Journal of Industrial and Engineering Chemistry 22 (2015) 296305

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Journal of Industrial and Engineering Chemistry

journal homepage: www.elsevier.com/locate/jiec

Extraction of endocrine disrupting compound propylparaben from

water by emulsion liquid membrane using trioctylphosphine oxide as
carrier
Sarah Chaouchi, Oualid Hamdaoui *
Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, Badji MokhtarAnnaba University, PO Box 12,
23000 Annaba, Algeria

A R T I C L E I N F O

Article history:
Received 9 December 2013
Received in revised form 13 May 2014
Accepted 13 July 2014
Available online 29 July 2014
Keywords:
Endocrine disrupting compound
Propylparaben
Extraction
Emulsion liquid membrane
Trioctylphosphine oxide (TOPO)

A B S T R A C T

The extraction of endocrine disrupting compound propylpraben (PP) from aqueous solution by emulsion
liquid membrane was investigated. The ELM contains trioctylphosphine oxide (TOPO) as extractant, nhexane as solvent and Span 80 as surfactant. Na2CO3 was used as internal aqueous phase. The effects of
operating parameters for the ELM process were examined. It was possible to perfectly remove all of PP
molecules from the external feed solution by using the best experimental conditions. ELM treatment
process represents an efcient advanced separation technique for the removal of PP even from complex
matrices such as natural water, seawater and sewage water efuent.
2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights
reserved.

Introduction
The development of society modernization leads to the
extensive use of pharmaceuticals and personal care products
(PPCPs). A large variety of PPCPs and metabolites thereof are
continually introduced into the environment through human
wastes by excretion, washings and manufacturing. PPCPs have
recently been detected in sewage efuents [14], surface and
ground water [36] and even drinking water [3,7].
Parabens, alkyl esters of p-hydroxybenzoic acid, are the most
commonly used preservatives and bactericides in the foods,
beverages, pharmaceuticals and cosmetic industries. These compounds are considered endocrine disrupting chemicals, because of
their endocrine activity [8,9], and have been detected in human
tissues, including breast tumors [10,11]. Moreover, parabens are
continuously released in urban wastewater at relatively high levels
and, despite being considerably removed during conventional
sewage treatments, they have been still detected in river water
samples [12]. Therefore, the U.S. Environmental Protection Agency

* Corresponding author. Tel.: +213 038876560; fax: +213 038876560.

E-mail addresses: ohamdaoui@yahoo.fr, oualid.hamdaoui@univ-annaba.dz
(O. Hamdaoui).

(USEPA) has classied parabens as emerging environmental

pollutants [13].
To avoid undesired accumulation of parabens in aquatic
environments, development of powerful treatment techniques is
underway to remove these compounds from water. From this point
of view, emulsion liquid membrane (ELM) has gained much
attention as an advanced extraction process for the removal of
contaminants present in wastewater. Compared to conventional
processes, the main advantages of ELM techniques are:
(a) simple operation, high extraction efciency and scope of
continuous operation;
(b) high interfacial area resulting in enhancement of mass transfer
rate, especially at the inner membranewater interface, due to
the small size of the aqueous phase droplets;
(c) simultaneous performance of extraction (at the outer interface)
and stripping (at the inner interface) in the same system, which
implies that in practice there would be no need to construct
separate circuits for stripping and extraction;
(d) capability of treating a variety of elements and compounds in
industrial setting at a greater speed and with and a high degree
of effectiveness, with varying contaminant concentrations and
volume requirements;
(e) relatively low cost and energy conservation due to its cycling
usage and non-dependence on heating consideration;

http://dx.doi.org/10.1016/j.jiec.2014.07.023
1226-086X/ 2014 The Korean Society of Industrial and Engineering Chemistry. Published by Elsevier B.V. All rights reserved.

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

297

(f) requirement of expensive extractant and organic solvent,

necessary to form an oil membrane, in small quantities.

volume ratio of internal aqueous phase to organic phase was

changed from 1/2 to 2/1.

ELM processes are those involving a selective liquid membrane

phase in which simultaneous extraction/stripping occurs. Separation is achieved by permeation of solute through this liquid phase
from a feed phase to a receiving phase. The feed and receiving
phases are normally miscible while the membrane phase is
immiscible in both. An ELM can be considered as a double emulsion
consisting of three phases: the external, membrane and internal
phases. Receiving phase is emulsied in an immiscible liquid
membrane with the use of surfactants and high-speed agitation.
Emulsion droplets range from 1 to 3 mm in diameter, thus
providing good stability [14]. The emulsion is then dispersed in the
feed solution with constant agitation and mass transfer from the
feed to the internal receiving phase takes place. Once dispersed in
the continuous phase, globules of the emulsion of a diameter of
1002000 mm form [14]. Hence, the liquid membrane serves a dual
purpose of permitting selective transfer of one or more components through it from external phase to internal droplets and vice
versa and preventing mixing of external and internal phases. After
the desired separation, the emulsion and the continuous phase are
separated in a settling step. The nal step in the ELM process
involves breaking the emulsion, whereby the internal phase is then
recovered and the membrane phase can be reused.
To the best of our knowledge, none of the earlier studies has
evaluated the extraction of parabens from aqueous phase by ELM.
Additionally, it is of considerable practical interest to examine the
removal of parabens from complex matrices such as natural water,
seawater and sewage water efuent. Therefore, the present
investigation aims to the development of an ELM system for the
extraction of PP from aqueous solutions. The inuence of operating
parameters such as surfactant and extractant concentrations,
emulsication time, sodium sulfate concentration in external
phase, salt type in external phase, internal phase concentration,
type of internal phase, stirring speed, volume ratio of internal
phase to membrane phase, treatment ratio, diluent type and PP
initial concentration on the extraction of PP by ELM was evaluated.
In addition, removal of PP by ELM from pure water, natural water,
seawater and sewage water efuent was examined. The effect of
internal phase concentration on the stripping of PP was studied.

Extraction

Materials and methods

Materials
Analytically pure PP (C10H12O3, Propyl 4-hydroxybenzoate) was
purchased from Fluka and has been used as received. Stock
solutions of PP were prepared by dissolving appropriate amount of
compound in distilled water. PP feed solutions from a known
amount of PP stock solution were diluted with distilled water to a
given concentration. Though PP occur in concentrations ranging
from ng/L up to mg/L in water, we chose higher concentrations to
check the feasibility of the ELM process.
Trioctylphosphine oxide (TOPO) used as extractant in this work
was of analytical grade and procured from Sigma-Aldrich.
All other chemicals used in this work were of the highest
available purity and were purchased from Sigma-Aldrich.
Internal aqueous standard solutions were prepared by taking
the required amount of alkaline solution (Na2CO3, NaOH or
NH4OH) in distilled water. The organic membrane phase was
prepared by dissolving the appropriate amount of Span 80 as a
surfactant in hexane under a gentle mixing by a magnetic stirrer.
The emulsion was prepared by mixing the internal aqueous
solution with the organic membrane phase using a high-speed
disperser (Ultra-Turrax IKA T18) for a xed mixing time. The

The extraction of PP using emulsion liquid membrane involves

three steps namely preparation of liquid membrane emulsion,
extraction of the solute from feed by contacting the emulsion and
separation of liquid emulsion from the external phase by settling.
The three-phase dispersion (W/O/W) was stirred with a
mechanic stirrer (Junke & Kunkel RW20) at 300 rpm (except
when the effect of stirring speed was studied). The agitator used
was a 458 pitch four blades down pumping impeller (diameter
5 cm). A volume of the prepared W/O emulsion was added to
250 mL of external aqueous solution in a cylindrical thermostated
vessel that was attached to an overhead mechanical stirrer. The
content of the vessel was stirred in order to disperse the W/O
emulsion in the external phase at variable speeds for different
contact times to make the W/O/W double emulsions. The external
phase solution was periodically sampled at various time intervals.
The concentration of pollutant in the solutions was determined by
a UVvis spectrophotometer set at the wavelength corresponding
to maximum absorbance of the studied pollutant. Each experiment
was performed twice at least and the mean values were presented.
The maximum standard deviation was 2%.
Extraction efciency was calculated using the following
equation:
Extraction efficiency %

C0  C
 100
C0

(1)

where C0 is the initial concentration of pollutant in the external

phase (mg/L) and C is the concentration of pollutant in the external
phase at any time (mg/L).
Stripping
The double emulsion (W/O/W) is allowed to be spontaneously
separated by gravity and the demulsication of W/O emulsion was
achieved by adding 10 mL of 2-methyl-2-propanol (tert-butyl
alcohol). The mixture (W/O emulsion and tert-butanol) was stirred
and poured in a separating funnel. The membrane phase and the
internal phase receiving the extracted PP were separated by
gravity in the separating funnel. The concentration of PP in the
internal aqueous phase was determined by using a UVvis
spectrophotometer.
Stripping efciency was calculated using Eq. (2) determined by
mass balance:
Stripping efficiency %

C0

C Fint V Fint
 100
 C Fext V Fext

ext V 0 ext

(2)

where CFint is the nal concentration of PP in the internal phase

(mg/L), C0ext is the initial concentration of PP in the external phase
(mg/L), CFext is the nal concentration of PP in the external phase
(mg/L), VFint is the nal volume of the internal phase (mL), V0ext is
the initial volume of the external phase (mL) and VFext is the nal
volume of the external phase (mL).
Results and discussion
Extraction mechanism
In a simple transport, solute passes through due to its solubility
in liquid membrane. Permeation stops when concentration
equilibrium is reached. The solute does not react chemically with
liquid membrane and is supposed to be in the same form in the
feed, membrane, and receiving phases.

[(Fig._1)TD$IG]

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

298

Feed phase

Membrane

Stripping phase
O Na+

OH

(C8H17)3PO

CH3

CH3

(C10H12O3)
((C8H17)3PO)(C10H12O3)

Na2CO3

Fig. 1. Extraction mechanism of PP by ELM using tri-n-octylphosphine oxide as extractant.

observed that increase of surfactant concentration increases the

degree of removal. At low surfactant concentration, the amount of
surfactant is insufcient for surrounding all the internal aqueous
phase, which leads to more break-ups and instability of the
membrane. From Fig. 2, when the surfactant concentration was 1%
(w/w), severe membrane rupture occurred leading to rapid phase
separation. Though 3% (w/w) Span 80 did not show total
membrane rupture, the removal efciency was 87.5%. It can be
seen that both the removal efciency and transfer rate increase by
increasing the surfactant concentration from 3 to 5% (w/w). A
surfactant concentration of 5% (w/w) caused complete removal of
PP from the feed solution (extraction efciency was 100%). The

[(Fig._2)TD$IG]
100

80

Extraction efficiency (%)

In facilitated transport, a reactive component or carrier is

incorporated in the membrane phase to carry the diffusing species
across the membrane to the internal phase thus promoting its
transfer through the membrane. The transport can be described by
subsequent partitioning, complexation, and diffusion. Solute,
partitioning (dissolving) in LM on a feed side-LM interface
chemically reacts with a carrier, dissolved in the liquid membrane,
to form complex. This complex reverse reacts on the LM-receiving
side interface releasing the solute which partitioning to the
receiving (strip) phase. Facilitated transport accelerates the
transport. At the same time, the simple transport can take place
also [15].
Carrier-facilitated transport of PP through the liquid membrane
is schematically represented in Fig. 1. The PP is transported from
the feed phase to the received phase via a liquid membrane in the
presence of TOPO. After complexation of PP with carrier on the feed
phase, the complex diffuses down its concentration gradient. On
the received phase, carrier PP complex is decomplexed by the
stripping reaction with Na2CO3 and PP sodium salt is released into
the received phase. PP sodium salt that is not soluble in the
membrane phase and so is retained in the internal aqueous phase.
The reaction maintains a low solute concentration in the internal
phase, providing a high driving force. The difference of electrolyte
concentrations between the internal and external phases is
increased by increasing Na2CO3 concentration, which causes an
osmotic pressure between these two phases. Water in the external
phase is then transferred to the internal phase that results in
swelling and breakage of the emulsion, and thus decreasing in
removal efciency. Therefore, sodium sulfate is used in the
external phase in order to avoid swelling phenomenon and
enhance the extraction efciency. The free carrier diffuses back
across the liquid membrane and the cycle starts again. The net
result is the transport of PP from the aqueous source phase to the
aqueous receiving phase across the bulk of the organic phase.

60

1% (w/w) Span 80
3% (w/w) Span 80
5% (w/w) Span 80
7% (w/w) Span 80
9% (w/w) Span 80

40

20

0
0

10

15

20

25

30

35

40

Time (min)

Effect of surfactant concentration

It is very important to determine the effect of surfactant
concentration on the behavior of solute extraction. The effect of
surfactant concentration on the extraction efciency of PP by ELM
was investigated and the results were exhibited in Fig. 2. It was

Fig. 2. Effect of surfactant concentration on the extraction of PP (20 mg/L) by ELM

(experimental conditionsemulsion volume: 30 mL; external phase (PP solution)
volume: 250 mL; TOPO concentration: 4% (w/w); volume ratio of internal phase to
organic phase: 1/1; emulsication time: 4 min; stirring speed: 300 rpm; volume
ratio of W/O emulsion to external phase: 30/250; internal phase concentration
(Na2CO3): 0.1 N; sodium sulfate concentration in the feed phase: 0.1 N; diluent:
hexane).

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

increment of surfactant concentration lowered the membranes

surface tension and yielded smaller globules, which led to a higher
contact area [16,17]. The addition of more surfactant lowers the
surface tension and results in smaller droplet size of the W/O
emulsion, which gives a larger mass transfer area with a maximum
extraction rate [18,19]. Further increase in surfactant concentration
from 5 to 9% (w/w) leads to a slight decrease in PP removal, probably
due to an increase in the liquid membrane thickness of the emulsion
globule. This would lead to an increase in the PP mass transfer
resistance, adversely inuencing PP removal. Hence, it was decided to
sustain 5% (w/w) surfactant concentration in all other experiments.
Effect of extractant concentration
Extractant or carrier concentration in the membrane phase
plays a decisive role in the overall extraction behavior of ELM
systems. In order to investigate the inuence of TOPO concentration on the extraction efciency, different concentrations of carrier
in the range of 210% (w/w) were tested. The obtained results are
shown in Fig. 3. It was observed that as the TOPO concentration
increased from 2 to 4% (w/w), the removal of PP increased from
86.1 to 100%. TOPO forms complex with PP at the external interface
between the feed and the membrane phases. The concentration
gradient of the complex across the membrane augments the ux of
PP through the membrane. Thus, the degree of extraction of PP
increased with an increase in TOPO concentration. However, when
TOPO concentration was increased in the range of 410% (w/w), the
removal percentage decreased. For higher carrier concentration, a
higher viscosity of the membrane phase lowered diffusion rate of PP
and its complexes through the membrane phase and reduced the
total mass transfer area between the feed phase and the emulsion
drops due to formation of larger emulsion globules [20,21].
Additionally, an excess of extractant concentration (8 and 10%
(w/w) promotes the permeation swelling, which dilutes the aqueous
receiving phase and decreases the efciency of the process, and leads
to membrane breakdown. Consequently, TOPO concentration of 4%
(w/w) was selected as the best carrier concentration.

Effect of emulsication time

Experiments were conducted to study the inuence of
emulsication time on the extraction of PP from aqueous solution
and the obtained results are shown in Fig. 4. It was observed that
with the increase in emulsication time from 2 to 4 min, PP
removal increased from 92.8 to 100%. An increase of the
emulsication time to 4 min leads to a reduction of the size of
aqueous internal phase droplets and improves the homogeneity of
the dispersed phase. The prolonged emulsication time (>4 min)
results in a signicant decrease of removal efciency, mainly due
to the coalescence of the internal phase droplets [22,23]. Thus, an
emulsication time of 5 min was chosen throughout this work.
Effect of sodium sulfate concentration in external phase
The effect of sodium sulfate concentration levels from 0.01 to
1 N in external feed phase on extraction of PP is shown in Fig. 5. The
extraction efciency increased from 88.4 to 100% with the increase
of sodium sulfate concentration from 0.01 to 0.1 N. At higher
sodium sulfate concentration in the feed phase, extraction
efciency was signicantly decreased. It has been observed that
in the absence of sodium sulfate, the phenomenon of swelling take
place conducting to the breakage of the emulsion and thus
decreasing in extraction efciency. This transport of water from
external phase to internal phase is mainly driven by the difference
in osmotic pressure between the external and the internal phases.
Therefore, sodium sulfate concentration of 0.1 N in external phase
was chosen as the best one.
Effect of salt type in external phase
The inuence of the presence of 0.1 N of different salts namely
sodium sulfate, sodium chloride and calcium chloride in the external
feed phase on the extraction of PP from aqueous solutions was
investigated. The obtained results, shown in Fig. 6, indicates that the
extraction efciencies showed the following tendency: sodium
sulfate
(100%) > sodium chloride (71.0%) > calcium chloride
[(Fig._4)TD$IG]

100

100

80

80

Extraction efficiency (%)

Extraction efficiency (%)

[(Fig._3)TD$IG]

60

2% (w/w) TOPO
4% (w/w) TOPO

40

6% (w/w) TOPO
8% (w/w) TOPO
10% (w/w) TOPO

20

10

15

20

25

30

60
2 min
4 min

40

6 min
8 min
10 min

20

0
0

299

35

40

Time (min)
Fig. 3. Effect of carrier concentration on the extraction of PP (20 mg/L) by ELM
(experimental conditionsemulsion volume: 30 mL; external phase (PP solution)
volume: 250 mL; surfactant concentration: 5% (w/w); volume ratio of internal
phase to organic phase: 1/1; emulsication time: 4 min; stirring speed: 300 rpm;
volume ratio of W/O emulsion to external phase: 30/250; internal phase
concentration (Na2CO3): 0.1 N; sodium sulfate concentration in the feed phase:
0.1 N; diluent: hexane).

0
0

10

15

20

25

30

35

40

Time (min)
Fig. 4. Effect of emulsication time on the extraction of PP (20 mg/L) by ELM
(experimental conditionsemulsion volume: 30 mL; external phase (PP solution)
volume: 250 mL; surfactant concentration: 5% (w/w); TOPO concentration: 4% (w/
w); volume ratio of internal phase to organic phase: 1/1; stirring speed: 300 rpm;
volume ratio of W/O emulsion to external phase: 30/250; internal phase
concentration (Na2CO3): 0.1 N; sodium sulfate concentration in the feed phase:
0.1 N; diluent: hexane).

[(Fig._5)TD$IG]

[(Fig._7)TD$IG]

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

100

100

80

80

Extraction efficiency (%)

Extraction efficiency (%)

300

60

40

0.01N Na SO
2

0.05N Na SO
2

0.1N Na SO
2

0.5N Na SO

20

1N Na SO
2

60

40
0.01N Na CO
2

0.05N Na CO
2

3
3

0.1N Na CO

20

0.5N Na CO

1N Na CO

2N Na CO
2

0
0

10

15

20

25

30

35

40

10

15

20

25

30

35

40

Time (min)

Time (min)
Fig. 5. Effect of sodium sulfate concentration in the external phase on the extraction
of PP (20 mg/L) by ELM (experimental conditionsemulsion volume: 30 mL;
external phase (PP solution) volume: 250 mL; surfactant concentration: 5% (w/w);
TOPO concentration: 4% (w/w); volume ratio of internal phase to organic phase: 1/
1; emulsication time: 4 min; stirring speed: 300 rpm; volume ratio of W/O
emulsion to external phase: 30/250; internal phase concentration (Na2CO3): 0.1 N;
diluent: hexane).

Fig. 7. Effect of internal phase concentration (Na2CO3) on the extraction of PP

(20 mg/L) by ELM (experimental conditionsemulsion volume: 30 mL; external
phase (PP solution) volume: 250 mL; surfactant concentration: 5% (w/w); TOPO
concentration: 4% (w/w); volume ratio of internal phase to organic phase: 1/1;
emulsication time: 4 min; stirring speed: 300 rpm; volume ratio of W/O emulsion
to external phase: 30/250; sodium sulfate concentration in the feed phase: 0.1 N;
diluent: hexane).

(64.9%). Thus, sodium sulfate was accepted as the best salt and was
used in the feed solution in the following experiments.

Na2CO3. It was observed that when Na2CO3 concentration

increased from 0.001 to 0.1 N, the removal percentage increased
from 93.5 to 100%. However, when the concentration of Na2CO3 in
the stripping solution was varied from 0.1 to 2 N, the extraction
efciency of PP was signicantly reduced. It was expected that
increasing the amount of Na2CO3 in the internal stripping phase
decreased the difference of densities and increased the emulsion
viscosity. The increasing of emulsion viscosity reected in an
increasing in the size of droplets. In addition, difference in ionic

Effect of internal phase concentration

The inuence of sodium carbonate concentration in the internal
phase on extraction of PP was examined at various concentration
levels from 0.001 to 2 N and shown in Fig. 7. This gure shows that
the best extraction efciency of PP can be achieved by using 0.1 N

[(Fig._6)TD$IG]

[(Fig._8)TD$IG]
100
100

80

60

Extraction efficiency (%)

Extraction efficiency (%)

80

0.1N Na 2SO4

40

0.1N NaCl
0.1N CaCl2
20

60

40
0.1N Na2CO3
0.1N NH4OH
20

0
0

10

15

20

25

30

35

40

Time (min)

0
0

10

15

20

25

30

35

40

Time (min)
Fig. 6. Effect of salt type in the external phase on the extraction of PP (20 mg/L) by
ELM (experimental conditionsemulsion volume: 30 mL; external phase (PP
solution) volume: 250 mL; surfactant concentration: 5% (w/w); TOPO
concentration: 4% (w/w); volume ratio of internal phase to organic phase: 1/1;
emulsication time: 4 min; stirring speed: 300 rpm; volume ratio of W/O emulsion
to external phase: 30/250; internal phase concentration (Na2CO3): 0.1 N; diluent:
hexane).

Fig. 8. Effect of type of internal phase on the extraction of PP (20 mg/L) by ELM
(experimental conditionsemulsion volume: 30 mL; external phase (PP solution)
volume: 250 mL; surfactant concentration: 5% (w/w); TOPO concentration: 4% (w/
w); volume ratio of internal phase to organic phase: 1/1; emulsication time:
4 min; stirring speed: 300 rpm; volume ratio of W/O emulsion to external phase:
30/250; sodium sulfate concentration in the feed phase: 0.1 N; diluent: hexane).

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

strength between external and internal phase led to internal phase

volume increasing, which promotes excess emulsion leakage [24].
Furthermore, at higher Na2CO3 concentrations, the decrease of the
removal percentage may be due to the reaction of Na2CO3 with
Span 80, which results in a partial loss of its surfactant properties.
Thus, the 0.1 N Na2CO3 concentration in internal stripping phase
was chosen for further study.

301

the extraction efciency was 56.4 and 100% for ammonia and
sodium carbonate, respectively. When 0.1 N NaOH was used as
stripping agent, multiple emulsion of water-in-oil-in-water (W/O/
W) type undergoes phase inversion to a simple water-in-oil (W/O)
emulsion. Therefore, 0.1 N Na2CO3 solution was selected as the
suitable stripping agent.
Effect of stirring speed

Effect of type of internal phase

The effect of aqueous internal phase composition for an efcient
stripping reaction at the membrane-internal solution interface was
studied. Although in the preliminary experiments sodium carbonate solution was used as the internal aqueous phase, other basic
substances were also tested. Since PP is weakly acidic (pKa = 8.4
[25]), the overall extraction was greatly affected by the solution
pH. Strong basic agent used inside the emulsion droplets as
internal stripping phase serves to convert neutral PP, which had
transported by carrier through the liquid membrane, into PP anion.
The latter compound, which is charged specie in basic aqueous
phase, could not diffuse back to the external phase and thus was
retained in the internal aqueous phase. The effect of the presence of
0.1 N of different stripping solutions namely Na2CO3, NaOH and
NH4OH in the internal phase on the extraction of PP was examined
and the obtained results are presented in Fig. 8. It was found that

[(Fig._9)TD$IG]

In order to examine the effect of agitation speed on the

extraction of PP, the feed solution and emulsion were mixed at
stirring speeds ranging from 150 to 400 rpm and the obtained
results are shown in Fig. 9. For the lower stirring speed (150 rpm),
the removal percentage was low because of the formation of larger
emulsion globules involving a decrease of the area for mass
transfer. By increasing the agitation speed from 150 to 300 rpm,
the PP in the feed solution was removed more rapidly during the
treatment. This might be because the size of droplets and the
membrane thickness are both reduced by increasing the stirring
speed. Emulsion liquid droplets with smaller size lead to better
dispersion. At the same time, more interfacial surface area is
available between the external phase and the membrane phase, so
the removal efciency and transfer rate are higher. However, when
the stirring speed was varied from 300 to 400 rpm, the extraction
efciency was reduced. Increasing the stirring speed above critical

100

Extraction efficiency (%)

80

60

40
150 rpm
200 rpm
250 rpm

20

300 rpm
350 rpm
400 rpm
0
0

10

15

20
Time (min)

25

30

35

40

Fig. 9. Effect of stirring speed on the extraction of PP (20 mg/L) by ELM (experimental conditionsemulsion volume: 30 mL; external phase (PP solution) volume: 250 mL;
surfactant concentration: 5% (w/w); TOPO concentration: 4% (w/w); volume ratio of internal phase to organic phase: 1/1; emulsication time: 4 min; volume ratio of W/O
emulsion to external phase: 30/250; sodium sulfate concentration in the feed phase: 0.1 N; internal phase concentration (Na2CO3): 0.1 N; diluent: hexane).

[(Fig._10)TD$IG]

[(Fig._1)TD$IG]

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

100

100

80

80

Extraction efficiency (%)

Extraction efficiency (%)

302

60
Vint /Vorg = 1/2
Vint /Vorg = 1/1

40

Vint /Vorg = 3/4

60

40
V /V
em

V /V
em

V /V
em

20

20

V /V
em

V /V
em

0
0

10

15

20

25

30

35

40

10

15

value not only decreases the extraction efciency, but also affects
the stability of the emulsion and makes the emulsion unstable.
Thus, 300 rpm was recommended as the most appropriate stirring
speed.
Effect of volume ratio of internal phase to membrane phase
To investigate the effect of volume ratio of internal phase to
organic phase on the extraction of PP by ELM, this ratio was varied
at 1/2, 3/4, 1/1, 3/2 and 2/1. The obtained results are shown in
Fig. 10. At low volume ratio, membrane thickness and viscosity of
the emulsion phase is high due to the relatively high organic
content. In addition, low volume ratio means less stripping agents
are available for solute stripping. It was observed that the
extraction efciency increased from 75.8 to 100% with increasing
volume ratio of internal phase to membrane phase from 1/2 to 1/1.
This can be attributed to the fact that an increase in the internal
phase volume fraction shifts the internal drop size distribution
toward larger size and decreases the thickness of the membrane
phase resulting in enhanced mass transfer. This results in increase
in the capacity of the membrane for enhanced permeation of the
solute. When the volume ratio of internal phase to membrane
phase increased to 3/2 and 2/1, phase inversion of multiple W/O/W
emulsion to simple W/O emulsion is observed after a certain period
of agitation. Theoretically, when the fraction of internal phase
exceeds 70%, it is possible to cause an inversion of the emulsion
initially W/O [23]. Thus, in order to obtain a uniform and
homogeneous distribution of the internal phase droplets in the
membrane space, the volume ratio of organic phase to internal
aqueous phase was taken to be 1 based on the highest removal of
PP.

25

ext
ext
ext
ext

30

= 5/250
= 10/250
= 30/250
= 60/250
= 90/250

35

40

Time (min)

Time (min)
Fig. 10. Effect of volume ratio of internal phase to organic phase on the extraction of
PP (20 mg/L) by ELM (experimental conditionsemulsion volume: 30 mL; external
phase (PP solution) volume: 250 mL; surfactant concentration: 5% (w/w); TOPO
concentration: 4% (w/w); emulsication time: 4 min; stirring speed: 300 rpm;
volume ratio of W/O emulsion to external phase: 30/250; sodium sulfate
concentration in the feed phase: 0.1 N; internal phase concentration (Na2CO3):
0.1 N; diluent: hexane).

20

ext

Fig. 11. Effect of volume ratio of emulsion to external phase on the extraction of PP
(20 mg/L) by ELM (experimental conditionsexternal phase (PP solution) volume:
250 mL; surfactant concentration: 5% (w/w); TOPO concentration: 4% (w/w);
emulsication time: 4 min; volume ratio of internal phase to organic phase: 1/1;
stirring speed: 300 rpm; sodium sulfate concentration in the feed phase: 0.1 N;
internal phase concentration (Na2CO3): 0.1 N; diluent: hexane).

efciency of PP. The treatment ratio was varied from 5/250 to 90/
250 as shown in Fig. 11. From this gure, it was observed that
the increase in treatment ratio from 5/250 to 30/250 resulted in
increase in percentage of PP extraction from 47.7 to 100%.
The increase in membrane emulsion to feed volume is expected
to increase the extraction efciency of PP. Further increase in
treatment ratio above 30/250 resulted in decrease in removal
percentage. This was due to improper mixing of phases because of
higher proportion of the more viscous emulsion phase. Consequently, in order to ensure a good dispersion of emulsion in the
external phase solution and to increase the concentration of the
solute in the stripping phase, volume ratio of emulsion to external
feed solution of 30/250 was selected as the best treatment ratio.
Effect of diluent type
It is recognized that the organic diluent inuences the
performance of many ELM systems. Extraction of PP by ELM using
n-hexane, n-heptane and kerosene as diluent was shown in Fig. 12.
It was observed that the extraction of PP showed the following
tendency: n-hexane > n-heptane > kerosene. This behavior is due
to the viscosities of n-hexane (0.200 mPa s) and n-heptane
(0.387 mPa s) that are much lower than that of kerosene
(1.383 mPa s), which conducted to higher rate of transfer. The
density of the diluents is another parameter that decides the
thickness and permeability of the membrane for the solute. The
extraction results may be also due to the values of diluents density
(0.66 g/mL for n-hexane, 0.70 g/mL for n-heptane and 0.78 g/mL
for kerosene), which are in the same order with those of the
removal efciencies. Further extraction studies of PP were
conducted using n-hexane as a diluent.
Effect of PP initial concentration

Effect of treatment ratio

The treatment ratio plays an important role in determining
effectiveness of emulsion liquid membranes. Experiments were
conducted to study the effect of treatment ratio on the extraction

The effect of initial concentration of PP on the extent of

extraction has been investigated. The experiments were performed
for different initial PP concentrations in the range of 580 mg/L.
Fig. 13 depicts the variation of extent of extraction with respect to

[(Fig._12)TD$IG]

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

100

internal droplets in the peripheral region of the emulsion is

attained more rapidly for high PP concentrations in the feed phase.
When initial PP concentration increases, the peripheral droplets
are rapidly exhausted, requiring the solute to permeate deeper
within the globule prior to being stripped. Therefore, an increase in
initial PP concentration also corresponds to an increase in
diffusional path lengths.

80

Extraction efficiency (%)

303

60

Extraction of PP from real waters

n-Hexane
40

n-Heptane
Kerosene

20

0
0

10

15

20

25

30

35

40

Time (min)
Fig. 12. Effect of diluent type on the extraction of PP (20 mg/L) by ELM (experimental
conditionsemulsion volume: 30 mL; external phase (PP solution) volume:
250 mL; surfactant concentration: 5% (w/w); TOPO concentration: 4% (w/w);
emulsication time: 4 min; volume ratio of internal phase to organic
phase: 1/1; stirring speed: 300 rpm; volume ratio of W/O emulsion to external
phase: 30/250; sodium sulfate concentration in the feed phase: 0.1 N; internal
phase concentration (Na2CO3): 0.1 N).

the initial concentration of PP. The removal percentage increases

with the increase of PP concentration from 5 to 20 mg/L. This may
be attributed to an increase in the driving force, the concentration
gradient, with the increase in the initial solute concentration [26].
When initial PP concentration is low, most of the solute diffusing
within the emulsion globule is stripped by the internal aqueous
phase droplets, which are situated in the peripheral regions of
the emulsion globule. For substrate concentrations higher than
20 mg/L, the extent of extraction decreased. The saturation of the

[(Fig._13)TD$IG]

The extraction effectiveness of PP was studied by dissolving

the solute in a natural mineral water, in seawater and in sewage
water efuent. Experiments were carried out using an initial PP
concentration of 20 mg/L. The main characteristics of the
natural water were: pH = 7.2, Ca2+ = 81 mg/L, Mg2+ = 24 mg/L,
Na+ = 15.8 mg/L, Cl = 72 mg/L, SO42 = 53 mg/L, HCO3 = 265 mg/L.
The sample of sewage treatment plant (STP) efuent was collected
in April 2013. This STP is based on activated sludge treatment and
serves a population of almost 600,000 inhabitants in the city of
Annaba, Algeria. The sample was collected after a complete
treatment and kept refrigerated. The obtained results are shown
in Fig. 14. In all cases, the extraction kinetics of PP in distilled
water was higher than those obtained in real matrices. The
removal percentage obtained after 40 min of contact time is 71.4%
in natural water, 79.6% in sewage water efuent, 91.9% in
seawater and 100% in distilled water. Thus, ELM treatment
process represents an efcient advanced separation technique for
the removal of PP from real waters.
Stripping
The effect of Na2CO3 concentration on the stripping efciency
was examined in order to improve the regeneration of membrane
and to concentrate PP in the stripping internal phase. The obtained
results are illustrated in Fig. 15. It was observed that the stripping
efciency increased with an increase in Na2CO3 concentration up
to
[(Fig._14)TD$IG] 0.1 N, above which stripping performance decreased. Thus, the
100

100

80

Extraction efficiency (%)

Extraction efficiency (%)

80

60

40

60

Distiled water
40
Seawater
Sewage water
20

Natural water

20

10

20

30

40

60

80

10

15

20

25

30

35

40

Time (min)

PP concentration (mg/L)
Fig. 13. Effect of PP initial concentration on the extraction efciency (experimental
conditionsemulsion volume: 30 mL; external phase (PP solution) volume:
250 mL; surfactant concentration: 5%(w/w); TOPO concentration: 4% (w/w);
volume ratio of internal phase to organic phase: 1/1; emulsication time: 4 min;
stirring speed: 300 rpm; volume ratio of W/O emulsion to external phase: 30/250;
internal phase concentration (Na2CO3): 0.1 N; sodium sulfate concentration in the
feed phase: 0.1 N; diluent: hexane).

Fig. 14. Removal of PP (20 mg/L) from distilled water, natural mineral water,
seawater and sewage water efuent by ELM (experimental conditionsemulsion
volume: 30 mL; external phase (PP solution) volume: 250 mL; surfactant
concentration: 5%(w/w); TOPO concentration: 4% (w/w); volume ratio of
internal phase to organic phase: 1/1; emulsication time: 4 min; stirring speed:
300 rpm; volume ratio of W/O emulsion to external phase: 30/250; internal phase
concentration (Na2CO3): 0.1 N; sodium sulfate concentration in the feed phase:
0.1 N; diluent: hexane).

[(Fig._15)TD$IG]

S. Chaouchi, O. Hamdaoui / Journal of Industrial and Engineering Chemistry 22 (2015) 296305

304

100

Dextraction efficiency (%)

80

60

40

20

0.001

0.005

0.1

0.5

Na CO concentration (N)
2

Fig. 15. Effect of sodium carbonate concentration in the internal aqueous phase on the stripping of PP (experimental conditionsemulsion volume: 30 mL; external phase (PP
solution) volume: 250 mL; surfactant concentration: 5%(w/w); TOPO concentration: 4% (w/w); volume ratio of internal phase to organic phase: 1/1; emulsication time:
4 min; stirring speed: 300 rpm; volume ratio of W/O emulsion to external phase: 30/250; sodium sulfate concentration in the feed phase: 0.1 N; diluent: hexane).

best concentration of Na2CO3 in the internal phase is 0.1 N due to

the excellent stripping efciency.
When the recovered membrane was emulsied with fresh
Na2CO3 solution (0.1 N), stable emulsion was obtained. This
recovered membrane phase was then used in subsequent
experiments. The recovery of the membrane phase was total by
this process. The extraction of PP was not decreased up to seven
runs. Emulsion was stable during these runs and there is no
swelling of the W/O emulsion.

PP was not decreased. ELM treatment process represents an

efcient advanced separation technique for the removal of PP from
real waters. Further experiments need to be conducted to test the
selective extraction of PP from waters.
Acknowledgement
The nancial support by the Ministry of Higher Education and
Scientic Research of Algeria (project no. J0101120120098) is
greatly acknowledged.

Conclusion
This work aimed to the extraction of PP from water by ELM
using TOPO as extractant. Best experimental conditions for higher
removal percentage are: emulsion volume: 30 mL; external phase
(PP solution) volume: 250 mL; surfactant concentration: 5%(w/w);
TOPO concentration: 4% (w/w); volume ratio of internal phase to
organic phase: 1/1; emulsication time: 4 min; stirring speed:
300 rpm; volume ratio of W/O emulsion to external phase: 30/250;
internal phase concentration (Na2CO3): 0.1 N; sodium sulfate
concentration in the feed phase: 0.1 N; diluent: hexane. By using
the optimal operating parameters, it was possible to wholly
remove all of PP molecules from the external feed solution. The
recovery of the membrane phase was total and the extraction of

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