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PHENOL REMOVAL BY EMULSION LIQUID MEMBRANE: A

MODIFIED DIFFUSION MODEL
a a
CHENG-CHU LIN & RICHARD L. LONG JR
a
New Mexico State University , Las Cruces, NM, 88003
Published online: 17 May 2010.

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

To link to this article: http://dx.doi.org/10.1080/00986449708936668

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 Chem. Eng. Comm., 1996, Vol. 156, pp.4S-58 <tl 1996 OPA [Oversees Publishers Association)
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PHENOL REMOVAL BY EMULSION

LIQUID MEMBRANE: A MODIFIED
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DIFFUSION MODEL
CHENG-CHU LIN and RICHARD L. LONG, JR*
New Mexico State University, Las Cruces, N M 88003

(Received 20 February 1995; In final form 10 March 1996)

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

Research in emulsion liquid membrane (ELM) technology has continued for

more than 20 years since Li [2J invented this technology in 1968. In this
period, many investigators have applied this technology to separate con-
taminants such as phenol, amine, and even heavy metal ions from waste
water or other sources. Mathematical models have been constructed to
simulate mass transfer processes for the solute in the ELM. Although the
application of liquid membranes still is not widespread, its treatment efficiency
is compelling as a separation technique and justifies continued research.
To visualize the liquid membrane system, a typical formation process of
water-oil-water ELM is illustrated in Figure 1. Two immiscible phases, the

°To whom correspondence should be addressed.

45
 46 c.c LIN AND R. L. LONG

surfactant

Organic phaa8
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FIGURE I The typical formation of water-oil-water ELM system.

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

An emulsion glouble is shown Figure 2, where the membrane phase

separates the internal droplet phase from the external bulk phase. The
solute A, phenol, diffuses through the membrane phase of the globule from
bulk phase to react with the internal reagent B, sodium hydroxide, and
produce the product P, sodium phenolate. It is allowable for solute A to
distribute through all of the three phases, but reagent B and product Pare
insoluble in the membrane phase.
The assumptions for Modified Diffusion Model are depicted as follows:
(1) The membrane and external phases are completely immiscible, and the
membrane and internal phases are also completely immiscible.
(2) All emulsion globules and internal phase droplets are spherical, and the
size of both globules and internal droplets can be represented by a single
 48 C.-C. LIN AND R. L. LONG

Membrane
phase
1st layer

Internal
droplet
2nd layer phase
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3rc! laylll' - ....~~ C"", • aCe

FIGURE 2 Modified Diffusion Model.

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:

PhOH + NaOH ~ PhONa + H 20

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)

From reagent conservation and reaction stoichiometry, we can derive

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(3)

where C~i is the initial concentration of B in the internal droplet phase.

Hence C Pi can be obtained by combining equations (2) and (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)

where rx is the distribution coefficient of the solute between the membrane

and the internal phases. On the surface of the globule, CAm can be related to
CAe by

CAm = rxCAe (6)

based on assumptions (8) and (9).

From these assumptions and conditions, the mathematical model for phen-
ol of extraction in the emulsion liquid membrane can be developed by deriving
the mass balance equations. One spherical thin shell in an emulsion globule is
illustrated in Figure 3. The complexity of the structures in the emulsion
globules can be neglected by applying the effective diffusivity to calculate
the mass diffusion, and the mass balance equation for that shell is

(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.

where C av is the average concentration of the solute in the emulsion glob-

ules, Deff.a)S the effective diffusivity based on Cav' Ho et al. [7] calculated
and obtained an effective diffusivity, Deff , based on the membrane phase
concentration, CAm' The relation between D eff •a v and D.rr is as follows:

(8)

and

C BFav BC
df.av = a;:- Am
= Derr---a;:- (9)

equation (7) is expressed in terms of CAm by substituting equations (8) and

(9) in (7), and equation (7) becomes

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)

Finally, the Modified Diffusion Model is as follows:

Globules:

~ oC Arn =~~(r2D
2 OC Arn) _ (~)(OCPi + OC Ar) (10)
Vrn + Yo ot r or err or Vrn + Yo ot ot

I.C.:t=O, O:s;;r<R, CArn=O (13)

B.C.: l.r = R, t;?; 0, CArn = <XC Ae (14)

2.r=0, t;?;O, oCArn/or=O (15)

External Phase:

(16)

t.C: t = 0, CAe = C~e (17)

Like Reversible Reaction Model, equation (10) can be transformed to

(18)

by applying equations (2) through (5).

 52 c.c LIN AND R. L. LONG

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

Dimensionless model is as follows:

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Globule:

(19)

I.e.: 0 ,,; y < 1, r = 0, G= 0 (20)

B.C.: l.y = 1, ,;;, 0, G =h (21)

2.y=0, ,;;'0, aG/ay=o (22)

External Phase:

(23)

I.e.:, = 0, h= 1 (24)

The effective diffusivity in the membrane phase (D 'ff) can be estimated

from the Jefferson-Witzell-Sibbett equation [1,3,7] as follows:

(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.

RESULTS AND DISCUSSION

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

TABLE I. Physical paramelers of Modified Diffusion Model

in batch extraction

Experimental parameters

C eo = 8.19 mol/rn' R=3 x 10-4 m

C~i = 375 eq/rn' dj = 1 0 - 6 m
Vm/( Vm+ "I) = 0.637
V;/( Vm + "I) = 0.363
VBI(Vm+ "1)= 15
,,= 0.52
Equilibrium constant and the relative effective diffusivity

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

·Calculated from Wilke-Chang correlation by Ho er al. [7]

··Calculated from Jeferson-Witzell-Sibbett equation by Bunge
and Noble [I]
 54 c.c LIN AND R. L. LONG

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

FIGURE 4 The results of Modified Diffusion Model.

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

For phenol removal by using emulsion liquid membrane, the Modified

Diffusion Model is a good model to explain the results of the experimental
extraction. The Advancing Front Model is the classic model but not the
best one to represent the extraction data. The Reversible Reaction Model
using average effective diffusivity made a near perfect fit with the experi-
mental data. However, when the effective diffusivity is allowed to depend on
local membrane phase concentration in this model, the comparison with
experimental data is much worse than the Advancing Front Model and the
Modified Diffusion Model.
Under practical experimental conditions, leakage of the internal droplet
phase into the external phase will propably occur. Although the Modified
Diffusion Model made better predictions than Advancing Front Model and
the corrected version of the Reversible Reaction Model, this factor has been
neglected in its assumptions. In the future, modeling of phenol or any solute
removal by using the emulsion liquid membrane should include consider-
ation of the internal phase droplet leakage. One suggestion is that a trace
element be applied in the experiment to check the exact leakage rate with
time.
 DIFFUSION MODEL FOR EMULSION LIQUID MEMBRANE 57

NOMENCLATURE

Concentration (mol/rn ')

Dimensionless effective diffusivity, = Deff/Deff,NR
Defined by equation (26)
Effective diffusivity (m 2/sec), based on the driving
force of solute concentration in the membrane phase
D err.u v Effective diffusivity (m 2/sec), based on the driving
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force of average solute concentration in the emulsion

solute diffusivity in the internal phase (m 2/sec)
solute diffusivity in the membrane phase (m 2/sec)
Dimensionless concentration
Dimensionless solute concentration in the external phase
Equilibrium constant
r Radial coordinate
R Sauter mean radius of the emulsion globules (m)
s Dimensionless constant
t Time (sec)
V Volume (m')
y Dimensionless radius coordinate

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

References

[1] Bunge, A. L. and Richard, D. Noble (1984)."A Diffusion Model for Reversible Consump-
tion in Emulsion Liquid Membranes," Journal of Membrane Science, 21, 55.
[2] Cahn, R. P. and Li, N. N. (1974). "Separation of Phenol from Wastewater by the Liquid
Membrane Technique," Separation Science, 9, 505.
Downloaded by [Washington University in St Louis] at 05:31 21 December 2014

[3] Crank, J. (1975). The Mathematics of Diffusion, 2nd ed., Chap. 12, Clarendon Press, Oxford.
[4] Fuller, E. J. and Li, N. N. (1984). "Extraction of Chromium and zinc from Cooling Tower
Blowdown by Liquid Membranes," Journal of Membrane Science, 18, 251.
[5] Gear, C. W. (1969). "The Automatic Integration of Stiff Ordinary Differential Equations,"
Information Processing 68 (Proceedings of the IFIP Congress 1968), 187, North Holland
Publishing Company.
[6] Harada, Makoto, Shiomi, N. and Yamazaki, F. (1984). "Separation of Metals by Liquid
Membrane with Tri-n-Octylarnine," Journal of Chemical Engineering of Japan, 17, 567.
[7] Ho, W. S., Hatton, T. A., Lightfoot, W. S. and Li, N. N. (1982). "Batch Extraction with
Liquid Surfactant Membranes: A Diffusion Controlled Model," AICHE Journal, 28, 662.
[8] Lin, C. C. (1992). "Model Design of Phenol Removal by Emulsion Liquid Membrane in
Batch and Continuous Flow Extraction," Master Thesis, Department of Chemical Engin-
eering, New Mexico State University.
[9] Matulevicius, E. S. and Li, N. N. (1975). "Facilitated Transport Through Liquid Mem-
branes," Separation and Purification Methods. 4. 73.
[10] Noble, Richard, D. and Douglas Way, J. (1987). Liquid Membranes, Chap. I, American
Chemical Society, Washington, DC.
[II] Stroeve, Pieter and Varanasi, P. P. (1984). "Extraction with Double Emulsion in a Batch
Reactor: Effect of Continuous-Phase Resistance," AICHE Journal, 30,1007.
[12] Ujita, Goro, Shibata, J. and Nishimura, S. (1984). "Extraction of Some Ions from Dilute
Aqueous Solution by Using a Liquid Membrane Process," Technology Reports of Kansai
Unieersit y, 25, 81.
[13] Teramoto, Masaaki, Sakai, T., Yanagawa, K. and Miyake, Y. (1983). "Modeling of the
permeation of copper through Liquid Surfactant Membranes by continuous Operations,"
Joumal of Chemical Enqineertnq of Japan, 18, 985.
[14] Ward ius, D. S. and Hallon, T. A. (1985). "A Model for Liquid Membrane Extraction
with Instantaneous Reaction in Cascaded Mixers," Chemical Engineering Communica-
tions, 37, 159. I