jounud o!

MIEMMIANE
SCIENCE
ELSEVIER Journal of Membrane Science 114 (1996) 171- 185

Mathematical modeling of silver extraction by an emulsion liquid

membrane process
Sang Cheol Lee a, Byoung Sung Ahn b,., Won Kook Lee c
a Department of Chemical Engineering, Kunsan National University, Kunsan, Chonbuk 573-701, South Korea
b Division of Environmental and CFC Technology, Korea Institute of Science and Technology Cheongryang, P.O. Box 131, Seoul, South
Korea
c Department of Chemical Engineering, Korea Advanced Institute of Science and Technology 373-1, Kusong Dong, Yusung Gu, Taejeon,
South Korea
Received 19 May 1995; accepted 8 November 1995

Abstract

A general physical model of a typical batch extraction system employing an emulsion liquid membrane process for the
extraction of silver has been developed. The model takes into account the extraction reaction between the silver ion and the
carder molecules at the external interface, the diffusion of the complex in the membrane phase, the stripping reaction at the
internal interface and the reaction of silver ion with the reagent, HC1, in the internal phase to yield silver chloride incapable
of permeating through the membrane phase. In addition, the leakage of the internal aqueous phase to the external aqueous
phase due to membrane breakage has been incorporated ih this model. The batch extraction of silver using D2EHPA as a
carrier has been carded out under various experimental conditions. The experimental data can be well explained by the
present model.

Keywords: Emulsion liquid membrane; Silver extraction; Facilitated transport; Permeation model

1. I n t r o d u c t i o n

A variety o f separation problems have been investigated over the last two decades by using an emulsion
liquid membrane (ELM) process. The process has the following advantages; extraction and stripping occur
simultaneously in one stage, so that it is easy to separate and concentrate a solute from very dilute solutions. In
addition, the requirement of organic solvent and carrier is small contrary to solvent extraction, and the mass
transfer rate is high due to large interfacial area. These include hydrometallurgical recovery o f metal ions [1-5],
removal o f weak acids and bases from waste water [6-9], and applications in biochemical and biomedical fields
[10-13]. However, a few troublesome problems, such as emulsion swelling and breakage, have limited the wide
uses of ELMs.

* Corresponding author.

0376-7388/96/$15.00 © 1996 Elsevier Science B.V. All rights reserved

SSDI 0376-7388(95)00315-0
172 S.C. Lee et al. / Journal of Membrane Science 114 (1996) 171-185

There are two types of facilitated transport mechanisms to enhance the mass transfer rate of a solute in an
ELM system. In the first mechanism, called carrier-facilitated transport mechanism, a carrier is incorporated in
the membrane phase to increase the mass transfer rates. Recovery of zinc from waste water using cation-ex-
change reagents is a typical example of cartier-facilitated transport [14]. In the second mechanism, the solute
dissolves in the membrane phase near the extemal interface, diffuses through it to the inward region of emulsion
drop in the dissolved state and is released into the internal phase by reversing the solution process. The solute
reacts with a reagent in the internal aqueous phase, resulting in a membrane-insoluble product. Thus a
concentration gradient is maintained across the membrane. For instance, phenol reacts with NaOH in the
internal phase to yield sodium phenolate [15], and then the concentration gradient of phenol between the
extemal and the intemal phases can be maintained high if a higher concentration NaOH solution is used as
internal phase.
Despite of much research on the extraction of various metals using ELMs, no attempts have been made so far
to study the transport mechanism of silver through ELM. Thus, we investigated the extraction of silver by the
ELM process using D2EHPA (di-2-ethylhexyl phosphoric acid) as a carder in this paper. The ELM system
involves the combination of the two facilitated transport mechanisms. That is, D2EHPA facilitates the transport
of silver through the former mechanism, and silver ion is simultaneously changed by internal reagent, HCI, to
silver chloride which has a low solubility in aqueous solution, so that the concentration gradient of silver
between two aqueous phases is maintained high through the latter mechanism. On the basis of such
mechanisms, a permeation model is presented in order to explain the effects of various experimental conditions
on the extraction of silver by the ELM process.

2. Transport mechanism

A schematic diagram of an ELM process for the extraction of silver is shown in Fig. 1. D2EHPA exists as a
dimer in the organic phase [16], and silver ion (Ag +) reacts with a carrier [(HR)2], a dimerized D2EHPA, at the
external interface to form silver-D2EHPA complex [AgR(HR)] and hydrogen ion (H+). The complex then
diffuses through the membrane phase to the intemal interface. Silver ion is released into the intemal phase by
the stripping reaction at the internal interface and reacts with chloride ion to form silver chloride which has a
low solubility in the internal aqueous solution. Finally, silver and hydrogen ions are counter-transported in this
system and the following reaction occurs at both interfaces:

Ag + + (HR)2 ¢* AgR(HR) + H + (1)

External phase Membrane phase Internal phase

(Phase m) (phase If) (phase I)

(HR~ lr-
S
x""---..-,. ~+ + HCl
/q[R(HR) --~ AgCl + I-P"

Fig. 1. Mechanismof transportof silveracross a liquid membranecontainingD2EHPAas a carrier.

 S.C. Lee et al./Journal of Membrane Science 114 (1996) 171-185 173

|i "x -~t 1
i',, o

Fit. 2. Perrriealion model of silver by an emulsion liquid nrenibr~e: 1, extraction reaction at the external interface; 2, diffusiorl in thin oil
layer, 3, diffusion in W / O emulsion phase; 4, sllSppint reaction at the internal inierfa~ accomp~yin t the ¢on~.,o.ltive reaction of silver
with internal reagent; 5, leakage of the internal phase to the externalphase.

Here, the equilibrium constant, K~, of reaction (1) is given by

CAgR(HR)CH ÷ CcCH
= C,,g.qHR 2 or (2)

In Eq. (2), CA, C a, Cc and C H denote the concentrations of Ag +, (HR) 2, AgR(HR) and H +, respectively.

3. Model development

On the basis of the transport mechanism presented in the previous section, a permeation model has been
developed considering the leakage of the internal aqueous phase to the external phase due to membrane
breakage, as shown in Fig. 2. In order to simplify the model we have made the following assumptions.
(1) Mass transfer resistances of silver and hydrogen ions in the external aqueous phase are negligible,
because stirring speed is very fast under the present experimental condition.
(2) The local reaction at the external interface between the external and the membrane phases is in
equilibrium.
(3) The diameters of emulsion drops and internal droplets are uniform and can be expressed as the Sauter
mean diameter.
(4) The internal aqueous phase droplets are immobile and so there is no circulation of the droplets within the
emulsion drop.
(5) The effects of coalescence a n d / o r breakage of the internal aqueous droplets or emulsion drops are
ignored.
(6) The mass transfer resistance in the internal aqueous phase is neglected because of very small size of the
internal droplets [2,3].
(7) Since the concentration of hydrochloric acid in the internal phase is maintained high through all the
experiments, the silver ion, released into the internal aqueous phase, reacts with chloride ion to form silver
chloride which is slightly soluble, so that the backward reaction rate of the stripping reaction is not considered.
Then, it is assumed that the following irreversible reaction occurs at the internal interface:
r s = ksCcfH, I (3)
where k s is the stripping reaction rate constant.
174 S.C. Lee et al. /Journal of Merabrane Science 114 (1996) 171-185

The mass balance equation of silver in the external aqueous phase is represented by
dC^ ,Ill
-Vm dt --kcS(Cc[~=R-- CC[~=R~)--MBCA'II~=R' (4)

where k c is the mass transfer coefficient of the silver-D2EHPA complex through the peripheral oil layer, S is
the total interfacial area between the external aqueous solution and W / O emulsion drops, R is the Sauter mean
radius of W / O emulsion drops, R i is the radius of inner core of W / O emulsion drops, M s is the volumetric
rate of the leakage of Phase I to Phase III due to membrane breakage and V is the volume of each phase, where
subscripts I, II and III denote the internal aqueous phase, the membrane phase and the external aqueous phase,
respectively. And Cc,IIr_R ~ is the silver chloride concentration in the internal aqueous droplets which are laid at
r = R i within the emulsion drop.
Also, the mass balance equation of hydrogen ion in the external aqueous phase is as follows.

dCn'm -- kcS(CcIr=R - Cc],-=R,) + MBCH.,I~.R , (5)

VIII dt
The mass balance equations of the carrier B and the complex C in the region of 0 < r < R~ within the
emulsion drop are expressed by using the effective diffusivities of complex and carder, D~c and Des.
aCc 1r a [ 2 OCc 3Vl
= - - - (6)
Vll'-~t (V'+V"~Tl~tO~r-Z-r )l R~ rs

OCB OCc =(V'+V")'-;-2[-O"r[Desr--~-'r +Decr -~-'r ]] (7)

VH Ot + Ot
where R~, is the Sauter mean radius of the internal droplets.
The mass balance equation of hydrogen ion in the internal phase is
OCn .l 3Vl
V, . . . . r~ (8)
Ot R~
Also, the following relation holds in the internal phase:
CAi=C°H,I -- CH,I
• (9)
where CA./ is the concentration of silver chloride and its initial concentration is 0. The initial and the boundary
conditions are as follows.
ICs:
CA,in o
C~.m, o 1 for t = 0
CH.m .= CH,II (10)
CB C0 , Cc=O, C A ,I = 0 , CHI, ~ C H,I
O fort=0, allr (11)
BCs:
0Cc
-- 0 for r = 0, all t (12)
Or
ka(Calr.t¢ ~-- CSIr=R ) = kc(Cclr. R - Cclr=R,) for r = R i, all t (13)
aC s
= - Des--0-?--r I,.. '

OCc
-- Do -- r I,.,, '
 S.C. Lee et al. / Journal of Membrane Science 114 (1996) 171-185 175

The above partial differential equations were transformed to ordinary differential equations using the
orthogonal collocation method [17]. The ordinary differential equations were solved with the initial and the
boundary conditions by the FORTRAN subroutine IVPAG available from IMSL M A T H / L I B R A R Y .

4. Experimental

The experimental apparatus used was a batch-type stirred glass cell of 10 cm inner diameter and 15 cm in
depth. The vessel was fitted with stainless steel baffles and set up in a water bath maintained at 25°C. Stirring
was carded out using a turbine impeller with four flat blades, each 5.5 cm diameter, connected with a speed
controller.
The internal aqueous solution was prepared by dissolving commercial EP grade hydrochloric acid in
deionized water. The organic solution was prepared by dissolving di-2-ethylhexyl phosphoric acid (D2EHPA) as
a carrier and Span 80 (sorbitan monooleate) as surfactant in commercial GR grade kerosene. A water-in-oil
( W / O ) type emulsion was made by slowly adding the internal aqueous solution to the organic solution with
mixing provided by a homogenizer (high speed generator, Tekmar Co.). The W / O emulsion was dispersed in
the vessel containing 600 cm 3 of feed solution of silver nitrate (AgNO 3) and stirred at 500 rpm. The initial pH
of the external aqueous solution was adjusted using nitric acid. Samples were taken from the vessels at intervals.
After the external aqueous phase was separated from the emulsion phase by filtration using a filter paper, the
silver concentration in the external phase was analyzed by an atomic absorption spectrophotometer. Experiments
were carried out at varying silver concentration in the external phase, volume fraction of the internal aqueous
phase in the W / O emulsion drop, volume ratio of the emulsion phase to the external aqueous phase, hydrogen
ion concentration in the external phase, and hydrogen ion concentration in the internal phase. Usually, one
parameter was changed and the others were fixed among the typical experimental conditions presented in Table
1. Unless otherwise stated, the initial concentration of silver in the internal phase was 0, the surfactant
concentration was 1.5% ( v / v ) , and the emulsification speed was 6000-7000 rpm. Total operation time was
selected as 30 min since the ELM process performed under the typical conditions of Table 1 reached
equilibrium in this time period.
Chromium ion (500 ppm) was added to the internal phase as a tracer to measure the degree of leakage of the
internal phase to the external phase due to membrane breakage. The experimental methods and the other
conditions were the same as described above. The concentration of chromium ion was analyzed at 375 nm
wavelength by a spectrophotometer (Baush and Lomb Co.).
The size distributions of the W / O emulsion drops and the internal aqueous droplets were measured by the
photographic method and Horiba CAPA-300 particle size analyzer, respectively.

Table 1
Experimental conditions
Parameters Conditions Typical condition
Silver concentration in the external phase 2.3, 4.6, 9.3 mmol/dm 3 4.6 mmol/dm 3
Carrier concentration in the membranephase 2, 5, 10 mmol/dm 3 5 mmol/dm 3
Volume fraction of internal phase in emulsiondrop I/3, 1/2, 2/3 1/2
Volume ratio of emulsion phase to external phase 1/9, 1/6, 1/3 1/6
Hydrogenion concentration 1.0 retool/din 3, 2.5/xmol/dm 3 2.5 p.mol/dm3
in the external phase 0.1 /xmol/dm3
HCI concentration 1.7× 10-2, 4.5× 10-z, 4.5X 10-2 tool/din 3
in the internal phase 1.8× 10- l tool/din 3
176 S.C. Lee et al. / Journal of Membrane Science 114 (1996) 171-185

5. Estimation of parameters

In this study, the effective diffusivity of the complex, Dec, was derived to modify Teramoto et al.'s model
[6]. The model is schematically shown in Fig. 3. A small cube represents an internal droplet, and a larger cube
represents an element consisting of an internal droplet and an organic membrane solution surrounding the
droplet. The fluxes through paths 1, 2 and 3 can be calculated in this model, and given by Eqs. (14)-(16),
respectively.

J, = ksCcoCHo (14)
OC
J2 = "d- (CcoCcm) (15)

Dc
J3 = 7 " ~ ( C c m - Ccf) (16)

where the subscripts, o, m and f, represent the position in the model of Fig. 3. Initially, Cco : ~ Ccm , and the
contribution of Jt on total mass transfer decreases rapidly with time. Also, Crto in Eq. (14) is equal to C H,
average hydrogen ion concentration in a small cube, because the size of internal droplet is very small. So, Jl
can be written as follows:

Jl =ksCH(Cco-Ccm) (17)
D c is the lumped parameter for the diffusivity of the silver-D2EI-IPA complex in the membrane phase. This
involves the circulating effect of the internal aqueous droplets inside the emulsion drop. In reality, at low
suffactant concentration like in the present experimental conditions, the internal aqueous droplets are mobile to
some degree inside the emulsion drop because of the low viscosity of the membrane phase. Such mobility
corresponds to the increase in the diffusion rate of the complex in the membrane phase. From the model, the
continuity of silver complex at steady state is expressed by
12j= d2j, + ( / 2 _ d2)j2 = 12j3 (18)

radial direction

\ :
----_.t_-~ I

Lth 1 ~ ,, . . . . ~ path 3
path 1 ]-[
I '""\,,

I I
I t
i i
0 m f

Fig. 3. Masstransfermodelin W/O emulsionphase.

 S.C. Lee et al./Journal of Membrane Science 114 (1996) 171-185 177

and the effective diffusivity is defined by

0co oo¢
J = O e c 0-"'7- = "7" - ( C c ° - Ccf) (19)

From Eqs. (15)-(18), the flux of the complex is obtained:

(Cco - Ccf)//l
J=
1 -- ~b 1/3
(20)
1
+ - -
[4 \ 1/3 Dc
+ ,,sC. t
where 4) is the volume fraction of internal aqueous phase in an emulsion drop. Finally, the reciprocal of the
denominator of Eq. (20) corresponds to D~c.

[4 ~]/3 + 1 - ~bt/3 (2l)

1/3_ qbl/3 + Dc

The lumped molecular diffusivity, D c, and the stripping reaction rate constant, k s, were determined by
optimization to obtain a minimum difference between the calculated results and the experimental data. D B was
assumed to be equal to D c because the molecular diffusivity of silver complex was almost equal to that of
carrier.
The thickness 8 of the thin oil layer is considered to be equivalent to the thickness l - d of the oil membrane
phase surrounding the internal aqueous droplet, and is expressed by
8 = l - d = ( 4~r/3) l/3 R~,( dp- ]/3 _ 1) (22)
Hence, the mass transfer coefficient k c and k B in the thin oil layer are given by
Dc DB
kc = - " 8 ' kB = 8 (23)
The amount of leakage of the internal phase to the external phase was obtained using chromium ion as a
tracer in the ELM. The influence of various experimental conditions on the leakage is shown in Fig. 4. The
volume fraction of internal phase in W / O emulsion drop and the volume ratio of emulsion phase to external

0 I
5 110 ll5 20 2i5 30
Time (rain)

Fig. 4. Effect of various experimentalconditions on the concentration of chromium ion leaked to the external phase with time. Experimental
conditions: O , typical conditions of Table 1 ( V e / V w = 1/6, ~b = 1/2); rq, V e / V * = 1/3; V, ~b = 1/3; O, V e / V . = 1 / 9 ; / X , ~b = 2 / 3 .
178 S.C. Lee et al. / J o u r n a l o f Membrane Science 114 (1996) 171-185

Table 2
Values of the parameters for the extraction of silver under the typical experimental conditions of Table 1
De.c = 9.187X 10 - s m2//s Keq = 0.0995
kc = 0.188 m / s k s = 1.225× 10 -8 m 4 / m o l s
M s = 2.093× 10 -9 m 3 / s 8 = 1.148X 10 -6 m
R = 7.135× 10 -5 m R~, = 2.74X l0 -6 m
4,= 0.5

phase mainly had effects on membrane breakage under the present experimental conditions. In the other cases of
Table 1, these results were similar to those of the experiment performed under the typical conditions. Membrane
breakage rate, M a is obtained as follows.
dV1 Vm dCcr,III
MS = d t - CCr.llt=O dt (24)
Considerable leakage was observed when the emulsion was dispersed, as shown in Fig. 4. Then, the initial
amount of hydrogen ion in the external phase was assumed to be equal to the amount of hydrogen ion in the
external solution before the dispersion plus the amount of hydrogen ion leaked from the internal phase
instantaneously after dispersion, which was calculated by extrapolation.
The distribution ratio of silver between the aqueous and the organic phases was obtained experimentally
varying pH, silver ion concentration and carder concentration at 25°C, and then the equilibrium constant, K~q,
was determined using Eq. (2). All the parameters estimated for the model are listed in Table 2.

6. Results and discussion

The effect of initial silver concentration in the external aqueous phase on extraction is shown in Fig. 5. Here,
solid lines are calculated results. The higher the initial silver concentration, the lower the degree of extraction.
This is because the internal droplets in the peripheral region of the emulsion drop are more rapidly saturated by
silver, and the complex must diffuse through the membrane phase to the more inner region of the drop to release

1.o i i i

0.8
Q

r.~" o.4

0.o ,~ 6
0 5 10 15 20 25 30
T i m e (rain)

Fig. 5. Effect of initial concentration of silver in the external phase on extraction. Initial concentration of silver in the external phase: Q, 9.3
mmol/dm3; O , 4.6 mmol/dm3; A, 2.3 mmol/dm3; - - , calculated results. The other typical conditions are described in Table 1.
 S.C. Lee et al. /Journal of Membrane Science 114 (1996) 171-185 179

t.0 ~ ~ ,

0.8

"- 0.6

rO~ 0.4

0.2

0.0 I I
5 10 la5 2~0 2t5 30
Time (min)
Fig. 6. Effect of carrierconcentration in the membrane phase on exla-acdon.Carderconcentration in the membrane phase: D, 2 mmol/dm3;
O, 5 mmol/dm3; A, 10 mmol/dm3; --, calculated results. The other typical conditions are described in Table 1.

silver in the internal phase, suggesting that the internal interfacial reaction in the emulsion drops and the
diffusion of complex are important.
Fig. 6 shows the effect of carrier, D2EHPA, concentration in the membrane phase on extraction. The initial
extraction rate increased, as the carrier concentration increased. In the case of higher concentration (0.01 M) of
the carrier, the initial extraction rate was so high that the extraction process reached equilibrium state within 5
min, as shown in Fig. 6. But the degree of extraction decreased adversely after 10 min. It was because the
leakage of the internal aqueous phase still continued. When membrane breakage occurs, the silver and hydrogen
ion concentration in the external phase increase and the concentration gradient of hydrogen ion between the
external and the internal phases is reduced. Consequently, these factors decrease the extraction rate in the
model.
The effect of the volume fraction of internal aqueous phase in the emulsion drop, th, on extraction is
displayed in Fig. 7. In general, the viscosity and the size of emulsion drop increase with this ratio, and the total
interfacial area between the external phase and emulsion drops decreases [2]. However, the extraction rate

1.0

0.8

0.6
ra D

0.4

O O
0.2

I I AI d~
0.0
0 5 1O 115 20 215 30
Time (min)
Fig. 7. Effect of volume fraction of internal phase in emulsion drop, ~b, on extraction. ~b: D, 1/3; O, 1/2; A, 2/3; --, calculated results.
The other typical conditions are described in Table 1.
180 S.C. Lee et al. / Journal of Membrane Science 114 (1996) 171-185

1.0

jo., - D

O2

0.0
0 5 I0 15 20 25 ~0

Time (rain)
Fig. 8. Effect of volume ratio of emulsion phase to external phase, V e / V w, on extraction. Ve/Vw: D, 1/9; ©, 1/6; A, 1/3; --,
calculated results. The other typical conditions are described in Table 1.

increased with the ratio regardless of the decrease in total interfacial area, because the increase in the capacity of
internal phase for trapping silver had a larger effect on extraction rate. Usually, this trend is shown when the
diffusional mass transfer in the membrane phase is fast. This result was identified by the fact that the lumped
molecular diffusivity of the complex in the membrane phase that was obtained by regression, was much larger
than its molecular diffusivity calculated by Wilke-Chang equation [ 18], which meant that actually the internal
aqueous droplets had large mobilities within emulsion drops.
The effect of the volume ratio of emulsion phase to external phase, V e / V w on extraction is shown in Fig. 8.
The extraction rate increased with the ratio, because the total interfacial area between the external phase and
emulsion drops and the capacity of internal phase for trapping silver increased simultaneously. However, a
reasonable V e / V w ratio should be selected for the purpose to be economically feasible.
The effect of initial hydrogen ion concentration in the external aqueous phase on extraction is shown in Fig.
9. Higher extraction rate was observed at lower hydrogen ion concentration in the external aqueous phase,

0.8

-___
b"
~- 0 . 6

0.4

0.2

0.0 6I 110 115 210 ~15 30

Time (rain)
Fig. 9. Effect of initial concentration of hydrogen ion in the extemal phase on extraction. Initial concentration of hydrogen ion in the
ex~mal phase: D, 1.0 mmol/dm3; O, 2.5 p,mol/dm3; A, 0.I p,mol/dm3; --, calculated results. The other typical conditions are
described in Table 1.
 S.C. Lee et al. / Journal of Membrane Science 114 (1996) 171-185 181

1.0

0.8~
""- 0.6
=
0.4
u o
0.2

0.0

Time (rain)
Fig. 10. Effect of initial concentration of hydrochloric acid in the internal phase on extraction. Initial concentration of hydrochloric acid in
the internal phase: n , 1.7X 10 -2 mol/dm3; O, 4.5X 10 -2 mol/dm3; A, 1.8X 10 -1 mol/dm3; - - , calculated results. The other typical
conditions are described in Table 1.

because the driving force for the extraction of silver was the gradient of hydrogen ion concentration between the
external and the internal phases. For the two lower initial hydrogen ion concentrations, the calculated results
were identical because the hydrogen ion concentrations in the external phase were almost the same as soon as
the emulsion phase was dispersed in the external phase.
The variation of the degree of extraction with changing the concentration of HC1 solution used as internal
reagent is shown in Fig. 10. As stated above, the hydrogen ion concentration difference between the external
and the internal phases has the main influence upon the driving force in the ELM process. Thus, the extraction
rate increased with the increase of the HCI concentration in the internal phase because the capacity of the
internal phase, a sink for silver, increased. Also, silver ion which is released into the internal phase reacts with
chloride ion to yield silver chloride incapable of permeation through the membrane phase, and so the

1.0 ~ , , i i

0.8 d

'-'- 0.6
rJ

~,.~ 0 . 4

0.2

0.0
I~o 1~5 r~o z~5 zo
Time (rain)
Fig. 11. Calculated result for the change of the hydrogen ion concentration in the external phase under the typical experimental condition in
Table 1: C), experimental data; - - , calculated results.
182 S.C. Lee et al./Journal of Membrane Science 114 (1996) 171-185

0.8 , b , ,

0.7

0.6

_ 0.5

0.4

0.3

/
---c - ~ , ,f
0.00.0 0.2 0.4 0.6 018 1.o
r/R
Fig. 12. Calculated results for the concentration profiles of siiver-D2EHPA complex in the membrane phase for the different times under
the typical experimental conditions of Table 1 (a, 0.001 s; b, 0.003 s; c, 0.1 s; d, 4 s; e, 60 s; f, 400 s).

concentration gradient of silver ion between the extemal and the internal phases is maintained high because the
silver ion concentration in the internal phase is almost equal to zero.
The change of the hydrogen ion concentration in the external phase under the typical experimental condition
of Table 1 are shown in Fig. 11. The experimental data slightly deviated from the calculated results on the
whole. The hydrogen ion concentration in the external phase increased with time because of the reaction at the
external interface and the leakage of hydrogen ion in the internal phase to the external phase. The slope of the
curve decreased with time, but did not become completely flat. This was because the leakage of the internal
phase due to membrane breakage continued even if the permeation rate of hydrogen ion from internal droplets
decreased with time.
The calculated results for the concentration profiles of silver-D2EHPA complex in the membrane phase
under the typical experimental condition of Table 1 are shown at different times in Fig. 12. Though the

10
g
f
8
e

d
6
b~
e
L~ 4
b

~t

Oo.o o12 o.4' oJ.8 o'.a i.o

r/Rt
Fig. 13. Calculated results for the concentration profiles of silver in the internal phase for the different times under the typical experimental
conditions of Table 1 (a, 0.06 min; b, 0.3 min; c, 1 rain; d, 2.5 rain; e, 6.7 rain; f, 10 rain; g, 30 min).
 S.C. Lee et al./Journal of Membrane Science 114 (1996) 171-185 183

concentration gradient through the emulsion drop is maintained high at the first, it becomes very low within
about 0.1 s. This is because the diffusion rate of the complex, which is produced at the external interface, is
much faster than its stripping reaction rate at the internal interface. Thereafter, the complexes at all radii of the
emulsion drop continue to be exhausted in the membrane phase. From the fact, it is known that the permeation
rate into the emulsion drop, derived by the hydrogen ion concentration difference between the external and the
internal phases, is lower than the stripping reaction rate.
The calculated results for the concentration profiles of silver in the internal phase under the typical
experimental condition of Table 1 are shown at different times in Fig. 13. The silver concentration in the
internal phase is highest on the surface of emulsion drop and decreases slightly toward center regardless of time.
That is, the silver concentrations at center of the emulsion drop for all lines are 0.002-0.36% lower than those
at R~. As described above, this can be explained by the fact that the diffusion rate of the complex through the
membrane is much higher than its stripping reaction rate at the internal interface. Also, the estimated
concentration of silver in the internal phase was nine times higher in 10 min than the initial concentration of
silver in the external phase and then the degree of extraction was about 80%. Thus, if the ELM process was
performed under appropriate operational conditions, a higher degree of extraction and a more concentrated
product can be obtained from the aqueous silver solution.

7. Conclusions

Various experimental data on the batch extraction of silver by emulsion liquid membranes using D2EHPA as
a carrier were analyzed on the basis of a general physical model, involving the combination of the two
facilitated transport mechanisms. Here, the diffusion of the complex in the membrane phase, the extraction and
the stripping reactions between the silver ion and the carder molecule, and the reaction of silver with the
chloride ion in the internal phase to yield silver chloride incapable of permeating through the membrane phase,
were taken into account. Also, the leakage of the internal aqueous phase to the external phase due to membrane
breakage was included in the model developed in this work. Here, the effects of various experimental conditions
such as silver concentration in the external aqueous phase, carrier concentration in the membrane phase, the
volume fraction of internal aqueous phase in emulsion drop, the volume ratio of external phase to emulsion
phase, initial hydrogen ion concentration in the external aqueous phase and hydrochloric acid concentration in
the internal aqueous phase were simulated by the present model. Using the effective diffusivity of complex,
Dec, and the stripping reaction rate constant, k s, obtained by comparing experimental data with calculated
results, the various experimental data could be satisfactorily explained.

8. List of symbols

AgR(HR) silver-D2EHPA complex

C concentration ( m o l / m 3)
d length of small cube in cubic unit element (m)
De lumped effective diffusivity defined by Eq. (21) (m2/s)
D Lumped molecular diffusivity (m2/s)
HR D2EHPA or carrier in the organic phase
J Flux (mol/m 2 s)
kB mass transfer coefficient of carrier in the peripheral thin oil layer (m/s)
kc mass transfer coefficient of complex in the peripheral thin oil layer (m/s)
Keq equilibrium constant
k~ stripping reaction rate constant (m4/mol s)
184 S.C. Lee et aL /Journal of Membrane Science 114 (1996) 171-185

l length of cubic unit element (m)

Ma volumetric rate of the leakage of phase I to phase III (m3//s)
r radius (m)
R Sauter mean radius of emulsion drops (m)
Ri radius of inner core of W / O emulsion drop (m)
rs irreversible reaction rate at the internal interface defined by Eq. (3) (mol/m 2 s)
R~ Sauter mean radius of internal droplet (m)
S total interfacial area between the external aqueous solution and W / O emulsion drops (m 2)
t time (s)
V volume (m 3)
Greek letters
8 thickness of thin oil layer (m)
volume fraction of internal aqueous phase in W / O emulsion drop
Subscripts
A Silver ion or Silver chloride
AgR(HR) silver-D2EHPA complex
B carrier or D2EHPA
C silver-carrier complex
Cr chromium ion
e emulsion phase
f,m,o position in unit element shown in Fig. 3
H hydrogen ion
HR D2EHPA or carrier in the organic phase
w external aqueous phase
1 internal aqueous phase 1 shown in Fig. 3
2 organic phase 2 shown in Fig. 3
3 organic phase 3 shown in Fig. 3
I internal aqueous phase
II membrane phase
III external aqueous phase
Superscript
o initial value

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