Advanced Materials Research Vols 791-793 (2013) pp 315-319 Online: 2013-09-04

© (2013) Trans Tech Publications, Switzerland

doi:10.4028/www.scientific.net/AMR.791-793.315

Mathematical modeling of chromium(Ш) extraction by emulsion liquid

membrane
Yao zhong Xie1,a, De jun Fei*1,b, Ya gu Dang1, Jian xun Wu2
1
College of Chemical Engineering, 2College of Polymer Science & Engineering, Sichuan University,
Chengdu 610065, China
a
xyz11409@163.com, bwwx-ffd@vip.sina.com

Keywords: Emulsion liquid membrane; Chromium(Ш); Extraction; Mathematic modeling; Mass

transfer

Abstract. Advancing front model, carrier-facilitated transfer model and reversible reaction model
were applied to simulate extracting chromium(Ш) from wastewater by emulsion liquid membrane
using di-(2-ethylhexyl) phosphoric acid as carrier and Span-80 as surfactant. Parameters of the
mathematic models were gained from the designed experiments, and the reversible reaction model
can be used with a reasonably accuracy as estimates of chromium(Ш) permeation. The
experimental results demonstrate that the role of reversibility of the chemical reaction between
internal phase and membrane phase should be considered, and the diffusion resistance is the
primary resistance of the mass transfer process.

Introduction
The rapid development of leather tanning, chemical, electroplating and other industries has
resulted in industrial wastewater containing chromium emissions increased year by year [1]. Thus,
removal of chromium due to economic and environment protection reasons is required [2,3]. One of
the promising methods for the separation of heavy metal ions from aqueous solutions is the
emulsion liquid membrane(ELM) process, invented by Li about 40 years ago [4].
Emulsion liquid membrane process has become as an attractive alternative to solvent extraction
for its selective separation and concentrating of compounds from dilute aqueous solutions. And this
process combines extraction and stripping reactions in a single process.
In our previous works, extraction of chromium(Ш) from wastewater have been studied. The
effect of parameters such as concentration of carrier, concentration of internal phase reagent, speed
of agitation and pH value of external phase on extraction efficiency have been investigated
thoroughly [5].
In the present work, mathematical modeling of chromium(Ш) extraction has been investigated.
A comparison of advancing front model, carrier-facilitated transfer model and reversible reaction
model prediction for the extraction of chromium(Ш) from aqueous solutions by ELM is determined
in this paper.

Models formulation
Advancing front model
Ho et al. [6] proposed the simplest model for phenol extraction by ELM from aqueous solution
named advancing front model. This model considers that there is a boundary inside the emulsion
globule called reaction front, which separates the internal region containing no solute from the
external region, and the reaction of the reagent with the solute in the internal droplets is
instantaneous and irreversible. There is local equilibrium between internal and membrane phases in
the reaction region of the globule. Because of not having any adjustable parameters, the model has
great advantage of being easy to implement. Advancing front model has different specific forms
through continuous improvement and change for the model.
The assumptions of the advancing front model are:
(1) The chemical reactions in reaction front are immicible;

All rights reserved. No part of contents of this paper may be reproduced or transmitted in any form or by any means without the written permission of Trans
Tech Publications, www.ttp.net. (ID: 128.210.126.199, Purdue University Libraries, West Lafayette, USA-13/04/15,13:26:49)
316 Chemical and Mechanical Engineering, Information Technologies

(2) No coalescence and redispersion occurs between all emulsion globules;

(3) The Sauter mean diameter is able to describe the system completely;
(4) The distribution coefficient and diffusivity are constant;
(5) The emulsion breakage and swelling are neglected;
(6) The amount of carrier dissolved in the aqueous phases is negligible.
Based on the above assumptions, we derive a set of simultaneous equations from which we
obtain the analytical solution.
V (C − Ct ) 1 / 3
X = [1 − o o ]
Vi Ci
3Deα (Vm + Vi ) Rf
J= ( )C1
Re2
R e −R f
Ct
C1 =
DeαR f
[1 + ]
k o Re ( Re − R f )
db
Jb = (C o − C t )Vo = Bm (C o − C t )Vo
dt
dCt
− Vo = J − Jb
dt

Carrier-facilitated transfer model

Carrier-facilitated transfer model for type II of facilitated mechanism is that carrier is
incorporated in the membrane phase to increase the mass transfer rates.
The assumptions for the model are as follows:
(1) Emulsion globule is spherical and monodisperse, the Sauter mean diameter is adequate for
describing the globule size;
(2) No coalescence and redispersion occurs between all emulsion globules;
(3) The mass transfer resistance in the internal phase is negligible;
(4) There is no internal circulation inside the emulsion globule. And effective diffusivity is
constant in the membrane phase;
(5) The concentration in the external phase is uniform;
(6) Emulsion leakage of the internal phase is negligible.
The five equations from carrier-facilitated transfer model are:
dC t
Vo = -N(4 π R e2 )k （
o C t - C 1）
dt
∂C
- N(4 π R e2 )D（ ） = -N(4 π R e2 )k （
o C t - C 1）
∂r r = R e
e

Ci = q ⋅ C

Vm
∂C
∂t
（ ）
= Vm + Vi De [ 2
1 ∂
r ∂r
r2
∂C
∂r
（
] - Vi R x ）
∂C（r，t）
Rx = i
∂t

Reversible reaction model

Bunge and Noble [7] proposed a reversible reaction model without any adjustable parameters.
Contrast to advancing front model, the model predicts non-zero reagent concentration and
interdependence with internal reagent, solute and product concentrations.
The assumptions for the model are as follows:
(1) Membrane phase is completely immiscible with both external and internal phases;
 Advanced Materials Research Vols. 791-793 317

(2) External phase mass transfer resistance is not considered, and membrane leakage is
neglected;
(3) There is local reaction equilibrium between membrane phase and internal phase;
(4) The concentration of internal phase droplets is independent of position;
(5) The Sauter mean diameter is able to describe the system completely;
(6) No internal circulation occurs in the emulsion globule.
The important equations from reversible reaction model are:
Vi C i + Vm C m Vi /α ' + Vm
C= =( )C m
Vi + Vm Vi + Vm
Vi + α‘Vm
α=
Vi + Vm
∂C ∂C m
De = D‘e
∂r ∂r
α‘ ’
De = De
α

Experimental
Emulsification
A certain amount of surfactant and carrier were added into kerosene as solvent, which were
added to 500 mL three-necked flask and were stirred together. Keep the stirring speed of 3000 rpm
and emulsification time of 10 min to obtain stable emulsion liquid membrane.
Mass transfer
The emulsion liquid membrane was poured in simulated wastewater containing chromium(III),
under certain stirring speed mixed fully, to make chromium(III) transfer into the internal phase via
the membrane phase.
Analytical method
The chromium(III) concentration in aqueous solution is determined by national standard
GB7466-87. 1,5-diphenylcarbazide is used as indicator. The chromium(III) concentration in the
membrane phase is calculated from mass balance. pH value is determined by pH meter.
Reproducibility was confirmed as ±3% or better.

Results and discussion

Model parameters determination
(1) Distribution coefficient
The distribution coefficient was determined by the extraction equilibrium method. Extraction
equilibrium time was obtained by the experiment of 15 min, and the extraction rate was measured,
which was 86.69%. Then, the distribution coefficient of extraction between membrane phase and
external phase was calculated of 6.67 by specific formula.
(2) Sauter mean diameter
Photographic method is used to calculate the Sauter mean diameter, and the experimental results
are shown in figure 1.

Droplet size calculated by the formula: d = ∑ N i d i3

. It can be calculated of 0.6221×10-3m,
∑ i i
N d 2

then the emulsion droplets mean radius is 0.3111×10-3 m.

(3) External mass transfer coefficient
The experimental conditions and experimental results of measuring external mass transfer
coefficient are shown in table 1 and table 2.
318 Chemical and Mechanical Engineering, Information Technologies

Fig.1 Shape of emulsion droplets from the observation

Table 1 Experimental conditions of measuring external mass transfer coefficient

C0 [mol/L] Ci [mol/L] (Vm+Vi)/Vo Vm/Vi Re [10-3m]
0.0003846 0.02 1/5 1/1 0.3111

Table 2 Experimental results of measuring external mass transfer coefficient

Time [s] 0 30 60 90 120
Concentration of 20 8.8434 6.7530 5.2362 4.4473
chromium(III) [mg/L]

The external mass transfer coefficient was calculated of 5.64×10-6 m/s.

(4) Membrane breakage coefficient
The experimental conditions and experimental results of measuring membrane breakage
coefficient are shown in table 3 and table 4.

Table 3 Experimental conditions of measuring membrane breakage coefficient

External phase pH value of (Vm+Vi)/Vo Vm/Vi Re [10-3m]
internal phase
distilled water 1.39 1/5 1/1 0.3111

Table 4 Experimental results of measuring membrane breakage coefficient

Time [min] 0 3 10 20
Breakage 0 0.1815 0.7845 0.9825
degree [%]

The membrane breakage rate was calculated of 0.0004 s-1.

(5) Effective diffusion coefficient
Direct measurement of the effective diffusion coefficient is quite difficult. One method is known
through some physical quantities to estimate, the other is to design a set of liquid membrane
extraction experiments. In this paper, the diffusion coefficient was estimated by the designed
experiment.
The effective diffusion coefficient was determined of 4.3291×10-11 m2/s.
Model validation
Experimental data simulated with three mathematic models compare to results are shown in
figure 2. The reversible reaction model has more reasonably accuracy than other two models as
estimates of chromium(Ш) permeation. It is inferred that extraction reaction not takes place on the
reaction front, but reaction within the whole droplet. The reversible reaction on the membrane phase
interface has a significant effect on the entire mass transfer process.
 Advanced Materials Research Vols. 791-793 319

Fig.2 Comparison between theoretical value of mathematic models and experimental results
(curve 1: advancing front model; curve 2: carrier-facilitated transfer model; curve 3: reversible reaction
model)

Conclusions
The reversible reaction model can be used with a reasonably accuracy as estimates of
chromium(Ш) permeation. The experimental results demonstrate that the role of reversibility of the
chemical reaction between internal phase and membrane phase should be considered, and the
diffusion resistance is the primary resistance of the mass transfer process.

References
[1] B.Zhang, T.Wu, T.Qin, et al. Leather and Chemicals. Vol.27 (2010), pp. 23-28(In Chinese)
[2] G.Arslan, A.Tor, Y.Cengeloglu, et al. Journal of Hazardous Materials. 165 (2009), pp. 729-735
[3] R.Gawronski, P.Religa: Journal of Membrane Science. 289 (2007), pp. 187-190
[4] Norman N.Li, Patent, U.S.CI.208-308 3410794, 1968.11.12.
[5] Lifeng Zhao, Dejun Fei, Yagu Dang, et al. Journal of Hazardous Materials. 178 (2010), pp.
130-135
[6] Ho W S, Hatton T A, et al. AIChE J, 28 (1982), pp. 662-670
[7] P.F.M.M.Correia, J.M.R.de Carvalho. Chemical Engineering Science. 56 (2001), pp. 5317-5325
Chemical and Mechanical Engineering, Information Technologies
10.4028/www.scientific.net/AMR.791-793

Mathematical Modeling of Chromium(Ш) Extraction by Emulsion Liquid Membrane

10.4028/www.scientific.net/AMR.791-793.315