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Separation of manganese from aqueous solution

using an emulsion liquid membrane
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Cite this: RSC Adv., 2015, 5, 84195

Saeed Laki,*a Ahmad Arabi Shamsabadi,b Sayed Siavash Madaenic
and Mohammad Niroomaneshd

The present study deals with the carrier-facilitated transport of manganese from this acidic leach solution in
an emulsion liquid membrane system. The ELM consists of MDEHPA as the extractant, industrial solvent as
the inert diluent, non-ionic polyethylene glycol as a surfactant and sulfuric acid as the stripping solution. The
main parameters inuencing the ELM stability and the extraction of manganese are the pH of the acidic
Received 8th May 2015
Accepted 15th September 2015
leach solution, mixing speed, concentrations of the stripping solution, extractant and surfactant, phase
ratio and treatment ratio. With respect to the parameters mentioned, the optimum conditions for the
DOI: 10.1039/c5ra08547k
process were determined. The results demonstrated the possibility of 93% extraction of manganese by
www.rsc.org/advances ELM from the acidic leach solutions at optimum operational conditions.

emulsiying the internal phase of an immiscible liquid and

Introduction
Manganese is associated with nickel in laterite waste euents1
and has industrial applications in the manufacture of various
chemicals, dry cell batteries, catalysts, adsorbents, plant fertil-
izers, animal feed, glass, ceramics, paints as well as numerous
medicinal purposes. In particular, within the steel industry,
manganese has distinctive properties compared to other metals
with respect to hardness, corrosive resistance, etc.2 The indus-
trial waste euents containing manganese are good potential
sources of this valuable metal. Therefore, due to economic and
environmental considerations, the recovery of manganese from
these streams is of interest.3
Solvent extraction is a common method of metal extraction
that has been extensively used in hydrometallurgical operations
in the treatment of wastewaters to remove soluble metals.
However, metal extraction with an emulsion liquid membrane
is an attractive process due to its high selectivity and it could be
used for a dilute metals system instead of solvent extraction.4,5
This process is technically favorable because of its low energy
consumption and negligible losses of organic liquid. For the
quantitative recovery of manganese and the co-recovery of other
associated metal ions, the emulsion liquid membrane process
may oer the cheapest and the most suitable technique.613
Emulsion liquid membranes are typically prepared by
a
Department of Chemical Engineering, Amirkabir University of Technology (Tehran
Polytechnic), Mahshahr Campus, Mahshahr, Iran. E-mail: saeedlaki@yahoo.com;
Fax: +98 831 4274542; Tel: +98 6152428380
b
Petroleum University of Technology, Ahwaz, Iran
c
Membrane Research Center, Department of Chemical Engineering, Razi University,
Kermanshah, Iran
d
Department of Chemical Engineering, Shahreza Branch, Islamic Azad University,
Shahreza, Iran
then dispersing this emulsion in a third liquid phase (called the
external phase); the internal and the external phases are
miscible, but both are immiscible with the membrane phase.14
In facilitated transport, the carrier promotes solute transfer
through the membrane. The carrier used in ELM can be
regenerated aer its reaction with the inner reagent at the
interface between the membrane and the internal phases, so it
diuses to the outer interface of the ELM and the cycle is
restarted.15 The carrier for metal ion recovery may be acidic,
basic or chelating.16 Some reported organic extractants for the
extraction of metal ions by ELM are D2EHPA, Cyanex 272,
Cyanex 302, LIX 63, LIX 860 and Aliquat 366.17 The
extraction of silver ions from neutral and weakly acidic solu-
tions by D2EHPA, Cyanex 272, Cyanex 302, LIX 63 has been
reported in the literature.1822 Extraction and separation of Ag(I),
Mn(II), Zn(II) and Co(II) using various extractants such as
D2EHPA, tri-n-butyl phosphate and Cyanex 272, Cyanex 302
from dierent solutions have been reported (Ritcey and Lucas,
1971; Devi et al., 1997). MDEHPA, a mixture of mono and di(2-
ethylhexyl) phosphoric acid, showed superior performance due
to its strong chelating capability and less sterically hindered
sites.14,23 However, so far there is no work reported on extraction
and separation of manganese ions with MDEHPA as an
extractant, even though economically MDEHPA is cheaper than
D2EHPA. For quantitative recovery of manganese and co-
recovery of other associated metal ions, the emulsion liquid
membrane process may oer the cheapest and the most suit-
able technique.12,13
As far as we know, no work has been conducted on the
extraction of manganese from the aqueous phase using a
mixture of mono and di(2-ethylhexyl) (MDEHPA) as the extrac-
tant in an ELM system. In this research, extraction of

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manganese from an aqueous solution by an emulsion liquid

membrane with MDEHPA as a carrier diluted with an industrial
paranic solvent and polyethylene glycol (PEG) as a non-ionic
surfactant was performed. The external phase was the source
of manganese.
Hence, the transport of manganese ions occurred from the
external to the internal phase. The parameters aecting the
transport of manganese ions through the ELM, such as
surfactant concentration, phase ratio, stripping phase concen-
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tration, carrier concentration and treatment ratio were studied

to determine the most suitable process conditions among those
investigated. Moreover, a real industrial wastewater sample
the euent of a steel plant (Esfahans Mobarakeh Steel Co.,
Iran) was employed for the extraction of manganese ions. Fig. 2 A scheme of the experimental set up.

Experimental Elmer model PinAAcle 900T) with deuterium background

Apparatus corrector equipped with a 10 cm long slot-burner head and an
airacetylene ame was used. Viscosity determinations were
The ELM experiments were carried out in a cylindrical glass
made on a programmable rheometer, Brookeld Model DV-III,
container of 105 mm diameter and 145 mm height equipped
at room temperature. The pH values of the aqueous solutions
with four round glass baes with 8 mm diameter and equally
were set by a digital pH meter (model Metrohm 780).
spaced in the tank. The impeller for the extraction experiments
was made of Teon with a 95 mm diameter and had three
pitched blades with 45
angles (Fig. 1). Reagents
For experiments with the emulsion system, a water in oil (W/
Span 80 and polyethylene glycol (PEG) were supplied by Fluka
O) emulsion was prepared using organic and strip solutions
and Marun Petrochemical Co. (Iran) respectively. PEG is a by-
using a high shear homogenizer (Omni Programmable Digital
product of the EO/EG plant of Marun Petrochemical
Homogenizer (PDH) model, USA) with variable speed (1000
Company. The chemical composition of PEG is shown in
28 000 rpm). An electric driven agitator, model Heidolph RZR
Table 1.
2020, Germany, with variable speed from 506000 rpm was used
The latter was used as a non-ionic surfactant for stabilizing
in the experiments (Fig. 2).
the emulsion. MDEHPA is a mixture of 55% di-2-ethyl hexyl-
In order to maintain a stable milky white W/O emulsion, a
phosphoric acid ester (D2EHPA) and 45% mono-2-ethyl hexyl-
sonicator (Elmasonic Germany, model: P60H) was used. The
phosphoric acid ester (M2EHPA). This was purchased from
samples were taken at pre-determined time intervals by
Sigma-Aldrich and used as the mobile carrier without further
disposable sanitary syringes and centrifuged by a laboratory
purication. MIPS, an industrial solvent supplied from Marun
centrifuge (ALC PK130 Bench Top Centrifuge) thus separating
Petrochemical Co. (Iran), was used as an inert diluent for the
the primary emulsion phase from the external phase. For the
extraction, with a consistent formulation, mainly of paranic
determination of the concentration of manganese ions in the
and naphthenic hydrocarbons in the range C10C14. The
aqueous samples, an atomic absorption spectrometer (Perkin
industrial solvent (MIPS) was mainly paran. A stock solution
of manganese (1000 mg L1) was prepared by dissolving 3076
mg of manganese sulphate in 1000 mL of demineralized water.
The source phases for various experimental runs were prepared
from this stock solution by dilution with water up to the desired
concentration. Manganese sulphate, sulfuric acid, sodium
hydroxide and other chemicals were of analytical grade and
bought from Chem-Lab NV, Belgium. Demineralized water

Table 1 The compositions and viscosities of PEG

Molecular weight of Viscosity,

PEG (g mol1) PEG cP

20 000 %74
12 000 %22
600010 000 %6 1960
Fig. 1 Dimensions of the preparation and processing tanks. PEG (mixture) 2850

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(conductivity < 0.5 mS cm1 and pH 5.56.0) was used for
preparation of the solutions.
Diluent
The diluent plays an important role in making an emulsion
liquid membrane. The importance of the correct diluent choice
for an extraction processes has been long recognized23 and since
the membrane organic phase consists of an extractant and a
diluent, the role of the diluent on the transport and in the
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membrane stability becomes the most important factor.
Cheapness, negligible loss, good solubility and reduced toxicity
are characteristics of a good diluent. In addition, some of the
other properties that should be considered when selecting a
suitable diluent are specic gravity, viscosity, ash point and
polarity. The most common diluents are n-hexane, kerosene,
cyclohexane, benzene, toluene, carbon tetrachloride, and
chloroform.24,25
In general, aromatic materials have higher specic gravities
than aliphatic materials, which could inhibit dispersion and
coalescence of the solvent. At high metal loading of the solvent,
the dierence between the specic gravity of the loaded solvent
and the aqueous phase is small, which might present problems
in separating the two phases. The density of the solvent usually
increases as the concentration of extractant is increased so the
density of the diluent is a factor that could be taken into
consideration.23
Polarity is one of the most important properties of a diluent.
The extraction of metal ions decreases with an increase in the
polarity of the diluent. Furthermore, the interaction between
diluent and extractant can result in lower extraction eciency.
Therefore diluents with lower dielectric constants are suggested
for the highest extraction. Likewise, aliphatic hydrocarbons are
less hydrophilic than aromatics. The solubility of these solvents
in water is typically on the order of one to ve parts per million.
Aliphatic diluents are generally preferred compared to aromatic
ones due to the polarity. The extraction of metals declines with
an increase in the polarity of the diluent. Interaction of the
diluent with the extractant can result in a lower extraction
coecient for metal ions. MIPS, a locally produced diluent, was
selected owing to its aliphatic character, which provides low
volatility. The chemical composition of MIPS is shown in
Table 2.
Table 2 Specications of the industrial paranic solvent
Parameter Value Unit
<n-C10 Max 0.5% % mol
n-C10+ to n-C11 Min 40% % mol
Max 50%
n-C12+ to n-C13 Min 43% % mol
Max 56%
>n-C13 Max 1.5% % mol
Aromatic and water Max 100 mg kg1
Total sulfur content Max 1 mg kg1
Kinematic viscosity 1.96 @ 20
C cSt
Density 0.83 g mL1
Dielectric constant 1.93
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Preparation of the ELM
The internal aqueous standard solution was prepared by dis-
solving the required amount of H2SO4 in demineralized water.
The organic phase was prepared by dissolving the required
quantity of carrier (MDEHPA) and non-ionic surfactants (PEG,
Span 80) in the MIPS solvent. To prepare a stable W/O emulsion
under stirring (7000 rpm) conditions, the internal or stripping
phase (aqueous H2SO4 solution) was added to the organic phase
to obtain the required volume ratio of organic phase to internal
phase. The blended solution with a volume of 50 mL was
sonicated for 12 h until a stable milky white W/O emulsion was
formed. During the sonication process, the temperature was
controlled below 30
C to avoid de-emulsication. The prepared
emulsion was dispersed into the continuous (source) phase
with a proper stirring arrangement. The organic membrane
phase was prepared by dissolving the appropriate amount of
PEG or Span 80 and MDEHPA in MIPS gently mixed by a
magnetic stirrer. A pre-determined volume ratio of 1 : 1 was
maintained for the organic phase to the internal stripping
phase.
Feed solution preparation
The steel plant euent (Esfahans Mobarakeh Steel Co., Iran)
consisted of 1045 ppm Fe, 970 ppm Mn, 134 ppm Ni, 113 ppm
Cd, 98 ppm Zn, 47 ppm Co and 40 ppm Cu. In order to obtain a
relatively rich solution in this process, with the exception of
manganese, cadmium, and nickel, the other metal ions in the
acidic leach solution were gradually precipitated by adding
various reagents and adjusting the solution pH. Aer adding
sulphuric acid to adjust the pH of the feed phase, re-analysis of
the feed phase concentration showed that apart from manga-
nese, cadmium, iron and nickel, the concentrations of other
metal ions in the acidic leach solution were changed. Moreover,
cadmium was selectively separated out by the emulsion liquid
membrane (ELM) process. The decrease of the concentrations
of Fe, Cu, Co, and Zn ions in the feed solution was not studied.
It was found that the corresponding concentration of Mn in the
feed solution scarcely changed. The Mn, Fe, Ni and Zn
concentrations in the prepared acidic leach solution were 939
ppm, 645 ppm, 104 ppm and 78 ppm, respectively. The
prepared acidic leach solution was used as the feed solution in
the ELM experiments.
Membrane stability
A certain volume of the prepared W/O emulsion was added to
500 mL of external aqueous solution (demineralized water) in a
cylindrical glass vessel attached to an overhead motor driver
(Fig. 2). The impeller agitator used had four 45
pitch blades for
down pumping (diameter 95 mm). The content of the vessel was
stirred in order to disperse the emulsion in the external phase
for dierent contact times to make a W/O/W double emulsion.
The pH of the external phase was continuously measured to
follow its evolution against time. The increase of H ions in the
external phase decreased with the pH of the aqueous solution
(demineralized water) and indicated rupture of the W/O
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emulsion. Each experiment was performed at least twice, and
the average value is reported.
Experimental procedure
The ELM experiments were carried out in a 1000 mL glass
beaker as shown in Fig. 1. A measured quantity of freshly
prepared W/O emulsion was poured slowly into 500 mL of the
continuous phase (aqueous manganese solution) in a glass
beaker. The solution in the beaker was stirred by a motor driven
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order to determine the formation mechanism of the metal
extractant complex during manganese ions extraction, an ideal
extraction system was assumed (liquid phase activity 1)13
leading us to propose eqn (1) for metalextractant complex
formation:
M(aq)n+ + m(HL)x(org) % MLn(HL)mxn(org) + nH(aq)+ (2)
In this equation, M(aq)n+ is the metal ion in the aqueous

mechanical stirrer regulated by a voltage regulator at 200600 phase, (HL)org is the extractant used, MLn(HL)mxn(org) is the
rpm to disperse the emulsion phase. To determine the eect of metalextractant complex and H(aq)+ is the hydrogen ion
the important governing variables on the permeation and the released during metal complex formation. Additionally, n is the
separation of the manganese, surfactant and carrier concen- oxidation number of the metal, m is the number of molecules of
trations, internal phase concentration, stirring speed, volume extractant engaged in the reaction (coordination number) and x
ratio of emulsion to external phase, manganese ions concen- is the polymerization degree of the extractant, i.e., it indicates
tration and pH of the feed solutions were investigated under how the molecules of the extractant are associated with them-
dierent conditions. selves (monomer, dimer, trimer, etc.)
The extraction reaction for Mn2+ can be written as:
Analytical method
First, samples were collected periodically from the beaker and Mn(aq)2+ + m(HL)x(org) % MnL2(HL)mx2(org) + 2H(aq)+ (3)
set aside for a few seconds (around 1020 seconds). As the
from eqn (3), the equilibrium constant (Kex) may be
continuous phase was heavier than the emulsion phase, it
expressed as:
settled at the bottom. Aer the separation of the phases, the
h i
aqueous phase was carefully separated from the organic phase 2
MnL2 HLmx2 : H aq
org
and the equilibrium pH was measured. The concentration of Kex  m (4)
manganese ions in the emulsion phase was calculated from the Mn2 aq $ HLx org
dierence between the external phase concentration before and
aer extraction. In all experiments the results were taken in
and eqn (3) can be also written as:
terms of the concentration of metal ions extracted to the 2h i 3
membrane at dierent time intervals. The extraction percentage MnL2 HLmx2  
6 org 7
(%E) was calculated by the relation: log4 5 log Kex m log HLx org

 Mn2 aq
C0  Ct
E  100 (1)
C0  2 logH aq (5)

where C0 is the initial concentration of metal ions in the feed

solution and Ct is the metal ion concentration in the feed For the extraction of manganese, the distribution coecient
solution aer time interval, t. All experiments were performed at (D) can be expressed as a function of metallic species concen-
the constant temperature of 28  0.1
C using a Shaking Water tration ratio in the organic and aqueous phases at the equilib-
Bath (Julabo, TW20). rium condition as:
h i
MnL2 HLmx2
Results and discussion D
org
(6)
Transport mechanism Mn2 aq

A scheme of the transport of manganese ions through the liquid

membrane facilitated by the carrier is depicted in Fig. 3. In By introduction of eqn (6) into eqn (5), the linear form of the
distribution coecient is obtained as:

log D log Kex + m log[(HL)x]org + 2pH (7)

The mechanism of separation by extraction and re-extraction

(stripping) in the ELM system considered here corresponds to a
liquidliquid cation exchange reaction. The loglog plot of the
distribution coecient (D) versus [HL]org gives an estimate of
the number of the extractant molecules associated with the
extracted manganese complex (Fig. 4).
Fig. 3 Extraction and stripping of manganese ions from the acidic
leach solutions by ELM process using MDEHPA as extractant or carrier.

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The slope in Fig. 4 (2.098) indicates that two molecules of
MDEHPA participated in the formation of the extractable
complex and this supports the proposed equilibrium expression
in eqn (3). The extraction reaction for manganese ions can be
written as:
M(aq)2+ + 2(HL)x(org) % ML2(HL)2(x1)(org) + 2H(aq)+ (8)
The 1 : 2 stoichiometry of the reaction was conrmed by the
result of the equilibrium experiment. The mechanism of the
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counter transport may be represented by the scheme shown in
Fig. 3. This shows transport of manganese ions from the feed
solution to the receiving solution facilitated by the carrier in a
solvent as the membrane phase. Aer the formation at the outer
interface, the complex diuses through the membrane phase to
the inner interface between the membrane and the stripping
phases. If reaction (8) occurs in reverse then the manganese
ions are released into the stripping phase.
Membrane stability
The stability of the ELM is one of the most important parame-
ters that aects the permeation process. Membrane break-up
causes a decrease in the separation eciency due to the
leakage of separated ions from the internal to the external
phase.16 First, stability tests were performed in order to under-
stand whether emulsion components such as surfactants,
diluent, extractant and stripping agent were compatible with
each other or not. Before each test, using trial-and-error,
stability testing was performed. The purpose of this experi-
ment was to choose appropriate diluents to stabilize the
emulsion during the experiments. Stability tests were con-
ducted on some diluents (MIPS, kerosene, toluene and chloro-
form) where the amount of each compound diered in the
organic phase. Equal volumes of organic and stripping phases
were mixed using a high speed homogenizer (10008000 rpm)
for 10 minutes.
Fig. 4 Plot of log(D) vs. log[MDEHPA], pH 6.0; [MDEHPA]0 10% (v/
v); [Mn(II)]0 1000 ppm; T 28  2
C.
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Aer that, the tracer method was used to determine the
stability of the liquid membrane. In order to determine the
stability of the ELM experiments were carried out with dierent
concentrations of PEG and emulsication time. Furthermore,
during the stability experiments we used demineralised water
with marked acidity as the external phase instead of an aqueous
solution containing the manganese ion. The concentration of H
ions was used as a tracer in the internal aqueous phase in all
stability experiments for controlling the eect of mass transfer.
Breakage results in transfer of the tracer from the internal to the
external phase. The stability of the ELM was quantied as the
percentage of H ions transferred from the internal to the
external phase. The breakage ratio is dened as follows:17
 
Ve  H e  H i
B (9)
Vi  H 0
where B is the breakage ratio of the emulsion which represents
the stability of the ELM system, [H+]0 is the initial concentration
of total H ions in the internal aqueous phase, [H+]e is the
concentration of H ions in the external aqueous phase at
contact time, [H+]i is the initial concentration of total H ions in
the external aqueous phase and Ve and Vi are the volume of the
external and the internal aqueous phases, respectively. By
measuring the concentration of H ions in the external phase at
various time intervals, the stability of the ELM with time can be
determined by eqn (9).
Eect of emulsication time on stability
In order to determine the inuence of emulsication time on
the stability of the ELM system, studies were conducted with
various emulsication times in the range of 5.020.0 min.
The eect of emulsication time on the emulsion stability
indicates that less breakage occurred for an emulsication time
of 10 to 15 min and further increases in emulsifying time
decreased the stability (Fig. 5). For insucient emulsication
times (<5 min), the breakage was high due to the large size
leading to the coalescence of the droplets. In contrast, for a long
emulsication time, breakage was important because of high
internal shearing conducive to a very high number of small
droplets by volume unit. This increases the contact frequency
between small droplets contributing to emulsion breakage.
Accordingly, to ensure the stability of the ELM, a 10 min
emulsication was selected as the optimum emulsication
time. Each stability test of the ELM system was conducted more
than twice.
Eect of surfactant concentration on stability
Surfactant concentration is an important factor aecting the
ELM stability, the extraction rate and the emulsion swelling.
The emulsion stability, in particular, is strongly dependent on
surfactant concentration. The stability of the emulsion is
determined by the molecular layer formed by the surfactant
between the oil and the aqueous phases. By increasing the
surfactant concentration, more surfactant molecules are
arrayed between the surface of the oil and the aqueous phase.
On the other hand, excessive surfactant increases the resistance
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Fig. 5 Eect of emulsication time on the stability of the ELM system
(PEG: 4% (w/v), MDEHPA: 10% (v/v), stripping solution: 25 mL 0.5 M
H2SO4; mixing speed: 500 rpm; feed phase (demineralized water;
pH 5.56.0); phase ratio: 5/5; treatment ratio: 1/10).
of the interface. This diminishes the rate of mass transfer (Tang
et al., 2010): Fig. 6 shows the variation of emulsion stability for
various surfactant concentrations. This indicates that the
breakup of the emulsion or emulsion stability was strongly
dependent on the surfactant concentration. From Fig. 6, it is
observed that the emulsion stability is improved by increasing
the surfactant concentration up to 6% (w/v). At low surfactant
concentrations (less than 2%), emulsions are easily broken.
This thin layer does not have a strong inuence on the inter-
action energy and produces no barrier on oil lm rupture. This
Fig. 6 Eect of surfactant (PEG) concentration on stability of the ELM
system (PEG: 36% (w/v), MDEHPA: 10% (v/v); stripping solution: 25
mL 0.5 M H2SO4; mixing speed: 500 rpm; feed phase (demineralized
water, pH 5.56.0); emulsication time: 12 min; phase ratio: 5/5;
treatment ratio: 1/10).
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is due to the fact that as the concentration of surfactant
decreases the surfactant is not adsorbed to a greater extent.
Therefore a more compact and more strongly adsorbed inter-
facial lm of surfactant molecules would not be formed. So this
amount is insucient for surrounding all of the internal
aqueous phase. Consequently, the quantity of surfactant in the
membrane must be adequate for emulsion stabilization.
When the concentration of PEG in the membrane phase was
3 or 4% (w/v), the breakage was remarkably enhanced aer 15
min. By increasing the concentration of PEG to 5 or 6% (w/v) a
linear relationship versus contact time during a 30 minute
period was obtained. There was no substantial dierence
between the breakage ratios for 5 and 6% surfactant concen-
tration (see Fig. 6). On the basis of the results shown in Fig. 6,
the concentration of surfactant was set at 5% (w/v) in all
subsequent experiments since the breakage ratio at 6% (w/v)
was rather close to that at 5.0% (w/v).
In summary, the optimal experimental conditions with the
aim of obtaining a stable W/O emulsion can be summarized as:
emulsion volume: 50 mL; external feed phase volume: 500 mL;
volume ratio of internal phase to organic phase: 1/1; emulsi-
cation time: 12 min; stirring speed 500 rpm; concentration of
PEG: 5% (w/v); feed phase pH 6; volume ratio of emulsion to
external phase: 50/500; internal phase concentration (H2SO4):
0.5 M; diluent: MIPS.
Extraction
Eects of surfactant type and surfactant concentration. The
nature of the surfactant and its concentration play an important
role in the ELM separation processes. The stability and emul-
sion type depend on the nature and concentration of the
surfactant.18 Surfactants are usually organic compounds that
are amphipathic, in that they contain both hydrophilic and
hydrophobic groups. Therefore, they are soluble in both organic
and water phases. The surfactant must be properly chosen in
order to minimize the co-transport of water during the extrac-
tion process. Increasing the concentration of the surfactant
increases the stability of the liquid membrane and decreases
the breakup rate. However, an increase in the surfactant
concentration decreases the removal eciency due to a greater
mass transfer resistance. Accordingly, there is an optimum
concentration for the surfactant.19 Span 80 (HLB 4.7) is a
widely used surfactant for the preparation of W/O type emul-
sions20 in various ELM processes. In this study, we considered
two non-ionic surfactants, one was the widely used Span 80 and
the other was a nonconventional surfactant i.e. PEG. PEG acts as
a bi-functional surfactant in the extraction of some metal ions
such as Zn, Mo, Co, Li, etc.21 In such separations, PEG functions
as a carrier as well as a surfactant. However, in the separation of
manganese ions, PEG acts only as a surfactant, as discussed in
the section on the eect of the carrier concentration.
First, the eect of Span 80 concentration was studied in the
range 47% (w/v). The experimental conditions were applied on
the basis of solvent extraction. Fig. 7 shows the extraction of
manganese ions at various Span 80 concentrations. At the
lowest surfactant concentration (4%), the extraction was
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enhanced for up to 2 minutes. This was followed by a sharp
decline. Increasing the surfactant concentration from 4 to 6%,
resulted in a sharp increase in the amount of extracted
manganese ions. However, aer 10 min due to the instability of
the emulsion, the amount of extracted manganese ions
decreased gradually. Furthermore, around 95% of manganese
ions were separated within 10 min; but at longer time, the
manganese ion concentration in the feed phase was increased.
This is more prominent at lower concentrations of Span 80. It is
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known that Span 80 aects solute transport due to its inuence
on water transport and swelling via osmotic eects.14 Swelling
results in breaking of the emulsion, and hence the manganese
ion concentration in the feed is increased over time. Moreover,
Span 80 is chemically unstable and undergoes the reaction of
hydrolysis in moderate acidic or basic media.20 Because of these
drawbacks of Span 80, we considered another surfactant; PEG.
Fig. 8 shows the extraction of manganese ions at various PEG
concentrations. The extraction of manganese ions was
improved over time reaching an almost constant rate aer 20
min of operation. However, in the case of Span 80 (at a lower
concentration, Fig. 7) the extraction of manganese ions
declined over time. On the other hand, at low concentration, the
emulsions are not stable for a long enough time to allow
separation of emulsion phase from the continuous phase.
Accordingly, PEG was selected as the surfactant of choice for
this separation.
Fig. 7 shows manganese ion extraction with various
concentrations of Span 80. The experiments were carried out
with a feed phase concentration of 1000 mg L1 of manganese
ions and a strip phase concentration of 0.5 M H2SO4. On the
basis of solvent extraction,23 the separation of manganese ions
was maximized at a pH of 6.0. Therefore, the feed phase pH was
maintained at 6.0 by adding the required quantity of H2SO4.
Surfactant concentration is very important in order for the ELM
Fig. 7 Eect of surfactant (Span 80) concentration on the extraction
rate of Mn (Span 80: 47% (w/v); MDEHPA: 10.0% (v/v); stripping
solution: 25 mL 0.5 M H2SO4; mixing speed: 500 rpm; Mn concen-
tration of feed solution: 1500 mg L1; feed solution pH: 6.0; phase
ratio: 5/5; treatment ratio: 1/10).
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Fig. 8 Eect of surfactant (PEG) concentration on the extraction rate
of Mn (PEG: 36% (w/v); MDEHPA: 10.0% (v/v); stripping solution: 25
mL 0.5 M H2SO4; mixing speed: 500 rpm; Mn concentration of feed
solution: 1500 mg L1; feed solution pH: 6.0; phase ratio: 5/5; treat-
ment ratio: 1/10).
to stabilize the emulsion during the process. The main disad-
vantage is the viscosity increment with an improvement in mass
transfer resistance.18
For PEG, Fig. 8 shows that at the lowest surfactant concen-
tration (3%), about 96% of manganese ions were separated
within 5 min but aer that, due to the instability of the emul-
sion, the amount of extracted manganese ions decreased
sharply. Increasing the surfactant concentration from 4 to 5%,
resulted in a sharp increase in the amount of extracted
manganese ions. When the surfactant concentration of the
organic phase was increased to 6%, the extraction eciency for
manganese ions was decreased. Excessive surfactant increases
the resistance at the interface and this can be attributed to a
number of possible factors caused by high interfacial occupancy
of the surfactant, including a decrease in metal ion extraction at
the membrane phasefeed phase interface, an increase in
interfacial viscosity and a decrease in the movement of inner
droplets within the emulsion globule.610 The extraction of
manganese ions using 5% surfactant was similar to that at 4%.
However, subsequent experiments were carried out at the
higher PEG concentration of 5% (w/v) to ensure the ELMs
stability.
Eect of feed solution pH. The extraction reaction on the
membranefeed solution side plays a vital role in the transfer of
metal ions from the feed side to membrane side. So the
extraction kinetics was studied with dierent feed phase pH
values varied from 5.07.0. Fig. 9 shows the eect of pH (H ion
concentration) on the kinetics of manganese ion extraction and
on the nal manganese ion concentration. It is clear from eqn
(7) that transport of ions through the ELM is dependent on the
H ion concentration in the feed solution. As seen from Fig. 9,
manganese extraction was increased by increasing the pH
between 5.0 and 6.0. However, for pH between 6.0 and 6.5, the
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Fig. 9 Eect of feed solution pH on the extraction rate of Mn (PEG: 5% Fig. 10 Eect of stripping solution type on the extraction rate of Mn
(w/v); MDEHPA: 10.0% (v/v); stripping solution: 25 mL 0.5 M H2SO4; (PEG: 5% (w/v); MDEHPA: 10.0% (v/v); stripping solution: 25 mL 0.5 M;
mixing speed: 500 rpm; Mn concentration of feed solution: 1500 mg L1; mixing speed: 500 rpm; Mn concentration of feed solution: 1500 mg L1;
feed solution pH: 5.07.0; phase ratio: 5/5; treatment ratio: 1/10). feed solution pH: 6.0; phase ratio: 5/5; treatment ratio: 1/10).

extraction eciency of manganese ions hardly changed when increasing the concentration of sulfuric acid from 0.5 to 0.6 M.
increasing the pH. When the pH of the feed phase was Again, the extraction eciency of manganese was increased
increased to 7.0, the extraction and enrichment of manganese (Fig. 11) by increasing the acidity in the stripping phase. The
ions decreased due to swelling of the emulsion. The osmotic dierences of the hydrogen ion chemical potentials between the
pressure dierence due to the pH increment was responsible for two aqueous phases are the main driving force in the emulsion
water transport into the internal phase leading to swelling. liquid membrane for the counter-transport mechanism. Thus,
Accordingly, an acidic feed phase facilitates manganese the extraction eciency was increased by enhancing the
enrichment. concentration of H2SO4 in the stripping solution from 0.3 to 0.5
The poor performance at low pH could be explained by the M. However, for a concentration of 0.6 M sulfuric acid, the
competition of H ions with the solute due to the release of H emulsion swells up due to osmosis, which may lead to the
ions from the extractant to the acidic leach solution. As a result,
maximum extraction was achieved at pH 6.5. At this pH,
swelling of the emulsion was not observed. Thus, pH 6.5 was
found to be the optimal pH.
Eect of stripping solution type. As a general rule, the most
important factor for application of an emulsion liquid
membrane is the emulsion stability. In addition to mixing
speed, extractant, and surfactant concentration, another
parameter is the type of stripping agent.26 The selection of a
suitable stripping solution is considered to be one of the key
factors for an eective ELM system. Initially we examined HCl,
H2SO4, and HNO3 as stripping solutions for the current ELM.
The results are presented in Fig. 10. The stripping solution with
0.5 M H2SO4 solution provided higher manganese extraction
and more stable emulsion. Therefore, 0.5 M sulfuric acid was
selected as the stripping solution of choice.
Eect of internal phase concentration. The solute extraction
rate increases with an increase in the concentration of the
internal reagent in the emulsion.19 The inuence of H2SO4
concentration in the strip phase on the transport of manganese Fig. 11 Eect of stripping solution acid concentration on the extrac-
was studied in the range of 0.30.6 M H2SO4. By increasing the tion rate of Mn (PEG: 5% (w/v); MDEHPA: 10.0% (v/v); stripping solu-
sulfuric acid concentration from 0.3 to 0.5 M, the extraction tion: 25 mL 0.30.6 M H2SO4; mixing speed: 500 rpm; Mn
eciency was improved. However, this was diminished by concentration of feed solution: 1500 mg L1; feed solution pH: 6.0;
phase ratio: 5/5; treatment ratio: 1/10).

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Paper
dilution of the internal phase and a decrease of its acidity
causing a lower stripping and a consequent lower extraction.
Additionally, for longer times the osmotic eect causes an
increase in external phase concentration and in the ratio C/C0.27
Eect of carrier concentration. Manganese ions are insol-
uble in organic solvents without the assistance of a mobile
carrier. The carrier in the membrane phase has two important
roles: one is to transport manganese ions between the external
and the internal interface of the membrane phase; and the
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other is to improve the selectivity of the ELM. Theoretically,
MDEHPA enhances the extraction by forming complexes with
manganese ions, which are permeable through the solvent
(membrane phase). The inuence of the carrier (MDEHPA)
concentration on the extraction of manganese was studied in
the range of 5.012.5% (v/v). The eect of carrier concentration
on the extraction of manganese ions is displayed in Fig. 12. It is
evident from Fig. 12 that extractant concentration has a
signicant eect on extraction of manganese ions from acidic
solution.
The transport of manganese ions was negligible in the
absence of a carrier. This indicates that PEG does not show any
capability as an extractant and acts as a surfactant in the present
study. With the increase of carrier concentration in the
membrane phase the extraction of manganese was improved.
This is in good agreement with eqn (3). An increase in extractant
concentration from 5% to 10% leads to an increase in extraction
eciency from 90 to 96%. However, increasing the extractant
concentration from 10% to 12.5% did not result in any signi-
cant change in the extraction eciency. The unchanged
extraction eciency can be also attributable to the increased
membrane phase viscosity as the carrier concentration
increases in this phase. The higher concentration of carrier at
Fig. 12 Eect of carrier concentration on the extraction rate of Mn
(PEG: 5% (w/v); MDEHPA: 0.012.5% (v/v); stripping solution: 25 mL 0.5
M H2SO4; mixing speed: 500 rpm; Mn concentration of feed solution:
1500 mg L1; feed solution pH: 6.0; phase ratio: 5/5; treatment ratio: 1/
10).
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the interface between the emulsion and external phase
promotes the transport of the solute. However, it is expected
that a very high content of carrier in the membrane does not
result in a benet due to the respective increase in viscosity,
which leads to larger globules. Consequently, the kinetics is
slower as shown in Fig. 12. Similar results have been obtained
by other researchers.8,9 Accordingly, an extractant concentration
of 10% was considered the optimum value for manganese ion
extraction.
Eect of mixing speed. A key parameter aecting the process
is the mixing speed. The eciency of ELM extraction was
improved by increasing the mixing speed. This is due to a
decline in the size of emulsion globules providing a higher
surface area for mass transfer. However, a large enhancement of
this speed aects the stability of the emulsion globules leading
to longer times and to their breakage because of the excessive
shearing energy input in the system.19,23
Therefore, the extraction eciency of manganese decreased
with long term operation. Fig. 13 indicates that the maximum
extraction (97%) occurred at 25 min with a mixing speed of 600
rpm. Beyond 10 min, extraction eciency was decreased for 700
rpm.
Eect of organic/internal phase volume ratio. The volume
ratio of the aqueous internal phase to the organic phase has a
signicant eect on extraction using ELMs. The phase ratio is
dened as:
volume of stripping solution VS
D (10)
volume of membrane solution VM
An increase in the stripping solution volume fraction results
in an enhancement of the capacity of the emulsion to extract the
solute. When the volume of the stripping solution increases (i.e.
Fig. 13 Eect of mixing speed on the extraction rate of Mn (PEG5% (w/
v); MDEHPA: 10.0% (v/v); stripping solution: 25 mL 0.5 M H2SO4;
mixing speed: 400700 rpm; Mn concentration of feed solution: 1500
mg L1; feed solution pH: 6.0; phase ratio: 5/5; treatment ratio: 1/10).
RSC Adv., 2015, 5, 8419584206 | 84203

RSC Advances
the phase ratio is increased), the thickness of the lm in
droplets becomes thinner due to dispersion of the stripping
solution in the membrane phase by mixing.28,29 This is favorable
to the transport of manganese ions into the stripping solution
and results in an increase in the extraction of manganese ions.
The eect of the volume ratios of the internal stripping solution
to the membrane phase in the range of 4/57/5 on extraction of
manganese ions, by maintaining a constant membrane volume,
is depicted in Fig. 14. The extraction eciency was improved by
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increasing the phase ratio from 4/5 to 6/5 because of the greater
availability of extractant for the manganese extraction. Beyond
the ratio of 6/5, a further increase in the volume of the internal
aqueous solution decreased both the rate and the eciency of
the extraction. This may be due to an increase in the emulsion
viscosity and an improvement in the diameter of the internal
droplets.8,28 The increase of the droplet diameter decreases the
interfacial contact area between the emulsion and feed solu-
tion. This decreases the extraction eciency. Additionally, the
emulsion stability may decrease rapidly with an increase of the
phase ratio from 6/5 to 7/5. Increasing the stripping phase
volume makes the emulsion unstable with a leakage of the
internal phase into the continuous phase.
In order to obtain a better extraction eciency in the
membrane solution, the volume ratio of the internal aqueous
phase to the membrane phase of 6/5 was selected as the
optimum volume ratio.
Eect of treatment ratio. The volume ratio of the primary
emulsion to the feed solution (VE/VF) aects the interfacial mass
transfer across an ELM. This is a measure of the emulsion
holdup in the system. Improving the treatment ratio (VE/VF)
results in an increase in the emulsion phase holdup and
simultaneously an increase in the extraction capacity of the
emulsion.8 As a general expectation, a higher treatment ratio
leads to higher extraction eciency.
Fig. 14 Eect of phase ratio on the extraction rate of Mn (PEG: 5% (w/v);
MDEHPA: 10.0% (v/v); stripping solution: 25 mL 0.5 M H2SO4; mixing
speed: 500 rpm; Mn concentration of feed solution: 1500 mg L1; feed
solution pH: 6.0; phase ratio: 4/57/5; treatment ratio: 1/10).
84204 | RSC Adv., 2015, 5, 8419584206
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Fig. 15 shows that, as the treatment ratio is varied from 0.1 to
0.2, while the emulsion phase holdup was low (treatment ratio
around 0.1), the rate of extraction was at its minimum. When
maintaining all other parameters as constant, there is an
increase in the rate of extraction. This increase occurs when the
phase ratio increases from 0.1 to 0.15, but increasing the
emulsion holdup to 0.16 slightly increased the extraction e-
ciency. Beyond the ratio of 0.16 (treatment ratio around 0.2) the
extraction eciency was diminished. This behavior can be
explained by two opposite phenomena occurring simulta-
neously. Increasing the treatment ratio increases the quantity of
membrane and internal phase, the amount of carrier in the
membrane phase and the membrane phase surface area for
transport. This enhances the permeation and stripping of
manganese.21,30 An increase in the emulsion volume leads to a
reduction of the mass transfer area and hence the rate of
extraction. In this case, a longer extraction time is required and
consequently more emulsion breakage is expected.21 This
reduces the permeability and stripping of manganese. There-
fore, a treatment ratio of 0.15 was selected as the treatment ratio
for optimum conditions.
Extraction of manganese from industrial wastewater at
optimum conditions
The optimum conditions for extraction of manganese ions,
obtained from the previous experiments using the specied
ELM, are presented in Table 3. The same process at optimum
conditions was employed for the extraction of manganese from
real industrial wastewater to elucidate the feasibility of the ELM
process in treating real euent.
The experiments were carried out by adjusting the pH of
industrial wastewater from 6.8 to 6.5 by adding H2SO4. The
eect of the optimum conditions on the extraction eciency of
manganese from the acidic leach solution-containing Mn, Fe,
Fig. 15 Eect of treatment ratio on the extraction rate of Mn (PEG: 5%
(w/v); MDEHPA: 10.0% (v/v); stripping solution: 25 mL 0.5 M H2SO4;
mixing speed: 500 rpm; Mn concentration of feed solution: 1500 mg L1;
feed solution pH: 6.0; phase ratio: 5/5; treatment ratio: 0.10.2).
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Table 3 Optimum conditions for the extraction of manganese with 2. The proposed ELM process was ecient in the separation
the ELM of manganese ions from industrial wastewater with removal of
9293% of manganese ions.
Parameter Value
3. The experimental results obtained also demonstrated the
Surfactant (PEG) 5% (w/v) validity of the ELM method for the treatment of industrial
Extractant (MDEHPA) 10.0% (v/v) wastewaters contaminated with manganese ions.
Diluent (MIPS) Table 1
Stripping solution type 25 mL H2SO4 solution
Stripping solution H2SO4 concentration 0.5 M References
pH of the feed solution 6.5
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Mixing speed 600 rpm
Phase ratio 6/5
Treatment ratio 0.15
Ni and Zn ions is presented in Fig. 16 indicating an extraction of
around 9293% of the manganese as well as low extraction of
iron, nickel and zinc within a period of 30 min of permeation.
This is expected due to the interference of other ions present in
the feed phase. The present work provides a basis for extraction
and removal of manganese ions from real industrial wastewater
using an emulsion liquid membrane indicating an acceptable
performance at the conditions established in this work.
Conclusions
An emulsion liquid membrane process using MDEHPA as an
extractant to selectively extract manganese ions from an acidic
leach solution containing various metal ions has been investi-
gated. From this study, the following conclusions can be drawn.
1. The extraction of manganese ions is inuenced by a
number of variables including the pH of the feed aqueous
solution, mixing speed, concentrations of surfactant, stripping
phase and carrier, and treatment ratio.
Fig. 16 Eect of the optimum conditions on the extraction rate of Mn
from real industrial wastewater (PEG: 5% (w/v); MDEHPA: 12.5% (v/v);
stripping solution: 25 mL 0.5 M H2SO4; mixing speed: 500 rpm; feed
solution: real industrial wastewater; feed solution pH: 6.5; phase ratio:
6/5; treatment ratio: 1/10).
1 W. Zhang and C. Y. Cheng, Manganese metallurgy review,
Part II: manganese separation and recovery from solution,
Hydrometallurgy, 2007, 89(34), 160177.
2 N. B. Devi and S. Mishra, Solvent extraction equilibrium
study of manganese(II) with Cyanex 302 in kerosene,
Hydrometallurgy, 2010, 103, 118123.
3 D. H. Fatmeshari, D. Darvishi, S. Etenadi, A. R. E. Hollagh,
E. K. Almadri and A. A. Salardini, Interaction between TBP
and D2EHPA during Zn, Cd, Mn, Cu, Co and Ni solvent
extraction: a thermodynamic and empirical approach,
Hydrometallurgy, 2009, 98, 143147.
4 J. Gega, W. Walkowiak and B. Gajda, Separation of Co(II) and
Ni(II) ions by supported and hybrid liquid membranes, Sep.
Purif. Technol., 2001, 2223, 551558.
5 R. A. Wood and R. V. Roscoe, The isolation of manganese in a
system between bis(2-ethyl-hexyl) hydrogen phosphate and
aqueous nitric acid, J. Inorg. Nucl. Chem., 1970, 32, 1351
1355.
6 P. S. Kulkarni and V. V. Mahajani, Application of liquid
emulsion membrane (LEM) process for enrichment of
molybdenum from aqueous solutions, J. Membr. Sci., 2002,
201, 123135.
7 L. Yang, Z. Zhang, Y. Guo, X. Gao and H. Takeuchi,
Uranium(VI) extraction by liquid surfactant membrane with
N-alkylcaprolactams as a carrier, Sep. Purif. Technol., 2005,
47, 8894.
8 R. A. Kumbasar, Extraction of chromium(VI) from
multicomponent acidic solutions by emulsion liquid
membranes using TOPO as extractant, J. Hazard. Mater.,
2009, 167, 11411147.
9 N. Othman, H. Mat and M. Goto, Separation of silver from
photographic wastes by emulsion liquid membrane
system, J. Membr. Sci., 2006, 282, 171177.
10 N. B. Devi, K. C. Nathsarma and V. Chakravortty, Separation
of divalent manganese and cobalt ions from sulfate
solutions using sodium salt of D2EHPA, PC 88A and
Cyanex 272, Hydrometallurgy, 2000, 54(23), 117131.
11 S. C. Lee, J. H. Chang, B. S. Ahn and W. K. Lee, Mathematical
modeling of silver extraction by an emulsion liquid
membrane process, J. Membr. Sci., 1996, 114, 171185.
12 A. P. Argekar and A. K. Shetty, Extraction of manganese(II)
with bis(2,4,4-trimethylpentyl) mono-thio-phosphinic acid
and its spectrophotometric determination with form
aldoxime, Anal. Sci., 1997, 13, 131135.
13 G. M. Ritcey and B. H. Lucas, Purication of manganese
solutions containing copper and zinc by liquidliquid
extraction, using di-(2-ethyl-hexyl) phosphoric acid, Can.
Metall. Q., 1971, 10, 223228.

This journal is The Royal Society of Chemistry 2015 RSC Adv., 2015, 5, 8419584206 | 84205

RSC Advances
14 G. C. Sahoo and N. N. Dutta, Studies on emulsion liquid
membrane extraction of cephalexin, J. Membr. Sci., 1998,
145, 1526.
15 A. Kargari, T. Kaghazchi, M. Sohrabi and M. Soleimani,
Experimental and modeling of selective separation of
gold(III) ions from aqueous solutions by emulsion liquid
membrane system, J. Membr. Sci., 2006, 279, 389393.
16 A. Kargari, T. Kaghazchi, M. Sohrabi and M. Soleimani,
Batch extraction of gold(III) ions from aqueous solutions
Published on 16 September 2015. Downloaded by Pamukkale University on 20/08/2017 11:50:40.
using emulsion liquid membrane via facilitated carrier
transport, J. Membr. Sci., 2004, 233, 110.
17 B. Tang, G. Yu, J. Fang and T. Shi, Recovery of high-purity
silver directly from dilute euents by an emulsion liquid
membrane-crystallization process, J. Hazard. Mater., 2010,
177, 377383.
18 K. Chakrabarty, P. Saha and A. K. Ghoshal, Separation of
lignosulfonate from its aqueous solution using emulsion
liquid membrane, J. Membr. Sci., 2010, 360, 3439.
19 H. J. Park and T. S. Chung, Removal of phenol from aqueous
solution by liquid emulsion membrane, Korean J. Chem.
Eng., 2003, 20, 731735.
20 I. A. Nemeh and A. P. V. Peteghem, Sorbitan monooleate
(Span 80) decomposition during membrane ageing, a
kinetic study, J. Membr. Sci., 1992, 74, 917.
21 C. F. Jee, T. B. Long, X. M. Xia, Q. Q. Jin and Z. L. Ying, A
study on a two components liquid membrane system, J.
Membr. Sci., 1985, 23, 137154.
22 R. Mohapatra and S. B. Kanungo, Kinetics of Mn(II) transport
from aqueous sulfate solution through a supported liquid
membrane containing di(2-ethylhexyl) phosphoric acid in
kerosene, Sep. Sci. Technol., 1992, 27, 17591773.
84206 | RSC Adv., 2015, 5, 8419584206
View Article Online
Paper
23 N. B. Devi, K. C. Nathsarma and V. Chakravortty, Extraction
and separation of Mn(II) and Zn (II) from sulfate solutions by
sodium salt of Cyanex 272, Hydrometallurgy, 1997, 45(12),
169179.
24 L. Soko, L. Chimuka, E. Cukrowska and S. Pole, Extraction
and preconcentration of manganese (II) from biological
uids (water, milk and blood serum) using supported
liquid membrane and membrane probe methods, Anal.
Chim. Acta, 2003, 485, 2535.
25 S. S. Kolekar and M. A. Anuse, Solvent extraction separation
of rhodium(III) with N-noctylaniline as an extractant,
Talanta, 2002, 58, 761771.
26 C. P. Mane and M. A. Anus, Extraction behaviour of 2-
octylaminopyridine towards lead(II) from succinate media
and its separation from other toxic metals, J. Hazard.
Mater., 2008, 152, 11461154.
27 A. Reis, M. Teresa and J. M. R. Carvalho, Recovery of zinc
from an industrial euent by emulsion liquid membranes,
J. Membr. Sci., 1993, 84(3), 201211.
28 C. Das, M. Rungta, G. Arya, S. DasGupta and S. De, Removal
of dyes and their mixtures from aqueous solution using
liquid emulsion membrane, J. Hazard. Mater., 2008, 159(2
3), 365371.
29 A. Daas and O. Hamdaoui, Extraction of anionic dye from
aqueous solutions by emulsion liquid membrane, J.
Hazard. Mater., 2010, 178, 973981.
30 L. Boyadzhiev and E. Bezenshek, Carrier mediated
extraction: application of double emulsion technique for
mercury removal from wastewater, J. Membr. Sci., 1983, 14,
1318.
This journal is The Royal Society of Chemistry 2015