Ultrasonics Sonochemistry 17 (2010) 318–325

Contents lists available at ScienceDirect

Ultrasonics Sonochemistry
journal homepage: www.elsevier.com/locate/ultsonch

Study on ultrasonically assisted emulsification and recovery of copper(II) from

wastewater using an emulsion liquid membrane process
Mahdi Chiha a,*, Oualid Hamdaoui a, Fatiha Ahmedchekkat b, Christian Pétrier c
a
Laboratory of Environmental Engineering, Department of Process Engineering, Faculty of Engineering, University of Annaba, P.O. Box 12, 23000 Annaba, Algeria
b
LARMACS, Faculty of Engineering, University of Skikda, P.O. Box 26, 21000 Skikda, Algeria
c
LEPMI, Université Joseph Fourier, 38402 Saint Martin d’Hères Cedex, France

a r t i c l e i n f o a b s t r a c t

Article history: The aim of this work was to study the emulsification assisted by ultrasonic probe (22.5 kHz) and inves-
Received 19 May 2009 tigate the removal of copper(II) ions from aqueous solution using water-in-oil-in-water (W/O/W)
Received in revised form 30 August 2009 emulsion liquid membrane process (ELM). The membrane was prepared by dissolving the extractant
Accepted 2 September 2009
bis(2-ethylhexyl)phosphoric acid (D2EHPA) and the hydrophobic surfactant sorbitan monooleate (Span
Available online 8 September 2009
80) in hexane (diluent). The internal phase consisted of an aqueous solution of sulfuric acid. Effects of
operating parameters such as emulsification time, ultrasonic power, probe position, stirring speed, carrier
Keywords:
(D2EHPA) and surfactant (Span 80) concentrations volume ratios of organic phase to internal striping
Wastewater
Copper(II)
phase and of external aqueous phase to membrane (W/O) phase, internal phase concentration and choice
Emulsion liquid membrane of diluent on the membrane stability were studied. With ultrasound, the W/O emulsion lifetime were
Ultrasound much higher than those reported previously by mechanical agitation. The effect of carrier and Cu(II) ini-
D2EHPA tial concentration on the extraction kinetics was also investigated. Nearly all of the Cu(II) ions present in
the continuous phase was extracted within a few minutes. Additionally, the influence of H2SO4 concen-
tration on the stripping efficiency was examined.
Ó 2009 Elsevier B.V. All rights reserved.

1. Introduction liquid membrane, efficiency of extraction and evaluating the inter-

Water contamination by heavy metals is a serious environmen-
tal problem, which has been extensively discussed. One of the
promising techniques for the separation of heavy metal ions from
wastewater is the emulsion liquid membrane (ELM) technique,
which is first described by Li [1] and other scientists [2]. Emulsion
liquid membrane separation process constitutes an emerging tech-
nology with a wide variety of applications, such as the removal,
recovery, and purification of many heavy metal ions from dilute
solutions of industrial interest.
In the ELM process, a simultaneous extraction and stripping are
accomplished through a large surface area (1000–3000 m2/m3) of a
liquid membrane prepared with a minimum quantity of selective
extractant [3]. Multiple emulsion systems are generally prepared
using a two-step process. In the W1/O/W2 multiple emulsion type,
primary water-in-oil (W1/O) emulsion is prepared in a first step
using a hydrophobic surfactant. The W1/O emulsion is then dis-
persed in a second aqueous phase W2 (Fig. 1). The size of the dis-
persed drops is important for determining the stability of the
* Corresponding author. Tel.: +213 790681263; fax: +213 38876560.
E-mail address: chiha_m_f@yahoo.fr (M. Chiha).
facial contact area. It is also important to obtain information about
the swelling, breakage and coalescence of dispersed drops.
Unfortunately, ELM process has not found widespread usage in
industrial application. The slow industrialization of this technology
is mainly due to the stability problems (i.e., the tendency of an
emulsion to remain dispersed and resist coalescence) associated
with the emulsion and their tendency to undergo swelling [4].
The main factors affecting emulsion stability encompass mem-
brane formulation, technique of emulsion preparation, and the
condition under which the emulsion is contacted with an external
phase. Energy must be supplied to produce such meta-stable mix-
tures. Energy may be provided through various means including
mechanical agitation (stirrer, colloid mill, mixer, valve homoge-
nizer) and ultrasound generation. In water/oil system, the process
of emulsification assisted by ultrasound initiates when the cavita-
tion threshold is attained. Ultrasound can provide an excess energy
for new interface formation; hence it is possible to obtain emul-
sions even in few quantities of surfactants (emulsifiers).
The sono-emulsification process is dependent upon a range of
parameters, notably the acoustic power, location of the energy dis-
sipating source and chemical composition of the system; beyond a
certain range of optimum conditions, ultrasound may cause the in-
verse effect (coagulation and precipitation phenomenon) [5].

1350-4177/$ - see front matter Ó 2009 Elsevier B.V. All rights reserved.
doi:10.1016/j.ultsonch.2009.09.001
 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325
Membrane phase
Internal aqueous phase
Emulsification
External aqueous phase
Extraction (Permeation)
Fig. 1. The emulsion liquid membrane process.
Ultrasound has been proved to be suitable for emulsification
[6]. Ultrasound emulsification was reported for the first time by
Wood and Loomis [7]. With ultrasound, for example, the size of
W/O emulsions (Sauter diameter d32) is much smaller than those
given by mechanical agitation under the same conditions, as con-
sequence it increase the stability [8].
Removal of copper ions from aqueous solution using ELMs has
been an area of interest ever since ELMs were invented. Most
investigators [9–12] preferred studying the effect of chemical com-
position of the system using chelating extractants, such as LIX 63,
LIX 64 N, LIX 65 and SME 529, because of their immiscibility with
water. Economic evaluation showed that ELM extraction of copper
using LIX 64 N turns out to be 40% cheaper than solvent extraction
[13].
Little work has been reported in the literature for the utilization
of ultrasound in all the steps of ELM process (emulsification,
extraction and demulsification). Chakravarti et al. [14] have inves-
tigated the extraction of copper by ELMs using mechanical emulsi-
fication. Also, Sengupta et al. [15] preferred using mechanical
agitation (12000 rpm) to prepare W/O emulsion for copper extrac-
tion with LIX 984 N-C as carrier. Valenzuela et al. [16,17] have
studied the removal of copper ions from a wastewater by a liquid
emulsion membrane method using an Ultraturrax Janke Kunkel
ultrasonic agitator in first step preparation of W/O emulsion and
an Elma Ultrasonic bath in second step was used to accelerate
the phase separation process by enhancing the coalescence of the
small droplets. Behrend et al. [18,19] have investigated vegetable
oil-in-water emulsion stability using ultrasonic emulsification be-
cause the power density sufficiently characterizes the process con-
ditions in terms of droplet disruption. Juang and Lin [20] have
studied the efficiency of emulsification with ultrasonic probe
(20 kHz) and the possibility of ultrasound demulsification. They
have indicated that emulsification can be realized with the supply
of a suitable form of energy. All the oil-in-water (O/W) emulsions
were prepared by the ultrasonic method (Ultrasonic 42, Branson)
by Zha et al. [21]. By understanding the relationship (ultrasound –
319
Splitting (demulsification)
Extract
Rafinate
Settling
emulsification), industrial processes involving ultrasound can be
optimized for scale up.
In the present work, the preparation of W/O emulsion assisted
by ultrasound and the extraction of copper from aqueous media
into ELMs using D2EHPA as carrier are reported. The influence of
operational conditions on the prepared W/O emulsion as well as
on the extraction efficiency by ELM was investigated.
2. Experimental section
2.1. Reagents
D2EHPA (bis(2-ethylhexyl) phosphoric acid) was analytical
grade product (Aldrich) and was used as received. The non-ionic
surfactant Span 80 (sorbitan monooleate, Aldrich) was used as an
emulsifier. Diluents (hexane, heptane and dodecane) were ob-
tained from Fluka. Copper(II) solutions were prepared by dissolv-
ing requisite amount of copper sulfate (CuSO45H2O, Prolabo) in
bidistilled water. Analytical pure sulfuric acid, obtained from
Merck, was employed for the preparation of the aqueous internal
phase.
2.2. Apparatus and measurement
The 22.5 kHz ultrasonic wave was emitted from a titanium horn
(tip diameter 3 mm) connected to a commercial supply (Microson
2000 XL). Acoustic power dissipated in the reactor was estimated
using standard calorimetric method [22,23]. The used experimental
set-up was shown in Fig. 2. The determination of Cu(II) concentra-
tion was carried out using atomic absorption spectrophotometer
(AAS, Shimadzu A. A-6601 F, Atomic Absorption Flame Emission
Spectrophotometer) at 325 nm. Each experiment was performed
twice at least and the mean values were presented. The reproduc-
ibility of the concentrations measurements was within 3%.
320 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325
To generator
Transducer
Ultrasound Probe
Tip
Cooling water inlet
Fig. 2. Experimental set-up for ultrasound-assisted preparation of the W/O emulsion.
2.3. Experimental procedures
The ELM used in this work was water-in-oil-in-water (W/O/W)
emulsion formed by dissolving the extractant (D2EHPA) and the
surfactant (Span 80) in diluents (hexane, heptane or dodecane).
Internal aqueous phase was a solution of H2SO4. Water-in-oil (W/
O) emulsion was made by slowly adding the internal phase to
the organic membrane phase upon intensive emulsification with
the ultrasonic probe.
A certain volume of the obtained stable emulsion (20 mL) was
dispersed in the feed phase (100 mL of aqueous solution). The
extraction runs were performed in a glass vessel of 61 mm diame-
ter using a mechanical agitator (Junke & Kunkel RW20) with four-
paddle impeller of 20 mm diameter. All experiments were carried
out at constant temperature (25 ± 1 °C) using water jacket around
the vessel. The concentration of copper in the aqueous external
phase was determined by AAS and in the internal phase was deter-
mined by mass balance.
3. Results and discussion
3.1. Emulsion stability
Several parameters can affect the stability of W/O emulsion
such as the ultrasound power, emulsification time, probe position,
stirring speed, surfactant and carrier concentrations, volume ratios
of organic phase to internal striping phase and of external aqueous
phase to membrane (W/O) phase, internal phase concentration and
choice of diluent were studied. The produced W/O emulsions
should be employed for the removal of copper(II) from aqueous
solutions.
The stability of emulsions was investigated by using the break-
up, e, defined by the following equation:
Vs
e¼  100
V int
The emulsion breakage represents the ratio in percentage of the
volume of internal phase leaked into the external phase by split-
ting (VS) to the initial volume of the internal phase (Vint). The vol-
ume VS is calculated by the mass balance.
Cooling water outlet
Vessel
10pH0  10pH
V s ¼ V ext
10pH  Cint
Hþ
Where Vext is the initial volume of external phase, Cint
Hþ the initial
concentration of H+ in the internal phase, pH0 the initial pH of the
external phase and pH is the external phase pH being in contact
with the emulsion after a certain time of stirring.
3.1.1. Effect of emulsification time
One of the most important parameter for ELM processes is the
emulsification time. Fig. 3 shows the effect of emulsification time
on the emulsion stability using a surfactant concentration of 4%
(w/w) in the membrane phase (oil phase). For emulsification times
higher than 3 min, it has been observed that the breakage percent-
age gradually increased because of the high internal shearing lead-
ing to a very high number of small droplets, which is conducive to
their diffusion into external phase (bidistilled water). For lower
emulsification times (<3 min), the relatively higher breakage per-
centage values are due to the large size of inner droplet that causes
30
25
20
Breakage (%)
15
10
5
0
0 2 4 6 8 10 12
Emulsification time (min)
Fig. 3. Effect of emulsification time on the W/O emulsions stability (experimental
conditions: emulsion volume: 20 mL; external phase (pure water) volume: 100 mL;
volume ratio of internal phase to organic phase: 1; emulsification time: 1–10 min;
ultrasound power: 20 W, stirring speed: 200 rpm; concentration of Span 80: 4% w/
w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to external
phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane; contact
time: 18 min; distance of the tip horn from the bottom of vessel: 20 mm).
 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325 321

coalescence phenomenon. The lower breakage is obtained for an 70

emulsification time of 3 min.
60

3.1.2. Effect of ultrasonic power 50

Breakage (%)
The emulsification efficiencies at different ultrasound powers
40
are shown in Fig. 4. The emulsion breakage profile shows the
important effect of ultrasound power on emulsion stability. For 30
low power values (5–15 W), the sound field is insufficient to give
the necessary energy for a good dispersion of aqueous droplets in 20
the membrane phase. The percentage of breakage decreases
10
with the increase of the power of ultrasound. 20 W is the optimum
value. Beyond this value, higher ultrasonic power produces higher 0
specific surface area of W/O emulsions, but the phenomenon of 0 100 200 300 400 500 600
Stirring speed (rpm)
coalescence is more significant. Freitas et al. [24] have found the
same behavior and showed that oil droplets of 5–10 lm diameters Fig. 5. Effect of stirring speed on the W/O emulsions stability (experimental
could be observed in emulsions processed at an ultrasonic power conditions: emulsion volume: 20 mL; external phase (pure water) volume: 100 mL;
of 25 W, and practically no droplets were microscopically visible volume ratio of internal phase to organic phase: 1; emulsification time: 3 min;
at 32 W, i.e. at full power. ultrasound power: 20 W, stirring speed: 100–500 rpm; concentration of Span 80:
4% w/w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to
external phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane;
3.1.3. Effect of stirring speed contact time: 18 min; distance of the tip horn from the bottom of vessel: 20 mm).
Stirring speed directly influences membrane stability behavior.
Since globule size gets affected by stirring, higher agitation speeds
lead to the formation of smaller sized globules, thereby increasing 16
the interfacial area between continuous phase and the membrane 14
phase, and accelerate the mass transfer for extraction. Also, higher
stirring speed may bring about higher breakage percentage. There- 12
fore, it is very important to select a suitable stirring speed and keep 10
Breakage (%)

stable mixing conditions during the process in order to maintain

8
adequate membrane stability and minimize the emulsion swelling.
According to Fig. 5, for lower stirring speeds (100 and 150 rpm con- 6
ditions), the breakage percentage is low because the size of the 4
emulsion globules increases and the interfacial area available for
mass transfer decreases. Increasing the stirring speed above a crit- 2
ical value (200 rpm) affects the stability of the emulsion and in- 0
creases the osmotic swelling of the membrane and makes the 0 0.2 0.4 0.6 0.8 1 1.2 1.4
emulsion unstable. Thus, 200 rpm was the best stirring speed to Sulfuric acid concentration (N)
ensure a good stability of the W/O emulsion and to enhance the
Fig. 6. Effect of internal aqueous phase (H2SO4) concentration on the W/O
interfacial area available for mass transfer for the subsequent emulsions stability (experimental conditions: emulsion volume: 20 mL; external
experiments to fulfill the demand of well dispersing and low phase (pure water) volume: 100 mL; volume ratio of internal phase to organic
breakage. phase: 1; emulsification time: 3 min; ultrasound power: 20 W, stirring speed:
200 rpm; concentration of Span 80: 4% w/w; carrier concentration: 20% w/w;
volume ratio of W/O emulsions to external phase: 0.2; internal phase concentration
3.1.4. Effect of internal phase concentration (H2SO4): 0.1–1.2 N; diluent: hexane; contact time: 18 min; distance of the tip horn
The effect of internal phase concentration (H2SO4) on the ELM from the bottom of vessel: 20 mm).
stability is illustrated in Fig. 6. When the sulfuric acid concentra-
tion increased from 0.1 to 0.3 N, the percentage of breakage de-
18 creased. A concentration of 0.1 N leads to high breakage
16 percentage because the ionic strength difference between internal
and external phases is not sufficient conducting in high emulsion
14
breakage. Concentration of the internal phase giving the weakest
12 breakage (0.3 N) was chosen in this study. Beyond this concentra-
Breakage (%)

10 tion the emulsion stability slightly decreased. The slight decrease

8 of the W/O emulsion stability may be due to the reaction of sulfuric
acid with Span 80, which results in a partial loss of its surfactant
6
properties [30].
4

2
3.1.5. Effect of extractant concentration
0 The effect of D2EHPA (carrier) concentration on the W/O emul-
0 5 10 15 20 25 30 35 40
sion stability is shown in Fig. 7. This figure shows that when the
Ultrasonic power (W)
carrier concentration in the membrane phase increased from 5%
Fig. 4. Effect of ultrasonic power on the W/O emulsions stability (experimental to 20% (w/w), the breakage percentage decreased. This behavior
conditions: emulsion volume: 20 mL; external phase (pure water) volume: 100 mL; is due to the interfacial properties of the D2EHPA that leads to a
volume ratio of internal phase to organic phase: 1; emulsification time: 3 min; good stability of the emulsion. A very high content of carrier in
ultrasound power: 10–35 W, stirring speed: 200 rpm; concentration of Span 80:
4% w/w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to
the membrane (higher than 20% (w/w)) does not result in a benefit
external phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane; due to the increase in viscosity, which leads to larger globules.
contact time: 18 min; distance of the tip horn from the bottom of vessel: 20 mm). Swelling phenomenon was observed when carrier concentration
322 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325

20 40
18 35
16
30
14

Breakage (%)
12 25
Breakage (%)

10 20
8
15
6
10
4
2 5
0 0
0 10 20 30 40 50 0 0.5 1 1.5 2 2.5
Extractant concentration (% w/w) Vint /Vorg

Fig. 7. Effect of carrier concentration on the W/O emulsions stability (experimental
conditions: emulsion volume: 20 mL; external phase (pure water) volume: 100 mL,
volume ratio of internal phase to organic phase: 1; emulsification time: 3 min;
ultrasound power: 20 W, stirring speed: 200 rpm; concentration of Span 80: 4% w/
w; carrier concentration: 5–40% w/w; volume ratio of W/O emulsions to external
phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane; contact
time: 18 min; distance of the tip horn from the bottom of vessel: 20 mm).
Fig. 9. Effect of the volume ratio of internal phase to organic phase on the W/O
emulsions stability (Experimental conditions: emulsion volume: 20 mL; external
phase (pure water) volume: 100 mL; volume ratio of internal phase to organic
phase: 0.5–2; emulsification time: 3 min; ultrasound power: 20 W, stirring speed:
200 rpm; concentration of Span 80: 4% w/w; carrier concentration: 20% w/w;
volume ratio of W/O emulsions to external phase: 0.2; internal phase concentration
(H2SO4): 0.3 N; diluent: hexane; contact time: 18 min; distance of the tip horn from
the bottom of vessel: 20 mm).

is 40% because D2EHPA is an anionic surfactant in nature, the

stability of W/O emulsion in its presence would decrease due to ganic solution in the emulsion phase. Fig. 9 shows the experimen-
water transport [20]. The optimum concentration of carrier was tal results of the membrane stability as a function of this ratio in
20% (w/w). the range 0.5–2. It can be seen that the breakage percentage is
dependent of the Vint/Vorg ratio. When the ratio increased from
0.5 to 0.8, the stability increased slightly, because the ejection of
3.1.6. Effect of surfactant concentration
the internal phase is easier when its proposition in the emulsion
Surfactant concentration has an important bearing on the sta-
is higher. These results may be explained on the basis that increas-
bility of the emulsion. Fig. 8 shows the effect of surfactant concen-
ing the internal phase volume in this interval makes the emulsion
tration on the W/O emulsion breakage after stirring at 200 rpm.
more stable. This quantity is insufficient for mass transfer in the
The percentage of breakage was less than 10% for Span 80 concen-
second step. Hence, in order to obtain a uniform and homogeneous
trations above 4% (w/w), indicating that the membrane was suffi-
distribution of the internal phase droplets in the membrane space
ciently stable, while the breakage percentage increases with the
and to avoid the influence of H2SO4 on the emulsion stability, the
decrease in surfactant concentration (less than 4% (w/w)). Below
optimum ratio of the internal aqueous phase to the organic phase
Span 80 concentration of 2% (w/w), no emulsion was formed owing
was taken to be 1. Beyond the ratio of 1.2, further increase in the
to a lack of the surfactant adsorbing the organic/aqueous interface.
volume of stripping solution leads to a decrease in membrane sta-
The concentration of surfactant chosen in this work to produce effi-
bility, because when the volume of the stripping phase increases,
ciently stabilized membrane was 4% (w/w).
the thickness of film in droplets thin off.

3.1.7. Effect of volume ratio of aqueous internal phase to organic phase 3.1.8. Effect of volume ratio of water-in-oil (W/O) emulsions to
(Vint/Vorg) aqueous external phase
Another important experimental parameter is the appropriate This parameter expresses the treatment ratio of the whole
volume ratio of inner aqueous solution (the stripping phase) to or- emulsion liquid membrane process. Its variation cannot be ran-
dom, because it is necessary to guarantee that the acid quantity
60
present in the internal phase is high enough to react with the sol-
ute present in the external phase. Experiments were conducted by
50
taking into account the parameters already optimized and using a
40
volume ratio of the organic phase to the aqueous internal phase of
Beakage (%)

1. The volume ratio of emulsion to external phase varied between

30 0.05 and 1. As shown in Fig. 10, the increase of volume ratio of
emulsion to aqueous external phase (Vem/Vext) leads to an increase
20 of the breakage percentage. The increase of volume ratio of the
membrane phase to the external phase beyond 0.4 led to an in-
10 crease of the emulsion coagulation. Indeed, with increasing the
volume ratio, the swelling phenomenon becomes remarkable, fast,
0 and accompanied by an embrittlement following a more signifi-
0 1 2 3 4 5 6 7 8 9
cant coalescence of the internal droplets which grow. This behavior
Surfactant concentration (% w/w)
involves an increase of the emulsion breakage. Therefore, it seems
Fig. 8. Effect of surfactant concentration on the W/O emulsions stability (exper- that the optimum volume ratio of emulsion to the external aque-
imental conditions: emulsion volume: 20 mL; external phase (pure water) volume: ous phase is 0.2.
100 mL; volume ratio of internal phase to organic phase: 1; emulsification time:
3 min; ultrasound power: 20 W, stirring speed: 200 rpm; concentration of Span 80:
2–8% w/w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to
3.1.9. Choice of diluent
external phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane; Although experiments have been performed with aromatic dil-
contact time: 18 min; distance of the tip horn from the bottom of vessel: 20 mm). uents [25], aliphatic diluents are generally preferred because of the
 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325
90
80
70
60
Breakage (%)
50
40
30
20
10
0 0
0 0.2 0.4 0.6 0.8 1 1.2
Vem /Vext
Fig. 10. Effect of the volume ratio of the emulsion to the external phase on the W/O
emulsions stability (experimental conditions: volume ratio of internal phase to
organic phase: 1; emulsification time: 3 min; ultrasound power: 20 W, stirring
speed: 200 rpm; concentration of Span 80: 4% w/w; carrier concentration: 20% w/
w; volume ratio of W/O emulsions to external phase: 0.05–1; internal phase
concentration (H2SO4): 0.3 N; diluent: hexane; contact time: 18 min; distance of
the tip horn from the bottom of vessel: 20 mm).
8
Dodecane
7 ena, in this work, the position of the tip of horn ultrasound (Fig. 1)
Heptane
6 from the bottom of vessel affects the emulsion stability. The dis-
Hexane
Breakage (%)
5
4 cavitation rich region. When the distance of probe from the bottom
3
2 rich region and the presence of turbulent regime due the reflection
1 of ultrasound wave.
0
0 50 100 150 200 250 300
Time (s)
Fig. 11. Effect of diluents nature on the W/O emulsions stability (experimental
conditions: emulsion volume: 20 mL; external phase (pure water) volume: 100 mL;
volume ratio of internal phase to organic phase: 1; emulsification time: 3 min;
ultrasound power: 20 W, stirring speed: 200 rpm; concentration of Span 80: 4% w/
w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to external
phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent: hexane, heptane
and dodecane; contact time: 18 min; distance of the tip horn from the bottom of
vessel: 20 mm).
insolubility in water and better emulsion stability. The mass trans-
fer is in many cases diffusion controlled, and therefore the viscosity
of the diluent is an important parameter. As shown in Fig. 11, suit-
able diluent for a good stability of the W/O emulsions is hexane
with viscosity of 0.294 cP, because hexane is less viscous than hep-
tane and dodecane (0.386 and 1.34 cP, respectively). This is in
agreement with the ultrasound theory; cavities are more readily
formed when using a solvent with a high vapor pressure and low
viscosity [26]. Because viscosity is a measure of resistance to shear,
it is more difficult to produce cavitation in a viscous liquid [27].
3.1.10. Effect of the probe position
Fig. 12 shows the effect of probe position in the emulsifying
vessel on the emulsion stability. It is well known that the ultra-
sonic energy produces an alternating adiabatic compression and
refraction of the liquid being irradiated. In the refraction part of
ultrasonic wave, micro-bubbles form due to sufficiently large neg-
ative pressures. These bubbles contain gas and vaporized liquid
and can be either stable about their mean size for many cycles or
transient as they grow to certain size and violently collapse during
the compression part of the wave, i.e. imploding cavitation bubbles
323
10
9
8
7
Breakage (%)
6
5
4
3
2
1
20 22 24 26 28 30 32 34 36
Distance of the tip of probe from the botom of vessel (mm)
Fig. 12. Effect of the tip of horn position on the W/O emulsions stability
(experimental conditions: emulsion volume: 20 mL; external phase (pure water)
volume: 100 mL; volume ratio of internal phase to organic phase: 1; emulsification
time: 3 min; ultrasound power: 20 W, stirring speed: 200 rpm; concentration of
Span 80: 4% w/w; carrier concentration: 20% w/w; volume ratio of W/O emulsions
to external phase: 0.2; internal phase concentration (H2SO4): 0.3 N; diluent:
hexane; contact time: 18 min; distance of the tip horn from the bottom of vessel:
20–35 mm).
cause intensive shock waves in the surrounding liquid and the for-
mation of liquid jets of high velocity. According to these phenom-
tance of this tip from vessel bottom (20 mm) that conducted to
the lower breakage is selected because this distance coincide to
is short, a good stability of emulsion was obtained. In this case, the
real microstreaming phenomenon is obtained by the cavitation
350
3.2. Copper extraction into ELM
Extraction of copper(II) by ELM process is governed by several
parameters and poses a challenging problem in the field of hydro-
metallurgy. The equations given below exhibit extraction (1) and
stripping (2) reactions of copper occurring in ELM technique [28]
Cu2þ þ
aq þ 2H2 R2org ¡ CuR2  2HR org þ 2Haq ð1Þ
CuR2  2HRorg þ 2Hþint ¡ Cu2þ
int þ 2H2 R 2org ð2Þ
where, (H2R2) represents the D2EHPA dimmer and the molecular
structure of the complex CuR22HRorg is shown in Fig. 13.
Facilitated transport of behavior through ELM, being permeated
from the external into the internal aqueous phase, consisted of four
steps: (1) diffusion of copper through the external aqueous bound-
ary film, (2) distribution of copper between the external aqueous
and liquid membrane phase, (3) diffusion of copper through the
membrane phase (Fig. 13), and (4) stripping of copper, accompa-
nied by reaction (2), into the internal aqueous phase.
The performance of the extraction depends on the nature of
emulsion (previously optimized) and various operational parame-
ters as detailed below.
3.2.1. Effect of copper concentration in the external aqueous phase
The effect of copper ion concentration (50, 100, 150 and
200 ppm) in the feed phase on the extraction efficiency was inves-
tigated. The extraction was performed at pH 2 using a stripping
acid concentration of 0.3 N. The obtained results are presented in
Fig. 14. It is observed that the percentage of extraction decreased
when the initial content of copper increased. At low copper con-
centrations (50–100 ppm), high extraction efficiency is obtained
324 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325

100
H17C8O O HO OC8H17
90
80

Extraction efficiency (%)

P P 70
60

H17C8O O O OC8H117 50
40

Cu 30
20
10
O O 0
5 10 15 20 25 30
D2EHPA (%)

CH3 Fig. 15. Effect of carrier concentration on the extraction efficiency (experimental
conditions: emulsion volume: 20 mL; external phase volume: 100 mL; volume ratio
Fig. 13. Molecular structure of the complex formed between coppper(II) and of internal phase to organic phase: 1; emulsification time: 3 min; ultrasound
D2EHPA dimmer in organic phase. power: 20 W, stirring speed: 200 rpm; concentration of Span 80: 4% w/w; carrier
concentration: 5–30% w/w; volume ratio of W/O emulsions to external phase: 0.2;
internal phase concentration (H2SO4): 0.3 N; diluent: hexane; contact time: 18 min;
Distance of the tip horn from the bottom of vessel: 20 mm).
100
90 (w/w)), the permeation efficiency decreases by increasing the car-
80 rier concentration because the extractant acts as a thinner for the
Extraction efficiency (%)

70 membrane phase (i.e. the increasing concentration of carrier pro-

60
50
40
30
20
10
0 3.2.3. Effect of stirring speed
0 5 10
Time (min)
Fig. 14. Effect of external phase concentration on the extraction efficiency and
extraction kinetics (experimental conditions: emulsion volume: 20 mL; external
phase volume: 100 mL; volume ratio of internal phase to organic phase: 1;
emulsification time: 3 min; ultrasound power: 20 W, stirring speed: 200 rpm;
concentration of Span 80: 4% w/w; carrier concentration: 20% w/w; volume ratio of
W/O emulsions to external phase: 0.2; internal phase concentration (H2SO4): 0.3 N;
diluent: hexane; contact time: 18 min; distance of the tip horn from the bottom of
vessel: 20 mm).
(95%). But for 200 ppm solutions, copper extraction reached about
74%. This is due the saturation of the internal droplets of the emul-
sion that is attained more rapidly for high concentrations in the
external phase. When the solute concentration is high, the copper
complex must diffuse through the membrane phase to the internal
phase. This suggests that the mass transfer resistance in the emul-
50ppm motes the permeation swelling, which dilutes the aqueous receiv-
100ppm ing phase and decreases the efficiency of the process). Additionally,
150ppm the stability of emulsion decreases by increasing the carrier con-
200ppm centration over a certain limit. The best value of D2EHPA concen-
tration was found to be 20% (w/w).
15 20 The stirring speed has a profound influence on the extraction
behavior. The effect of this parameter on the extraction of copper
ions by ELM is shown in Fig. 16. By increasing the stirring speed
from 100 to 200 rpm, the shear force, which acts on the emulsion
globules, increases and this makes the globules smaller resulting
in an enhancement of the mass transfer and extraction efficiency.
Increasing the stirring speed in the range 200–500 rpm not only
decreases the extraction efficiency slightly, but also affects the sta-
bility of the emulsion and makes the emulsion unstable. When the
level of stirring speed is increased above 500 rpm, the extraction
efficiency significantly decreased because high stirring speed
produced coalescence and finally rupture of globules, making the
100
90
80
Extraction efficiency (%)

70
sion globule is important. In the extraction kinetic process, the
60
contact time between W/O emulsion and feed aqueous phase has
a significant influence on the extraction of copper. According to 50
Fig. 14, it was observed that the kinetics of the process is very fast. 40
The level of extraction increased with the increase in contact time. 30
For copper concentrations of 50 and 100 ppm, the removal per- 20
centage is good and exceeded 95% after 18 min. 10
0
100 200 250 300 400 500 600 800 1000 1200
3.2.2. Effect of carrier concentration
Stirring speed (rpm)
Fig. 15 shows the effect of D2EHPA concentration on the ELM
extraction of copper. It was found that extraction increased with Fig. 16. Effect of Stirring speed on the extraction efficiency (experimental condi-
increasing carrier concentration. This is because increase in tions: emulsion volume: 20 mL; external phase volume: 100 mL; volume ratio of
D2EHPA concentration will increase the mass transfer. On the internal phase to organic phase: 1; emulsification time: 3 min; ultrasound power:
20 W, stirring speed: 100–1200 rpm; concentration of Span 80: 4% w/w; carrier
other hand, an increase in carrier concentration in the membrane concentration: 20% w/w; volume ratio of W/O emulsions to external phase: 0.2;
phase increases the viscosity of this membrane, which limits the internal phase concentration (H2SO4): 0.3 N; diluent: hexane; contact time: 18 min;
extraction rate of the metal ions. Above a certain value (20% distance of the tip horn from the bottom of vessel: 20 mm).
 M. Chiha et al. / Ultrasonics Sonochemistry 17 (2010) 318–325
100
90
80
Extraction efficiency (%)
70
60
50
40
30
20
10
0 emulsion liquid membrane: the effect of resistance to mass transfer at the
0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
Sulfuric acid concentration (N)
Fig. 17. Effect of H2SO4 concentration in the internal phase on Cu(II) stripping.
(experimental conditions: emulsion volume: 20 mL; external phase volume:
100 mL; volume ratio of internal phase to organic phase: 1; emulsification time:
3 min; ultrasound power: 20 W, stirring speed: 200 rpm; concentration of Span 80:
4% w/w; carrier concentration: 20% w/w; volume ratio of W/O emulsions to
external phase: 0.2; internal phase concentration (H2SO4): 0.1–1.4 N; diluent:
hexane; contact time: 18 min; distance of the tip horn from the bottom of vessel:
20 mm).
primary emulsion unstable. A stirring speed of 200 rpm was cho-
sen in this study.
3.2.4. Effect of H2SO4 concentration in the internal phase on Cu(II)
stripping
The capacity of the emulsion to extract solute is limited by the
internal phase stripping acid concentration. The influence of the
internal phase reagent concentration on the extraction efficiency
is shown in Fig. 17. It was found that the extraction increased when
the concentration of sulfuric acid in the internal phase increased
from 0.1 to 0.3 N. However, further increases in the concentration
reduce the level of copper extraction. This is a result of the increase
in the ionic strength difference between internal and external
phases that resulted in an increase in swelling, which conducted
in greater amounts of water to permeate through the membrane
causing the internal phase droplets to swell and coalesce and final-
ly breakdown of globules. On the other hand, high acid content in
stripping solution would cause a faster degradation of both
extractant and surfactant compounds. Internal phase concentra-
tion of 0.3 N was chosen in the present study.
4. Conclusions
Sonication can be used to produce stable W/O emulsion in ELM
process. This is possible because cavitational collapse at or near the
interface disrupts it and impels jets of one liquid into the other to
form the emulsion. Optimum sonication parameters giving stable
emulsion are an ultrasonic power of 20 W and a distance of
20 mm of the probe from the bottom of emulsification cell. The
concentrations of carrier and surfactant leading to stable emul-
sions were 20% and 4% w/w, respectively. The concentration of sul-
furic acid which conducts to the lower breakage was 0.3 N. The
volume ratio of organic phase to aqueous internal phase giving a
stable emulsion was selected to be 1. The effect of the volume ratio
of water-in-oil (W/O) emulsions to aqueous external phase on the
stability was 0.2. The stirring speed which ensures a good stability
of the emulsion and an acceptable size of the globules ensuring fast
removal kinetics from aqueous external solution was 200 rpm.
Hexane has a low viscosity compared to heptane and dodecane,
which facilitates ultrasonic cavitation and ensures a good emulsifi-
cation. The W/O emulsion lifetime produced by ultrasonication is
much higher than that prepared previously by mechanical agita-
tion compared with previous studies [29]. The exact process of
droplet disruption due to ultrasound, especially as a result of
325
cavitation, is not yet fully understood. D2EHPA can be used to sep-
arate copper ions from aqueous solutions in an ELM process with
95% of extraction efficiency. An extractant concentration of 20%
(w/w) in the membrane phase and a concentration of H2SO4 of
0.3 N in the internal solution were found to be optimum conditions
for obtaining a higher separation factor. It was found that 200 rpm
can be recommended as the best stirring speed.
References
[1] N.N. Li, Separating hydrocarbons with liquid membranes, U.S. Patent 3, 1968,
pp. 410–794.
[2] G. Sznejer, A. Marmur, Cadmium removal from aqueous solution by an
1 1.2 1.4 outer oil–water interface, Collo Surf. A: Physicochem. Eng. Asp. 151 (1999) 77–
83.
[3] G. Schulz, Separation techniques with supported liquid membranes,
Desalination 68 (1988) 191–202.
[4] J. Yang, R. Pal, Effects of aqueous-phase acidity and salinity on isotonic swelling
of W/O/W emulsion liquid membranes under agitation conditions, J. Membr.
Sci. 244 (2004) 193–203.
[5] J.D. Wadhawan, F. Marken, R.G. Compton, Biphasic sonoelectrosynthesis. A
review, Pure Appl. Chem. 73 (2001) 1947–1955.
[6] D. Ensminger, Ultrasonic: the Low- and High-Intensity Applications, Marcel
Dekker, New York, 1973.
[7] W. Wood, A.L. Loomis, The physical and biological effects of high frequency
sound waves of great intensity, Philos. Mag. J. Sci. 44 (22) (1927), pp. 2E–2F3.
[8] B. Abismail, J.P. Conselier, A.M. Wilhelm, H. Delmas, C. Gourdon, Emulsification
by ultrasound: drops size distribution and stability, Ultrason. Sonochem. 6
(1999) 75–83.
[9] T. Kitagawa, Y. Nishikawa, J.W. Frankenfeld, N.N. Li, Waster water treatment by
liquid membrane process, Environ. Sci. Technol. 11 (1977) 602–605.
[10] B.A. Mikucki, K. Osseo-Asare, The liquid surfactant membrane process: effect
of the membrane process: effect of the emulsifier type on copper extraction by
LIX65 N-LIX 63 mixtures, Hydrometallurgy 16 (1986) 209–229.
[11] T.P. Martin, G.A. Davies, The extraction of copper from dilute aqueous
solutions using a liquid membrane process, Hydrometallurgy 2 (1977) 315–
334.
[12] W. Volkel, W. Halwachs, K. Schugerl, Copper extraction by means of a liquid
surfactant membrane process, J. Membr. Sci. 6 (1980) 19–31.
[13] J.W. Frankenfeld, R.P. Cahn, N.N. Li, Extraction of copper by liquid membranes,
Sep. Sci. Technol. 16 (4) (1981) 385–402.
[14] A.K. Chakravarti, S.B. Chowdhury, D.C. Mukherjee, Liquid membrane multiple
emulsion process of separation of copper(II) from waste waters, Colloids Surf.
A: Physicochem. Eng. Asp. 166 (2000) 7–25.
[15] B. Sengupta, R. Sengupta, N. Subrahmanyam, Copper extraction into emulsion
liquid membranes using LIX 984N-C, Hydrometallurgy 81 (2006) 67–73.
[16] F. Valenzuela, C. Fonesca, C. Basualto, O. Correa, C. Tapia, J. Sapag, Removal of
copper ions from a waste mine water by a liquid emulsion membrane method,
Miner. Eng. 18 (2005) 33–40.
[17] F. Valenzuela, J. Cabrera, C. Basualto, J.S. Hagar, Kinetics of copper removal
from acidic mine drainage by a liquid emulsion membrane, Miner. Eng. 18
(2005) 1224–1232.
[18] O. Behrend, K. Ax, H. Schubert, Influence of continuous phase viscosity on
emulsification by ultrasound, Ultrason. Sonochem. 7 (2000) 77–85.
[19] O. Behrend, H. Schubert, Influence of ultrasonic pressure and gas content on
continuous ultrasound emulsification, Ultrason. Sonochem. 8 (2001) 271–276.
[20] R.S. Juang, K.H. Lin, Ultrasound-assisted production of W/O emulsions in liquid
surfactant membrane process, Colloids Surf. A: Physicochem. Eng. Asp. 238
(2004) 43–49.
[21] F.F. Zha, A.G. Fane, C.J.D. Fell, Instability mechanisms of supported liquid
membranes in phenol transport process, J. Membr. Sci. 107 (1995) 59–74.
[22] S. Koda, T. Kimura, H. Kondo, H. Mitone, A standard method to calibrate
sonochemical efficiency of an individual reaction system, Ultrason. Sonochem.
10 (2003) 149–156.
[23] T.J. Mason, J.P. Lorimer, D.M. Bates, Quantifying sonochemistry: casting some
light on a ‘black art’, Ultrasonics 30 (1992) 40–42.
[24] S. Freitas, G. Hielscher, H.P. Merkle, B. Gander, Continuous contact-and
contaminant-free ultrasonic emulsification- a useful tool for pharmaceutical
development and production, Ultrason. Sonochem 13 (2006) 76–85.
[25] J. Draxler, R. Marr, Emulsion liquid membranes, Part I: phenomenon and
industrial application, Chem. Eng. Process. 20 (1986) 319–329.
[26] L.H. Tompson, L.K. Doraiswamy, Sonochemistry: science and engineering, Ind.
Eng. Chem. Res. 38 (1999) 1215–1249.
[27] T.J. Mason, Sonochemistry, Oxford University, 1999, New York.
[28] E.A. Fouad, Zinc and copper separation through an emulsion liquid membrane
containing di-(2-ethylhexyl)phosphoric acid as a carrier, Chem. Eng. Technol.
31 (3) (2008) 370–376.
[29] M. Chiha, M.H. Samar, O. Hamdaoui, Extraction of chromium(VI) from acid
aqueous solution by a liquid surfactant membrane (LSM), Desalination 194
(2006) 69–80.
[30] R. Sabry, A. Hafez, M. Khedr, A. El-Hassanin, Removal of lead by an emulsion
liquid membrane Part I, Desalination 212 (2007) 165–175.