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To cite this article: CHENG-CHU LIN & RICHARD L. LONG JR (1997) PHENOL REMOVAL BY EMULSION LIQUID MEMBRANE: A
MODIFIED DIFFUSION MODEL, Chemical Engineering Communications, 156:1, 45-58, DOI: 10.1080/00986449708936668
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Chem. Eng. Comm., 1996, Vol. 156, pp.4S-58 <tl 1996 OPA [Oversees Publishers Association)
Reprints available directly from the publisher Amsterdam B.V. Published in The Netherlands under
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Printed in Malaysia
DIFFUSION MODEL
CHENG-CHU LIN and RICHARD L. LONG, JR*
New Mexico State University, Las Cruces, N M 88003
A diffusion model is developed to simulated the behavior of mass transport of the solute in the
emulsion liquid membrane. The solute is allowed to react reversiblely with the internal reagent,
and the effective diffusivity of the solute in membrane phase is dependent on local solute
concentration in membrane phase. A numerical solution is presented for the non-linear equa-
tions of this model. The results are compared with those of two previous models, and it is
found that the Modified Diffusion Model represents more accurately than other earlier models.
Keywords: Phenol; emulsion liquid membrane; diffusion model; reaction reversibility; effective
diffusivity
INTRODUCTION
45
46 c.c LIN AND R. L. LONG
surfactant
Organic phaa8
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membrane phase and internal phase, are mixed with a surfactant, additives,
and a base to produce an emulsion by agitation. This emulsion is then
dispersed in a continuous phase by agitation. Mass transfer takes place
between the continuous phase and the internal phase through the mem-
brane phase [12].
In the process of making ELM, two factors should be considered: (1) shear,
which is produced by agitation and (2) addition of surfactant, additives, and a
base to the membrane phase. When membrane phase and internal phase are
mixed together, the introduction of high shear to the mixture of two phases
permits the droplet size to be small. This factor increases the mass transfer
rate in the liquid membrane because it increases the surface to volume ratio.
On the other hand, the utility of the surfactant, additives, and a base are to
stabilize liquid membrane system [4,11]. When organic phase and internal
reagent are mixed to produce the emulsion, the presence of surfactant pre-
vents dispersed droplets from coalescing at once in the membrane phase.
Further, the integrity of the emulsion during the process can be maintained
by having added these chemicals to the emulsion. The amounts and kinds of
the surfactant, additive, and base which are most suitable for the liquid
membrane system are often selected by the experimental trial.
When the emulsion is dispersed by agitation in the external phase, many
small globules of emulsion are formed. The size of the globules strongly
depends on the nature and concentration of the surfactant in the emulsion,
DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 47
emulsion viscosity, and the mode and intensity of mixing [11]. From experi-
mental results [14], the emulsion globules are typically in the range of 0.05
to 0.2cm in diameter, and the diameter of internal droplets is about 10- 2 to
IO-'cm. Various sizes of globules exist in the continuous phase, and in one
globule there exist many various sizes of internal droplets.
Many mathemactical models (1,6,7,13,14,15,16) for the solute transport
in liquid membrane have been proposed. The Advancing Front Model (7) is
regarded as the standard model for simulating the transport of phenol from
water into an internal phase containing sodium hydroxide. Bunge and
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Noble (1) developed the Reversible Reaction Model in which the reaction
between solute and internal reagent is an reversible one. The Reversible
Reaction Model is an excellent model to simulate phenol removal by emul-
sion liquid membrane. However, the results of the Reversible Reaction
Model were obtained by using a droplet averaged effective diffusivity. A
complete version of the Reversible Reaction Model would allow spatial
variation of effective diffusivity in the globule. When this variable effective
diffusivity is applied in the Reversible Reaction Model, the model results are
drastically changed. In addition, there appears to be some problems with
the mass balance in the Reversible Reaction model. Therefore, in this work
we develop a new model where the spatial variation of effective diffusivity is
applied across the membrane globule. The results of this new model will be
compared with those of Advancing Front Model (7) and Reversible Reac-
tion Model (1).
MODEL DEVELOPMENT
Membrane
phase
1st layer
Internal
droplet
2nd layer phase
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Sauter mean diameter for globules and a single Sauter mean diameter
for droplets.
(3) The chemical reaction rate is much faster than diffusion within the
globule. Thus local reaction equilibrium applies throughout the glob-
ules.
(4) Local phase equilibrium holds between membrane and internal droplet
phase.
(5) Concentration within the internal droplets of any layer is independent of
position (spherical symmetry).
(6) No internal circulation occurs within the globule.
(7) Membrane leakage is neglected.
(8) The system is well-agitated, so external phase mass transfer resistance
can be neglected.
(9) The distribution coefficient at the interface between external and mem-
brane phases is equal to that at the interface between membrane and
internal phases.
From Bunge and Noble [I], the reaction between the solute A and the
internal reagent B is a reversible one and shown as follows:
A+B~P (I)
DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 49
Because Band P can not dissolve in the membrane phase, the reaction
equilibrium just occurs in the internal droplet phase. Further, the activity
effects are neglected, so the equilibrium constant K for reaction (I) is
(2)
(3)
(4)
Owing to assumptions (3) and (4), the membrane phase concentration, CAm'
at a given radial position inside the globule can be related to the internal
phase concentration of solute A at the same position by the following
equation:
CAi=CAm!rx (5)
(7)
50 c-c LIN AND R. L. LONG
IlmulsIon
~--- globule
"'\:I!lr--+-- Membrane
phase
~--1~-- Internal
droplet phase
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FIGURE 3 Mass balance consideration of a thin shell inside the emulsion globules.
(8)
and
C BFav BC
df.av = a;:- Am
= Derr---a;:- (9)
The mass balance also can be derived for the external phase. Because the
solutes which disappear in the external phase with time should be equal to
those entering the emulsion globules, mass balance equation in the external
DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 51
phase is
(II)
where the total diffusion flux on the surface of the emulsion globules is
considered also by using Cap and Derr.ap, Substitute equations (9) in (11) to
yield
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(12)
~ oC Arn =~~(r2D
2 OC Arn) _ (~)(OCPi + OC Ar) (10)
Vrn + Yo ot r or err or Vrn + Yo ot ot
External Phase:
(16)
(18)
This model is casted into the dimensionless forms by using the following
definitions.
y=r/R ,= D'ff.NR t / R 2
G = e Am/(exe~,)
h = eAe/e~e <1>1 = l-';/exVm <1>2 = (Vm + 1-';)/ Vm
<1>3 = 3ex(Vm + 1-';)/ Ve D = D'frl D'ff,NR
sl=KQi S2 = Ke~e
Globule:
(19)
External Phase:
(23)
I.e.:, = 0, h= 1 (24)
(25)
where
o; [Dr y/ex
DA = 2(Dry/ex) (DiY/ex) _ Dm (DrY/ex) _ Dm In
(DrY/ex)
v:: - 1] (26)
DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 53
fJ = 0.403 _ _
I -
V )-1 /3 - 0.5 (27)
( V + II;
m
(28)
When y = I in equation (28), D'ff obtained from equation (25) is the effective
diffusivity of the solute in the membrane phase without solute A/internal
reagent B reaction (i.e. D d f •N R) [I]. From equations (25) through (28), it can
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be found that the effective diffusivity D'ff depends upon G, that is, the local
membrane phase concentration, CAm'
The model can be solved on the computer with the program DIVPAG
available from IMSL (International Mathematical and Statistical Libraries,
Inc, Houston, TX). The basic method used by DIVPAG is Gear's method
[5]. This program finds approximations to the solutions of a system of the
differential equations with initial conditions.
All parameters in the Modified Diffusion Model are shown in Table I, and
were obtained from Ho et al. [7] and Bunge and Noble [I]. The predictions
of the Modified Diffusion Model are shown in Figure 4 which also shows
the results of the Advancing Front Model and the Reversible Reaction
Experimental parameters
K = 11 m'/eq
• Vm = 0.65 X 10- 10 m 2 Is
"V",.NR= 1.65 X 10-
10
m 2/s 'Vi = 9.98 X 10- 10 m 2 Is
0.9
0.8
0.7
0.6
~ Modifieddiffusion model
h 0.5 ___ Reversiblereaction model
- AdvancingFrontModel
0.4
.......... Experimental data
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0.3
0.2
0.1 .
0
0 2 3 4
Model. From Bunge and Noble [1], there is a good approximation to the
experimental data for the Reversible Reaction Model using the average
effective diffusivity. Figure 4 shows that the results for the Reversible Reac-
tion Model with variable effective diffusivity include the significant devi-
ation from the experimental data. The variable effective diffusivity in the
emulsion globule is dependent on the local membrane phase concentration,
which changes with time and position in the emulsion globule. This variable
effective diffusivity is used in the Modified Diffusion Model. It is seen that
the results or the Modified Diffusion Model give the best prediction of
experimental data of these three diffusion models. The Advancing Front
Model overpredicts and the Reversible Reaction Model underpredicts the
experimental data.
From assumption (7), all of the internal droplets should be surrounded by
the membrane phase. There just exists the organic membrane phase over
the surface of the emulsion globules, so the transport of the solute on the
globule surface also should be just based on the membrane phase according
these ideas. For the purpose of proving the correctness of this physical
condition, solute diffusivity in the membrane phase, D m , is used instead of
Deff in equation (16) to calculate the results of the model. Figure 5 shows
that this change increases the deviation of the Modified Diffusion Model
with the experimental data, compared with the predictions of the model in
Figure 4. Based on these calculations, Defr should be used in equation (16).
DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 55
0.9
0.8
0.7
0.6
0.5
• -+- Modeling results
h
• • Experimental data
0.'
•
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0.3
•
0.2 •
0.1
0
0 3
~
FIGURE 5 The results of the Modified Diffusion Model where D; represents the diffusivity
on the surface of the emulsion globues.
This fact can be explained from the model deviation. Because the diffusion
behavior of the solute inside the emulsion globules is explained by the
effective diffusivity, it must be used over the surface of the emulsion
globules.
Because the profile of the local membrane phase concentration of the
solute can be obtained by solving the Modified Diffusion Model, all internal
phase concentrations including solutes, internal reagents, and products can
be calculated according to Bunge and Noble [IJ as follows:
(29)
(30)
(31)
Figure 6 shows GAi' GBi and Gp i versus y at T = 4.6 which is the practical
extraction time for the experimental data in Ho et al. [7]. It is difficult to
obtain these data from experiment, but easy from model results. We found
that the emulsion is not exhausted completely and can be applied for ex-
tracting more solute. This condition coincides with the trends of the Modi-
fied Diffusion Model and experimental data in Figure 4 at longer time.
56 c.c LIN AND R. L. LONO
0.9
0.8
0.7
0.8 --+-OAi
0.5 ---08i
G, .: GPi
0.4
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0.3
02 I
i
0.1 ,J.
I
l
o 0.2 0.4 0.6 0.8
y
FIGURE 6 The concentrations of the internal phase at the extraction time r = 4.6.
CONCLUSION
NOMENCLATURE
Greek Letter
Distribution coefficient for the solute between the
membrane phase and the water phase
1: Dimensionless time
<I> Dimensionless coefficient
y Defined by equation (28)
13 Defined by equation (27)
Subscripts
A Solutes
au Average
B Internal reagents
e External phase
Internal phase
m Membrane phase
p Product
58 c-c. LIN AND R. L. LONG
Superscript
o Initial condition
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