di!erent from the equations reported by
SzeH pvoK lgyi and Ujhidy (1978), the activation energy ob-
tained for the main reaction is remarkably similar to the
one determined by Wachi and Morikawa (1986, 1987) for
the temperature range between 298.15 and 303.15 K. As
to the velocity constant for the secondary reaction, the
support that guarantees the quality of the equation is
purely empirical. In the author's knowledge, no other
studies that might give additional justi"cation to the
517
resulting parameters have been published in the litera-
ture for the temperature range under consideration.
6. Parameter adjustment results
As described in the previous section, the adjustment of
the kinetic parameters was carried out exclusively on the
basis of the model for the heterogeneous zone, also as-
suming isothermal operation. It naturally comes into
question whether the parameters thus obtained succeed
in predicting the right ethylene conversions when the
complete model is used for reactor simulation. Besides,
another point in question is whether focusing the modi"-
cations solely on the improvement of one speci"c predic-
tion is not detrimental to the estimation of the remaining
performance variables. In view of these considerations,
this section has been devoted to a comparison between
the experimental data and the estimations obtained by
means of the complete model. On one hand, the extra-
polation of the kinetics reported by SzeH pvoK lgyi and
Ujhidy (1978) was employed and on the other, the kinet-
ics determined in the previous section (Eqs. (2) and (3))
were applied. The corresponding results are shown in
Figs. 8}15, where estimated values have been plotted
versus experimental values for each one of the operating
conditions described in Table 1.
It is clear from Fig. 8 that the ethylene conversion has
improved for all the experimental conditions owing to
the adjustment in the kinetic parameters. Apart from the
reductions in the errors, which always became lower than
0.26%, an additional advantage is that the model with
ence of changes in operating conditions.
Regarding chlorine conversions, which were already
acceptable even without corrections in the kinetic para-
meters, Fig. 9 reveals that the adjustment leads to a fur-
ther decrease in relative errors for all the experiments
under consideration. The program still overestimates
chlorine conversion values, but the maximum error for
this prediction merely amounts to 0.08%.
Fig. 8. Ethylene conversion.
518 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522

Fig. 9. Chlorine conversion.

Fig. 12. EDC in the gaseous e%uent.

Fig. 10. ETC production.

Fig. 13. O in the gaseous e%uent.



Fig. 11. EDC in the liquid product.

Fig. 14. Heat production in the heterogeneous zone.

Fig. 10 shows the predictions for the production of the
main secondary product (ETC). It can be noticed that the
estimations always remain closely similar to the original
ones, in good agreement with the experimental values.
As to EDC production, it is interesting to point out
that the kinetic adjustment does not cause signi"cant
variations in the prediction of the amount of EDC in the
liquid product (see Fig. 11), while the estimation of the
quantity of EDC in the gaseous e%uent has improved in
general (Fig. 12).
 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522
Fig. 15. Recirculation rate.
As regards oxygen contents in the gaseous e%uent,
Fig. 13 shows that model adjustment improves the
predictions signi"cantly. The oxygen enters the reactor
as an impurity in the chlorine gas stream. Lower
estimated values for ethylene conversion lead to higher
mass #ow rates for the gaseous e%uent. As a result, given
the same amount of oxygen fed to the process, its com-
position in that stream becomes lower. Errors in the
order of 10% still persist for concentrations higher than
3%, but these quantities are conservative. In industrial
practice, the oxygen contents should be kept lower than
1 m. The di!erences between the ex-
a maximum admissible value during operation in order
to avoid the formation of explosive mixtures down-
stream.
With respect to the amount of heat generated in the
heterogeneous zone, Fig. 14 shows that the complete
model with adjustment leads to a reduction in relative
errors for all the operating conditions considered in this
work. The prediction errors are now in the 3}11.5%
range, which is not only acceptable but also conservative
because the transfer capacity required in the heat ex-
changer is higher than the necessary quantity. This was
to be expected, since the heat generated in the heterogen-
eous zone is related to the ethylene conversion in a direct
way.
Finally, Fig. 15 concerns the predictions for recircula-
tion rate. This variable is evaluated from the global
mechanical-energy balance (Eqs. (29)}(31) in Orejas,
1999), whose parameters have not yet been adjusted
empirically. It can be observed that the adjustment of the
kinetic parameters, which are directly involved only in
the model of the heterogeneous zone, leads to an increase
in the estimated recirculation rates for all the experi-
ments. This globally improves their prediction. The rea-
son that justi"es this behaviour is that when the gaseous
reactants in a bubble column with external recirculation
loop are totally consumed in the heterogeneous zone (left
branch in Fig. 1), there are signi"cant volumetric vari-
519
ations that a!ect the global mechanical-energy balance in
a direct way. This relationship between the kinetic para-
meters, which determine the volumetric variations in the
gas phase, and the recirculation rate estimated from the
global mechanical-energy balance gives physical consist-
ency to the parameter adjustment methodology carried
out in this work.
7. Behaviour in the heterogeneous zone
It is clear from Section 5 that the adjustment of the
kinetic parameters led to reaction rate constants
whose values were much lower than those resulting from
the extrapolation of the kinetics reported by SzeH pvoK lgyi
and Ujhidy (1978). This lower consumption rate for the
gaseous reactants, C H and Cl , in the liquid phase
  
alters the axial variations in all the variables that charac-
terise the performance of the heterogeneous zone. Never-
theless, from a qualitative point of view, its behaviour
coincides with the descriptions given in the previous
paper (see Figs. 4}11, Orejas, 1999).
By way of illustration, the predicted axial temperature
pro"les for experiment 6 from Table 1 are presented in
Fig. 16. It can be observed that there is a lower temper-
ature increment in the distributors zone (z"0) when the
kinetic parameters have been adjusted, with smaller axial
temperature gradients at the initial stages of the unit,
namely up to z
treme temperatures ( ! ) are alike, however,
** *
amounting to 6.21 and 6.30 K before and after the adjust-
ment, respectively. In consequence, the total amount of
heat that must be transferred in the heat exchanger is
similar in both cases, as shown in Fig. 14.
The most important e!ect arises when predicting the
axial composition pro"les of the gaseous reactants in the
liquid phase. Fig. 17, which also corresponds to experi-
ment 6, shows the in#uence of the lowest values of the
kinetic constants.
Fig. 16. Axial pro"le for temperature in the heterogeneous zone.
520 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522

which notoriously reduces the complexity of the model.

The numerical resolution of the model becomes simpler,
with signi"cant reductions in the run-times required to
simulate the reactor's operation.
The other important "nal consequence of parameter
adjustment is that it indicates that the reactor's produc-
tion capacity will be determined by the liquid-phase
volume. Under other circumstances, the key factor is to
obtain high interfacial areas. In this case, this becomes
unimportant and therefore, the way in which the ethy-
lene-gas stream is fed and distributed into the reactor
does not require special considerations.

Fig. 17. Axial composition pro"les for C H and Cl in the liquid

   8. Conclusions
phase.

An industrial process for the production of 1,2-dich-

The predictions are qualitatively similar, but the lower
values in the reaction rate constants make the composi-
tion of these reactants in the liquid phase higher. The
Hatta number (Westerterp, van Swaaij & Beenackers,
1984), whose axial pro"le originally exhibited values
ranging from 0.29 to 0.35 without kinetics adjustment
(see Fig. 4 in Orejas, 1999), now lies in the 0.06}0.11 range
with the adjusted kinetics. This implies that the new
values for the reaction rate constants have introduced
a change in the kinetic regime that prevails in the di!u-
sion "lms for the interphase between the ethylene gas and
the liquid phase. In contrast with the behaviour before
the kinetic adjustment, the speed of the chemical reac-
tions becomes signi"cantly lower than the mass transfer
velocity for C H when the kinetics has been adjusted.
 
This change has two signi"cant consequences. In the
"rst place, from the viewpoint of both the model struc-
ture and the numerical simulation program, it implies
that it is no longer necessary to consider the absorption
and chemical reaction phenomena at the interphase be-
tween the ethylene gas and the liquid phase in detail. As
a result, the mass transfer for di!erent components can
be represented as a physical absorption process. Eqs.
(9)}(16) in the previous work by Orejas (1999) can, there-
fore, be replaced by the following expressions:
loroethane by direct chlorination of ethylene at low tem-
peratures has been considered. A mathematical model
and the corresponding numerical simulation program
developed in a previous work were evaluated, employing
a di!erent analysis of the experimental data. This ap-
proach made it possible to detect faults in the original
formulation that eventually resulted in an inadequate
representation of the e!ects of changes in the operating
variables on the conversion of one of the main reactives.
Although the predictions for ethylene conversion were
rather close, its errors never exceeding 0.85%, they were
insensitive to changes in the operating conditions.
Based on the analysis of model structure, together with
various numerical simulations as well as the use of ex-
perimental data obtained for di!erent reactor zones, it
could be established that the errors in the predictions of
ethylene conversion were exclusively due to problems in
the model for the heterogeneous zone.
Assuming the hypothesis that the structure of the
model proposed for that zone was correct, a parametric
sensitivity analysis was carried out. The main conclusion
from this study was that the kinetic parameters were the
only ones that had signi"cant in#uence on these errors.
In fact, the kinetic constants originally employed were
being used outside the temperature range for which they
had been determined because better information was


1P 2>c o w n " j "
N ""k R ? * ! * ? " ?V B
? B , (4) unavailable.
?V  *? H PM PM PM The sole adjustment of these two parameters led to
C? ? ? ?
a better model with a simpler numerical simulation pro-


1P 2>c o w n " j "
N ""k R @ * ! * @ " @V B
@ B , (5) gram, which was not only capable of predicting the
@V  *@ H PM PM PM
C@ @ @ @ values of various performance variables with good ap-


1P 2>c o w n " j " proximations in terms of relative errors, but also suc-
N ""k R F * ! * F " FV B
F B , (6) ceeded in representing the in#uence of changes in the
FV  *F H PM PM PM
CF F F F variables that de"ne the reactor's operation adequately
n " j " for the entire technically feasible range.
N "" RV B
R B "0, (7)
RV  PM PM The kinetic expressions obtained as a result of this
R R study are surely far from representing the intrinsic


k 1P 2 P  n " chemical kinetics for the reactions involved in this pro-
N "" %A R >! A " AV B , (8)
AV  R12 A 1P 2 PM cess. Nevertheless, they have at least allowed a highly
R A
 J. A. Orejas / Chemical Engineering Science 56 (2001) 513}522 521

satisfactory description of the complex relationship x coordinate inside the di!usion "lms, m
among the various physical, chemical, thermodynamic, > gas-phase molar fraction for the ith species
G
#uid dynamic and transport phenomena that exist in this X ,X ethylene and chlorine conversion, respec-
? @
kind of reactors. Finally, it is important to remark that tively
the improvements achieved in the estimation of the recir- w weight fraction for the ith compound
G
culation rate, which is an experimental variable that is
determined in a totally independent way, provide phys- Greek letters
ical consistency to the parameter adjustment carried out
in the present work. 1e 2 total volumetric fraction in the gas phase
%
U ,U total mass #ow for the gaseous and liquid
+% +*
phases, respectively, kg s\
Notation U ,U mass #ow for the liquid phase at z"0 and
+* +**
z", respectively, kg s\
C molar composition for the ith species, U liquid mass #ow produced by the reactor,
G +*.
kmol m\ kg s\
c molar concentration of the liquid phase, o density in the liquid phase, kg m\
* *
kmol m\ X objective function de"ned in Eq. (1)
D mass axial dispersion coe$cient, m s\
+X Subscripts
d Sauter mean bubble diameter, m
TQ
H Henry's law constant for the ith species,
AG a ethylene
Pa mol-frac\
j interfacial mass #ow density for the ith b chlorine
G c 1,2-dichloroethane
species with respect to the average mass
velocity, kg i m\ s\ h hydrogen chloride
k chemical reaction rate constant, t 1,1,2-trichloroethane

m kmol\ s\
Superscripts
k chemical reaction rate constant,

m kmol\ s\
A gas stream initially rich in ethylene
k gas-phase mass transfer coe$cient for the
%G est., exp. estimated and experimental value, respec-
ith species, m s\
tively
k liquid-phase mass transfer coe$cient for
*G
the ith species, m s\ Other symbols
N interfacial molar #ow density for the ith
GV
species, kmol m\ s\ 1t2 t", t" mean value for variable t in a given cross-
n interfacial mass #ow density for the ith  B
GV section variable t evaluated at the liquid
species, kg m\ s\ di!usion "lm for gas A, at x"0 and d,
PM molecular weight of the ith species,
G respectively
kmol kg\
P total pressure, kPa
R Acknowledgements
R gas constant
R reaction rate of the ith chemical reaction,
G The author wishes to thank the support given by the
kmol m\ s\ Science and Technology Secretary of National Univer-
temperature, K sity of RmH o Cuarto (UNRC) and by the Council of Scient-
, cooling water temperatures at the input
!5 !5* i"c and Technological Research of the Province of
and output, respectively, K CoH rdoba (CONICOR) } Argentina.
temperature of the gas phase at the reac-
%
tor's feed, K
References
, liquid-phase temperature at z"0 and
* **
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