ASIA-PACIFIC JOURNAL OF CHEMICAL ENGINEERING

Asia-Pac. J. Chem. Eng. 2008; 3: 387–399

Published online 8 July 2008 in Wiley InterScience
([Link]) DOI:10.1002/apj.160

Research Article
Removal of copper and zinc from aqueous solutions
and industrial effluents using emulsion liquid membrane
technique
S. Venkatesan and K. M. Meera Sheriffa Begum*
Department of Chemical Engineering, National Institute of Technology, Tiruchirapalli, Tamil Nadu 620015, India

Received 10 October 2007; Revised 15 February 2008; Accepted 18 April 2008

ABSTRACT: Copper and zinc were removed from dilute aqueous solutions together with recovery of copper from
electroplating wastewater containing copper ions by emulsion liquid membrane (ELM) technique. The effects of
surfactant concentration, carrier concentration, emulsification speed, emulsification time, internal phase stripping agent
concentration, and aqueous-to-organic phase (A/O) volume ratio on the emulsion stability and breakup have been
studied in detail and reported. A mixture of kerosene as diluent, span 80 as surfactant, di-(2-ethylhexyl) phosphate as
carrier was used. An experimental study was performed to optimize the pH of the aqueous external phase based on
distribution coefficient of solute between aqueous external phase and organic (membrane) phase. The batch extraction
was carried out under various experimental conditions such as agitation time, agitation speed, membrane-to-external
phase (M /E ) ratio, solute concentration in the feed phase and carrier concentration in membrane phase on the percentage
recovery of zinc and copper ions in their respective feed streams and the operating parameters have been optimized
for maximum recovery. It was found that 84% of copper and 86% of zinc were removed from aqueous solution with
a concentration factor of 5. It was also found that ELM extraction of copper from wastewater was around 8–17% less
than that of the synthetic solution.  2008 Curtin University of Technology and John Wiley & Sons, Ltd.

KEYWORDS: zinc; copper; emulsion liquid membrane; D2EHPA; electroplating effluent

INTRODUCTION essential to find effective and efficient methods for the

recovery of metal ions even at very low concentration
The strong release of heavy metals into the environment in wastewaters.[2]
by several industries has meant that their recovery from Liquid membranes for the separation and concentra-
wastewater has become a major topic of research in tion of metal ions have received considerable attention
wastewater treatment. According to the World Health throughout the past three decades due to its charac-
Organization[1] the most toxic metals are aluminum, teristics such as ease of operation, low energy, higher
chromium, iron, cobalt, nickel, copper, zinc, cadmium, diffusive flux and low-cost operation factors.[3] Usage
mercury and lead. The major industries that contribute of electrochemical recovery is a viable option. How-
to water pollution by chromium are mining, leather ever, its application in dilute feed streams are not
tanning, textile dyeing, electroplating, aluminum con- encouraging.[4] Solvent extraction is another option but
version, coating operations, plants producing industrial it has a number of disadvantages. The mass transfer
inorganic chemicals and pigments and wood preser-
efficiency and minimizing solvent losses depend on the
vatives. Removal of metals from their effluents has
operating parameters of the equipment. A higher solvent
assumed higher significance in the recent past due to
the decreasing availability of natural resources and the loss during the process of extraction reduces not only
increasing contamination of metal ions in the environ- transport efficiency considerably, but also more number
ment. Water contamination by traces of heavy metal of stages for the separation of pure products.[5,6] Emul-
ions is a major environmental hazard and its removal is sion liquid membranes (ELM) on the other hand exhibit
highly essential. The increasing demand for most of the greater potential, particularly in processing dilute feed
heavy metals and the depletion of ores globally make it streams for the separation and removal or recovery
of metal ions.[7] ELMs proved to be an effective
and inexpensive method in a variety of fields such
*Correspondence to: K. M. Meera Sheriffa Begum, Department of
Chemical Engineering, National Institute of Technology, Tiruchirap- as the recovery of various metal ions,[8 – 14] removal
palli, Tamil Nadu, India. E-mail: meera@[Link] of acetic acid,[15] removal of phenolic compounds
 2008 Curtin University of Technology and John Wiley & Sons, Ltd.
388 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

and lactic acid[16,17] and recovery of pharmaceutical sulfate and zinc sulfate were obtained from Merck
substances.[18] In this method, the diffusion of the metal (M). An aqueous solution of 1 N H2 SO4 was used as
ions is facilitated by the presence of an oil-soluble car- stripping agent and an aqueous solution of citrate buffer
rier. This forms a complex with the outer oil–membrane (pH = 5) was obtained from Merck (M). The extractant,
interface. The complex then diffuses through the mem- diluent and strip agents used were of analytical grade.
brane and there the metal ions replace the counter To maintain a low pH in external phase, an aqueous
ion, which in most cases is H+ . Copper is recovered solution of citrate buffer (pH = 5) was added to the
from low-grade ores by hydrometallurgical process, for external phase. The organic chemicals for analytical
which solvent extraction is currently practiced. The purposes used were of AR grade and the water used
extraction of zinc from sulfuric media has experienced was distilled.
a renewed interest because of the use of this process
on a commercial scale for treating wastewater streams
and secondary materials.[19] In our earlier work, the
Characterization of feed solutions
flow pattern and velocity profile during the formation
of emulsion at high speed were studied using computa-
Three types of feeds chosen for this study are syntheti-
tional fluid dynamics (CFD) and reported.[20] This will
cally prepared zinc, copper aqueous solutions and elec-
largely help to enhance further studies in the area of
troplating effluent (which were collected from a nearby
phase inversion of emulsion and dispersion. Although
industry) containing Cu2+ ions. The industrial efflu-
numerous papers have already been reported on ELM
ent was then converted to Cu2+ ions of 100, 200 and
extraction process, no literature was reported on detailed
300 ppm for our studies. Synthetic aqueous zinc and
study on various factors affecting the emulsion breakup
copper feed solutions with concentrations of 100, 200
and stability time.
and 300 ppm were prepared and used for ELM extrac-
In our present work, the ELM system was used to
tion process. The properties of electroplating effluent
remove zinc and copper from their respective feed solu-
used are given in Table 1.
tions and copper from electroplating wastewater. Var-
ious factors affecting the emulsion stability, emulsion
breakup and factors affecting ELM extraction was stud-
ied in detail. Emulsion liquid membrane preparation

During the formulation of ELM, the organic phase (dilu-

Transport mechanism ent, carrier and emulsifier) was prepared by dissolving
the required concentration of carrier and surfactant with
Most of the ELM extraction process is governed by appropriate diluent. The ELM used in this study was
coupled-transport mechanism. In coupled transport, the water–oil–water (w/o/w) type of emulsion formed by
heavy metal ions are coupled with carriers present in the mixing 50% by volume of 1 N H2 SO4 internal stripping
membrane, and the carriers exchange the heavy metals solution with 50% by volume of organic phase. Initially,
with suitable ions present inside the strip phase.[21 – 23] the organic phase was stirred at 10 500 rpm for 3 min in
In a coupled transport, zinc is extracted by di-(2- a high-speed homogenizer to form a uniform mixture.
ethylhexyl) phosphate (D2EHPA) from sulfate media Then the internal phase was added dropwise and again
according to the following reaction (Reis et al ., 2003). stirred at about 10 500 rpm for 5 min to form a stable
The complexation and stripping reactions are given in milky white emulsion.
Eqns (1) and (2).

Zn2+ + 1.5(HR)2 ↔ ZnR2 (HR) + 2H+ (1) Experimental procedure

where the extractant is (HR) assumed to react as a The batch operation was carried out in an extractor of
dimer. Copper is transported according to the equation. diameter 150 mm with 1 l capacity. An impeller fitted
with a variable speed motor was used for agitation. The
Cu2+ + 1.5(HR)2 ↔ CuR2 (HR) + 2H+ (2) schematic layout is shown in Fig. 1. The effluent to be
treated consisted of an aqueous solution of zinc sulfate
containing Zn2+ ions. This was contacted through
MATERIALS agitation with an emulsion dispersed in globules in
a batch extractor for a known time at a particular
D2EHPA extractant and Span 80 (sorbiton mono oleate) speed. During the contact between aqueous solution
surfactant were obtained from Sigma. Kerosene used as and the emulsion, solute transport occurred through
a diluent was obtained from Fluka Chemika. Copper the membrane phase into the internal receiving phase,
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 389

where it was concentrated. The mixture was then The emulsion breakage represents the ratio in per-
allowed to separate. The treated effluent from the centage of the volume of internal phase leaked into the
emulsion was decanted. Similar procedure was used external phase by splitting (Vs ) to the initial volume of
to recover the copper (II) ions. Thus, extraction and the internal phase (Vi ). The volume Vs was calculated
stripping are carried out in a single step. Copper and by material balance.
zinc analysis in aqueous and organic phases have been
performed using with a Perkin-Elmer atomic absorption
spectrophotometer model 290. pH measurements were
carried out by combined electrode pH meter. Changes in Emulsion swelling and breakage
the volume of internal phase were estimated by material
balance after breaking the emulsion at the end of the Emulsion swelling and breakage are the undesirable
experiments. phenomena that affect the ELM extraction. Entrainment
swelling is caused by the entrainment of the external
phase into the internal phase due to the repeated coales-
cence and redispersion of emulsion globules during the
RESULTS AND DISCUSSION dispersion operation, thus always causing an increase in
the volume of the internal phase. Entrainment swelling
Emulsion stability is normally neglected because ELM extraction is car-
ried out at mild agitations only. Osmotic swelling is
When the W/O emulsion is dispersed by stirring in driven by difference in the osmotic pressure between
the continuous aqueous solution, the emulsion must be the external and internal phases. In most ELM systems,
sufficiently stable to extract the solute ions into the osmotic swelling causes an increase in volume of the
internal aqueous droplets. In ELMs, emulsion globules internal phase because the ionic strength in the internal
are stabilized by surfactants and the degree of extraction phase is greater than that in the external phase, lead-
for a solute ion into a stripping phase is influenced by ing to the transport of water from the external phase to
the stability of the emulsion. Therefore, the stability of the internal phase. This is important only at the initial
the emulsion was investigated by using the breakup, E, time of ELM extraction because in a counter-current
defined by the following Eqn (3): coupled-transport process, ions are getting exchanged
from internal phase to external phase. The variation
E = (VS /VI ) × 100 (3) of the pH of this phase with time is an indication of
the emulsion breaking. Ultimately, difference in ionic
strength is very low. It is clear that water in the inter-
Table 1. The properties of raw effluent from nal phase can also be transported to the external phase
electroplating industry.
when the ionic strength in the external phase is greater
Electroplating than that in the internal phase. Accordingly, emulsion
Properties effluent swelling may be ‘positive’ or ‘negative.’ The negative
swelling is called membrane breakage. In the deter-
pH 4.5
mination of the membrane breakage, many different
Cu2+ ions (ppm) 2800
methods are employed for the measurement of emul-
COD (mg dm−3 ) 2700
BOD (mg dm−3 ) 945
sion breakage such as the volume variation method,
Odor Very high internal phase droplet size variation method, viscos-
Color Dark brown ity variation method, density variation method, tracer
method and Carl–Fisher method. In our study, we used

Figure 1. Schematic layout of emulsion liquid membrane extraction process.

 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
390 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

volume variation method for measuring the membrane 200

Emulsion stability Time Vs Mixing time
10
breakage. 180 Emulsion Break up Vs Mixing Time 9
160 8

Emulsion Break up (%)

Stability time (mins)
140 7
Effect of surfactant concentration
120 6
Surfactant plays a vital role in maintaining the stability 100 5
of the emulsion. The amount of surfactant was varied 80 4
from 0.4 to 3.2% (v/v) and the results are shown in
60 3
Fig. 2. It indicates that the increase in amount of sur-
factant up to 2.5% (v/v) increased the stability time up 40 2
to 140 min, and further increase in surfactant amount 20 1
decreased the stability time. As the surfactant amount 0 0
was increased, interfacial tension between the phases 0 2 4 6 8 10 12
decreased, which increased the stability of emulsion due Mixing time (mins)
to the prevention of droplet coalescence. Most of the
surfactants tend to form aggregates and decrease the Figure 3. Effect of mixing time on emulsion stability
and breakup (surfactant concentration = 2.5% v/v, carrier
stability of the emulsion, and this particular concen- concentration = 0% v/v, internal phase = 1 N H2 SO4 ).
tration is called critical micelles concentration (CMC).
Beyond CMC, the stability of emulsion decreases with
increase in surfactant concentration.[24,25] due to high internal shearing and prolonged exposure of
the emulsion to high speed.

Effect of mixing time

The effect of agitation time during emulsification on Effect of emulsification speed

emulsion stability is shown in Fig. 3. Emulsification
time was varied from 3 to 10 min. It indicates that the Experiments were conducted at different emulsification
increase in emulsification time up to 6 min increased speeds from 2000 to 12 000 rpm. Figure 4 shows the
the stability of emulsion up to 140 min, and a fur- effect of emulsification speed on the stability of the
ther increase in emulsification time decreases the stabil- emulsion. The emulsion breakage decreases with the
ity. For insufficient emulsification time (<6 min), the increase of the emulsification speed up to a particular
breakage is high because the droplets have larger size, speed. An efficient emulsification gives good dispersion
which is conducive for their coalescence. In contrast, of the internal phase to membrane phase. The fact
for longer emulsification time, the breakage is increased that these droplets become smaller and take more time
to coalesce provides good stability of the emulsion.
In addition, the size of the internal phase droplets is
200
Emulsion stability Time Vs Surfactant concentration
25 smaller at greater agitation intensity, creating a larger
180 Emulsion Break up Vs Surfactant Concentration surface area for extraction and hence obtaining higher
recovery. In general, the internal phase droplets are
160 20
small, having diameters of about 1–10 µm. It is clearly
Emulsion Break up (%)
Stability Time (mins)

140 observed that only at the speed of around 10 000 rpm

120 15 stable emulsion is formed, and with further increase
100 in speed the cream formation takes place. At lower
speeds de-emulsification takes place because of less
80 10
stability.
60
40 5
20 Effect of carrier concentration
0 0
0 0.5 1 1.5 2 2.5 3 3.5 With the above optimized results of surfactant concen-
Surfactant Concentartion (v/v) tration 2.5% (v/v), emulsification time of 6 min, and
at speed 10 000 rpm, the amount of carrier was varied
Figure 2. Effect of surfactant concentration on emulsion
stability and breakup (emulsification time = 6 min, car- from 0.2 to 1.5% (v/v). The effect of carrier concentra-
rier concentration = 0%, internal phase concentration = tion on emulsion stability is shown in Fig. 5. Increasing
1 N H2 SO4 ). the amount of carrier leads to a decrease in the stability
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 391

200 16 6
Emulsion stability time Vs Emulsification speed
180 Emulsion break up Vs Emulsification speed
14
Emulsion Stability Time (mins)

160 5

Emulsion Break up (%)

12
140

Emulsion break up(%)

120 10 4
100 8
80 3
6
60
4
40 2
20 2

0 0 1
0 2000 4000 6000 8000 10000 12000 14000
Emulsification speed (rpm)
0
0 0.5 1 1.5 2 2.5
Figure 4. Effect of emulsification speed on emulsion stability
H2SO4 Concentration (N)
and breakup (surfactant concentration = 2.5% v/v, carrier
concentration = 0.5% v/v, emulsification time = 6 min,
internal phase = 1 N H2 SO4 ). Figure 6. Effect of internal phase H2 SO4 concentration on
emulsion breakup (surfactant concentration = 2.5%, carrier
concentration = 0.5% (v/v), emulsification time = 6 min).

of the emulsion. This is due to reduction of viscos-

ity of the membrane phase. A very high content of
the carrier in the membrane phase results in swelling Effect of internal phase concentration
and breakup of internal phase into the external phase
and decreases the efficiency of the process. The value Experiments were conducted under the same conditions
of the carrier that was chosen for this ELM extraction as mentioned previously, by varying the concentrations
study was 0.5–1.0% (v/v). From the results, it could be of the internal phase (0.2, 0.4, 0.5 and 1.0 M of
observed that increasing the amount of carrier has two H2 SO4 ). Figure 6 shows the effect of internal phase
effects: the viscosity of membrane phase, which limits concentration on emulsion stability. When the H2 SO4
the extraction rate, decreases by increasing the carrier concentration increases, the stability of the emulsion
concentration, and hence, the carrier acts as a thinner decreases. This may be due to the reduction in the
for the membrane phase. At the same time, increasing properties of the surfactant by acidity of the internal
the carrier concentration over a certain limit decreases phase that consequently led to a destabilization of the
the stability of the emulsion.[26 – 30] emulsion.

160 20
Emulsion stability Time Vs Carrier concentration Effect of volume ratio of the organic phase
Emulsion Breakup Vs Emulsion stability time 18
140 to the aqueous internal phase
16
120
Emulsion Break up (%)
Stability Time ( mins)

14 With the above optimized emulsification conditions,

100 12 the volume ratios of the membrane phase to stripping
phase varied between 0.25 and 2.0. Figure 7 shows
80 10
the effect of variation of this ratio on the stability of
60 8 the emulsion. It is evident that the increase in volume
6 ratio of the organic phase to aqueous internal phase
40 leads to an increase in the stability of the emulsion.
4
20
The results may be explained on the basis of the fact
2
that increasing the stripping phase volume makes the
0 0 emulsion unstable and there is leakage of the internal
0 0.2 0.4 0.6 0.8 1 1.2 1.4 1.6
phase into the continuous phase, and eventually phase
Carrier concentration ( v/v)
inversion occurs. This may be due to increase in drop
Figure 5. Effect of carrier concentration on emulsion diameter and insufficient membrane phase to hold all the
stability and breakup (surfactant concentration = 2.5% v/v, internal phase (Ohtake et al ., 1988). Volume ratio of 1
emulsification time = 6 min, internal phase = 1 N H2 SO4 ). is chosen as optimum for further pertraction studies.
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
392 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

9 1.2
zinc concentration in feed = 100 ppm
8 copper concentration in feed = 100 ppm
1

Dimensionless concentration of
zinc and copper in feed (C/Co)
7
Emulsion break up (%)

6
0.8
5

4 0.6

3
0.4
2

1 0.2
0
0 0.5 1 1.5 2 2.5
0
V(organic phase)/ V(aqueous phase) 0 5 10 15 20 25 30 35
Agitation time (mins)
Figure 7. Effect of volume ratio of organic phase
to aqueous phase on emulsion breakup (%) (surfac- Figure 8. Effect of agitation time on extraction of copper
tant concentration = 2.5%, carrier concentration = 0.5%, and zinc from aqueous solution (carrier concentration =
emulsification speed = 10 000 rpm, emulsification time = 0.5% v/v, agitation speed = 300 rpm, M/E ratio = 1.00,
6 min, internal phase = 1 N H2 SO4 ). pH of the aqueous external phase = 4.5, pH of the internal
phase = 2.0).

ELM extraction
In ELM extraction, the effects of various parameters
such as pH of the external phase, agitation time, agi-
tation speed, membrane-to-external phase (M /E ) ratio, ELM system, the results of equilibrium studies were
feed concentration and carrier concentration on extrac- used as the guideline. The membrane solution contain-
tion performance were studied, and optimum conditions ing kerosene, emulsifier and carrier were mixed with
for maximum solute recovery was established for syn- an equal volume of aqueous solution of metal ions at
thetic effluents of zinc and copper and industrial effluent low agitation speed without emulsification and peri-
of copper. The results of the above studies are reported odical sampling until equilibrium was reached. After
and discussed below. equilibrium the membrane phase was separated from
the aqueous phase. Values of distribution coefficient
were calculated from experimental data. The results are
Effect of agitation time for pertraction shown in Figs 9 and 10 for various pH values. The dis-
tribution coefficients increase with increase in pH and
Experimental studies were carried out for optimizing then decrease. When the initial pH of the aqueous phase
the agitation time for maximum ELM extraction at a equals 4.44, a maximum distribution coefficient of 186
particular agitation speed and M /E ratio. The results occurred for copper solution which is reported.[31] The
are presented in Fig. 8. The dimensionless concentra- pH of the aqueous solution depends on the ratio of
tions of zinc and copper in the external phase (C /Co) acetic acid and sodium acetate in the buffer solution.
are plotted against time. It was observed from the figure At lower pH, the media becomes more acidic, more
that as the time for extraction was increased, the per- H+ ions present in the aqueous phase favors the for-
centage recovery of solute was found to be high at mation of Cu2+ from CuR2 and metal is released from
16 min. After 20 min, slight decrease in recovery due the organic phase to aqueous phase. At high pH, H+
to breakage of emulsion into external phase because concentration is lower, which favors the formation of
of prolonged exposure of emulsion into agitation was metal complex. Distribution coefficient increases with
found. From the above results, agitation time of 16 min increasing the pH up to a certain value, beyond which
was found to be optimum for maximum recovery of dissociation of copper into Cu2+ form is low, which
zinc and copper. reduces the distribution coefficient. Similar trend was
observed in the case of zinc also. The maximum distri-
bution coefficient of 124 occurred at a pH of 4 for zinc,
Effect of pH on distribution coefficient which is consistent with the reported value.[32] From
the above studies, pH of the aqueous phase optimized
In order to establish the optimal pH values for both the at 4.5 for zinc and copper, which was used throughout
feed and the receiving aqueous phases for an optimal the studies.
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 393

200 40
Acetate buffer concentration = 0.97 mol/lit M/E ratio = 0.75 M/E ratio = 1.00
180 Acetate buffer concentration = 0.19 mol/lit M/E ratio = 0.5 M/E ratio = 0.33

Percentage recovey of zinc from feed

160 35
Distribution coefficient

140

120 30
100

80
25
60

40
20
20

0
1 1.5 2 2.5 3 3.5 4 4.5 5 5.5 15
0 50 100 150 200 250 300 350 400 450
pH of aqueous phase
Agitation speed (rpm)
Figure 9. Effect of aqueous external phase pH on
distribution coefficient of copper (II) with D2EHPA carrier in Figure 11. Effect of agitation speed and M/E ratio on
kerosene (carrier concentration = 0.5% v/v, A/O ratio = 1). percentage recovery of zinc from synthetic feed (zinc
concentration in feed = 100 ppm, carrier concentration in
membrane phase = 0% v/v, pH of the external phase = 4.5,
pH of the internal phase = 2.0).
140

120
100
M/E ratio = 0.75 M/E ratio = 1.00
100
Distribution coefficient

95 M/E ratio = 0.5 M/E ratio = 0.33

percentage recovery of zinc from feed

90
80
85
60 80

40 75

70
20
65

0 60
0 1 2 3 4 5 6
pH of aqueous phase 55

50
Figure 10. Effect of aqueous phase pH on distribution 0 50 100 150 200 250 300 350 400 450
coefficient of zinc (II) with D2EHPA carrier in kerosene (carrier Agitation speed (rpm)
concentration = 0.5% v/v acetate buffer concentration =
0.2 mol/l, A/O ratio = 1). Figure 12. Effect of agitation speed and M/E ratio on
percentage recovery of zinc from synthetic feed (zinc
concentration in feed = 100 ppm, carrier concentration in
Effect of agitation speed membrane = 0.5% v/v, pH of the external phase = 4.5, pH
of the internal phase = 2.0).
Experimental studies were carried out at various
impeller speeds for different M /E ratios and car-
rier concentrations using synthetic feed solution. The from external phase increased to a maximum, and on
results obtained are shown in Figs 11–13 for synthetic further increase in agitation speed to 400 rpm the recov-
zinc solution and Figs 14–16 are for synthetic copper ery decreased, at a specific M /E ratio for 0, 0.5 and
feed. The percentage recovery of solute is defined as 1% (v/v) carrier concentrations. Similar results were
the ratio of difference between initial and final solute obtained for various M /E ratios and carrier concen-
concentration to the initial solute concentration. It is trations. The agitator speed of 300 rpm is found to be
observed from the figures that as the speed is increased the most effective to recover 32.5, 86.2 and 80.23%
from 100 to 300 rpm, the percentage solute recovered of zinc for 0, 0.5 and 1% (v/v) carrier concentrations,
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
394 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

100 100
M/E ratio = 0.75 M/E ratio = 1.00 M/E ratio = 0.75 M/E ratio = 1.00
95

Percentage recovery of copper from feed

M/E ratio = 0.5 M/E ratio = 0.33 M/E ratio = 0.5 M/E ratio = 0.33
percentage recovery of zinc from feed

90
90
80 85

70 80

75
60
70

50 65

60
40
55
30 50
0 100 200 300 400 500 0 100 200 300 400 500
Agitation speed (rpm) Agitation speed (rpm)

Figure 13. Effect of agitation speed and M/E ratio on Figure 15. Effect of agitation speed and M/E ratio on
percentage recovery of zinc from synthetic feed (zinc percentage recovery of copper from synthetic feed (copper
concentration in feed = 100 ppm, carrier concentration in concentration in feed = 100 ppm, carrier concentration in
membrane phase = 1% v/v, pH of the external phase = 4.5, membrane = 0.5% v/v, pH of the external phase = 4.5, pH
pH of the internal phase = 2.0). of the internal phase = 2.00).

40 100
M/E ratio = 0.75 M/E ratio = 1.00 M/E ratio = 0.75 M/E ratio = 1.00
38 M/E ratio = 0.5 M/E ratio = 0.33 M/E ratio = 0.5 M/E ratio = 0.33
Percentage recovery of copper from feed
Percentage recovery of copper from feed

90
36

34 80

32
70
30

28
60
26

24 50

22
40
20 0 100 200 300 400 500
0 100 200 300 400 500 Agitator speed (rpm)
Agitation speed (rpm)
Figure 16. Effect of agitation speed and M/E ratio on
Figure 14. Effect of agitation speed and M/E ratio on percentage recovery of copper from synthetic feed (copper
percentage recovery of copper from synthetic feed (copper concentration in feed = 100 ppm, carrier concentration in
concentration in feed = 100 ppm, carrier concentration in membrane phase = 1% v/v, pH of the external phase = 4.5,
membrane phase = 0% v/v, pH of the external phase = 4.5, pH of the internal phase = 2.0).
pH of the internal phase = 2.0).
is due to de-emulsification induced by higher shear of
respectively, at M /E ratio of 1.00 for a synthetic zinc the impeller and leakage from internal stripping phase.
solution of feed concentration of 100 ppm. For the syn-
thetic feed solution of copper the percentage recovery
was found to be 32.1, 84.36 and 78.12% of solute Effect of M/E ratio
for 0, 0.5 and 1% (v/v) carrier concentrations, respec-
tively, at M /E ratio of 1.00 for a feed concentration When the M /E ratio was varied from 0.33 to 1.00
of 100 ppm. The reason for the drop in percentage the observations from Figs 11–16 clearly indicate that
solute extracted from external phase beyond 300 rpm the percentage solute recovered from external phase
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 395

increases as the M /E ratio increases to 1.00 at a partic- 90

zinc con. in feed = 200 ppm
ular carrier concentration. Similar trend was observed zinc con. in feed = 100 ppm

Percentage recovery of zinc from feed

88 zinc con. in feed = 300 ppm
for various carrier concentrations at different impeller
speeds. This is due to the interfacial area of contact 86
between the external phase and emulsion increases as
the volume of emulsion increases. It is uneconomical 84
to increase M /E ratio above 1.00 because of the high 82
cost of chemicals involved in.
80

78
Effect of carrier concentration 76

The effect of carrier concentration in the membrane 74

phase on percentage of solute extracted from external 72
phase at 300 rpm and M /E ratio of 1.00 is shown in 0 50 100 150 200 250 300 350 400 450
Table 2. In order to balance the stability and transfer Agitator speed (rpm)
rate enhancement, it has been found that the optimum
carrier concentration of about 0.5% (v/v) is based on Figure 17. Effect of feed concentration on percentage
emulsion phase in the present investigation. recovery of zinc from synthetic feed (carrier concentration
in membrane = 0.5%, M/E ratio = 1.00, pH of the external
phase = 4.5, pH of the internal phase = 2.0).

Effect of feed concentration

75
zinc con. in feed = 200 ppm
The effect of feed concentration on the recovery of zinc con. in feed = 100 ppm
Percentage recovery of zinc from feed

zinc con. in feed = 300 ppm

solute from external phase for various agitator speeds
70
and M /E ratios was studied. Figures 17–20 show the
performance of extraction with feed concentrations for
synthetic feed solution of zinc, and Figs 21–24 for 65
synthetic feed solution of copper, respectively. From
these figures it is observed that the percentage extraction
of solute increases as the feed concentration decreases 60
from 300 to 100 ppm for various M /E ratios and carrier
concentration of 0.5%. This is due to the fact that the
ELM is more effective in separation of dilute streams. 55
The maximum extraction obtained in the case of zinc
solution is 86.2% for a feed concentration of 100 ppm,
at an agitator speed of 300 rpm and an M /E ratio of 50
1.00 with 0.5% carrier concentration. The maximum 0 100 200 300 400 500
extraction performance obtained in the case of copper Agitator speed (rpm)
solution is 84.36% for a feed concentration of 100 ppm,
Figure 18. Effect of feed concentration on percentage
at an agitation speed of 300 rpm and an M /E ratio of recovery of zinc from synthetic feed (carrier concentration
1.00 with 0.5% carrier concentration. in membrane = 0.5%, M/E ratio = 0.75, pH of the external
phase = 4.5, pH of the internal phase = 2.0).

Table 2. Effect of carrier concentration on percentage

recovery for zinc and copper (agitator speed = Effect of parameters on ELM extraction
300 rpm, M/E ratio = 1.00, feed concentration =
100 ppm). of copper from electroplating effluent

Effect of agitation speed and M/E ratio

Percentage Experimental studies on ELM pertraction were carried
Carrier recovery
concentration out at various impeller speeds for different M /E ratios
(%) Zinc Copper and carrier concentrations using electroplating effluent
0 32.5 32.1
containing copper ions. The raw effluent, initially with
0.5 86.2 84.36 2800 ppm of copper ions, was diluted to 100, 200 and
1 80.23 78.12 300 ppm. The experimental results obtained are shown
in Figs 25–27. It is observed from the figures that as
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
396 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

66 88
zinc con. in feed = 200 ppm copper con. in feed = 200 ppm
zinc con. in feed = 100 ppm copper con. in feed = 100 ppm

Percentage recovery of copper from feed

Percentage recovery of zinc from feed

64 zinc con. in feed = 300 ppm 86 copper con. in feed = 300 ppm

62 84

60 82

58 80

56 78

54 76

52
74

50
0 100 200 300 400 500 72
0 50 100 150 200 250 300 350 400 450
Agitator speed (rpm)
Agitator speed (rpm)

Figure 19. Effect of feed concentration on percentage Figure 21. Effect of feed concentration on percentage
recovery of zinc from synthetic feed (carrier concentration recovery of copper from synthetic feed (carrier concentration
in membrane = 0.5, M/E ratio = 0.5, pH of the external in membrane = 0.5%, M/E ratio = 1.00, pH of the external
phase = 4.5, pH of the internal phase = 2.5). phase = 4.5, pH of the external phase = 2.5).

65 80
zinc con. in feed = 200 ppm copper con. in feed = 200 ppm
zinc con. in feed = 100 ppm copper con. in feed = 100 ppm
Percentage recovery of copper from feed

zinc con. in feed = 300 ppm copper con. in feed = 300 ppm
Percentage recovery of zinc from feed

75
60

70

55
65

50 60

55
45

50
0 100 200 300 400 500
40
0 100 200 300 400 500 Agitator speed (rpm)
Agitator speed (rpm)
Figure 22. Effect of feed concentration on percentage
Figure 20. Effect of feed concentration on percentage recovery of copper from synthetic feed (carrier concentration
recovery of zinc from synthetic feed (carrier concentration in membrane = 0.5%, M/E ratio = 0.75, pH of the external
in membrane = 0.5%, M/E ratio = 0.33, pH of the external phase = 4.5, pH of the internal phase = 2.5).
phase = 4.5, pH of the internal phase = 2.5).

is due to the interfacial area of contact between exter-

nal phase and emulsion increases because of volume
the speed was increased from 100 to 300 rpm, the per-
of emulsion. The M /E ratio is optimized at 1.00 to
centage solute recovered from external phase increased
achieve maximum performance for this present study.
to a maximum and on further increase in agitation speed
to 400 rpm the recovery decreases at a specified M /E
ratio for an optimum carrier concentration of 0.5% (v/v).
When the M /E ratio was varied from 0.33 to 1.00, the Effect of feed concentration
percentage of copper recovered from external phase was
increased. Similar trend have been obtained for various The effects of feed concentration on the recovery of
carrier concentrations at different impeller speeds. This solute from external phase for varying agitation speed
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 397

70 90
copper con. in feed = 200 ppm M/E ratio = 0.75
copper con. in feed = 100 ppm

Percentage recovery of copper from effluent

M/E ratio = 1.00
Percentage recovery of copper from feed

copper con. in feed = 300 ppm 85

65 M/E ratio = 0.5
M/E ratio = 0.33
80
60
75

55 70

65
50
60
45
55

40 50
0 100 200 300 400 500 0 100 200 300 400 500
Agitator speed (rpm) Agitator speed ( rpm)

Figure 23. Effect of feed concentration on percent- Figure 25. Effect of M/E ratio and agitation speed on
age recovery of copper from synthetic feed (carrier percentage recovery of copper from electroplating effluent
concentration = 0.5%, M/E ratio = 0.5, pH of the external (carrier concentration in membrane = 0.5% v/v, copper
phase = 4.5, pH of the internal phase = 2.5). concentration in feed = 100 ppm, pH of the external
phase = 4.5, pH of the internal phase = 2.0).

70
copper con. in feed = 200 ppm
Percentage recovery of copper from feed

copper con. in feed = 100 ppm 85

copper con. in feed = 300 ppm M/E ratio = 0.75
Percentage recovery of copper from effluent

65 M/E ratio = 1.00

80 M/E ratio = 0.5
M/E ratio = 0.33
60
75

55
70

50 65

45 60

40 55
0 100 200 300 400 500
Agitator speed (rpm) 50
0 50 100 150 200 250 300 350 400 450
Figure 24. Effect of feed concentration on percentage Agitation speed (rpm)
recovery of copper from synthetic feed (carrier concentration
in membrane = 0.5%, M/E ratio = 0.33, pH of the external Figure 26. Effect of M/E ratio and agitation speed on
phase = 4.5, pH of the internal phase = 2.5). percentage recovery of copper from electroplating effluent
(carrier concentration in membrane = 0.5% v/v, copper
concentration in feed = 200 ppm, pH of the external
phase = 4.5, pH of the internal phase = 2.0).
at optimum M /E ratio were studied and are shown in
Fig. 28. It was found that the percentage recovery of
copper increased to a maximum and then decreased
beyond 300 rpm for a given M /E ratio at a carrier Comparison of copper synthetic solution
concentration of 0.5% v/v. The results also indicate and electroplating effluent at the same feed
the variation of recovery with feed concentrations. The concentration
maximum solute recovery obtained is 73.56% for a Figure 29 indicates the comparison of performance
feed concentration of 100 ppm, at an agitator speed between synthetic and industrial effluent. The recovery
of 300 rpm with M /E ratio of 1.00 and 0.5% carrier from effluent was around 8–17% less than that of the
concentration. synthetic solution under optimum conditions. This can
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
398 S. VENKATESAN AND K. M. MEERA SHERIFFA BEGUM Asia-Pacific Journal of Chemical Engineering

85 90
M/E ratio = 0.75 Industrial effluent
percentage recovery of copper from effluent

Percentage recovery of copper from feed

80 M/E ratio = 1.00 Synthetic feed
M/E ratio = 0.5 85
75 M/E ratio = 0.33

70 80

65
75
60

55 70

50
65
45

40 60
0 100 200 300 400 500 0 100 200 300 400 500
Agitator speed (rpm) Agitator speed (rpm)

Figure 27. Effect of M/E ratio and agitation speed on Figure 29. Comparison of synthetic and electroplating
percentage recovery of copper from electroplating effluent effluent at optimum conditions (copper in feed = 200 ppm,
(carrier concentration in membrane = 0.5% v/v, copper carrier concentration in membrane phase = 0.5% v/v,
concentration in feed = 300 ppm, pH of the external M/E ratio = 1.00).
phase = 4.5, pH of the internal phase = 2.0).

the emulsion stability. The following results were

90 obtained.
Copper con. in effluent feed = 100 ppm
• Optimal parameters giving stable emulsion are emul-
percentage recovery of copper from effluent

Copper con. in effluent feed = 200 ppm

85 Copper con. in effluent feed = 300 ppm sification speed: 10 500 rpm; emulsification time:
80
8 min; surfactant concentration: 2.5% v/v; carrier
concentration: 0–1% v/v; volume ratio of membrane
75 phase to internal phase: 1.00; and internal phase
(H2 SO4 ) concentration: 1 N.
70 • Optimal parameters for maximum recovery of copper
and zinc from aqueous solutions are agitation time:
65 16 min; pH of the external phase: 4.5; pH of the
internal phase: 2.0, agitation speed: 300 rpm; internal
60 phase (H2 SO4 ) concentration: 1 N; carrier concentra-
tion: 0.5% (v/v); volume ratio of emulsion-to-external
55 phase: 1.00; feed concentration: 100 ppm.
• Under optimum conditions, recovery of copper and
50
0 100 200 300 400 500 zinc from synthetic solution was 84.36 and 86.2%,
Agitator speed (rpm) respectively. The comparison of synthetic and elec-
troplating effluent of copper indicated that the recov-
Figure 28. Effect of feed concentration on percentage ery was 8–17% less for the plating effluent when
recovery of copper from electroplating effluent (M/E ratio = compared to the synthetic effluent.
1.00, carrier concentration in membrane phase = 0.5% v/v).

be attributed to the presence of organic materials and NOMENCLATURE

other components than copper in the effluent.
Abbreviations

M /E ratio Emulsion-to-external phase ratio

CONCLUSION A/O ratio Aqueous-to-organic phase ratio
CFD Computational fluid dynamics
The removal of zinc and copper from dilute aqueous rpm Rotations per minute
solutions by using a W/O/W emulsion was investigated. ELM Emulsion liquid membrane
System parameters were studied with a view to optimize D2EHPA Di-(2 ethyl hexyl) phosphate
 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj
Asia-Pacific Journal of Chemical Engineering EMULSION LIQUID MEMBRANE TECHNIQUE TO REMOVE CU AND ZN 399

COD Chemical oxygen demand ‘90) (Eds.: T. Sekine, S. Kusakabe), Elsevier Science Ltd.:
Amsterdam, Part A, 1990; p. pp.37–48.
BOD Biological oxygen demand [12] M.T.A. Reis, J.M.R. Carvalho. J. Membr. Sci., 1993; 84,
ppm Parts per million 201–211.
Vs Volume of internal phase leaked into the [13] S. Ilias, K.A. Schimmel, P.M. Yezek. Sep. Sci. Technol., 1999;
34(6–7), 1007–1019.
external phase [14] S.M.K. Mohammad. Sep. Purif. Technol., 2000; 19, 3–9.
Vi Volume of internal phase [15] T. Kumaresan, K.M. Meera Sherifa Begum, P. Siva
shanmugam, N. Anatharaman, S. Sundaram. Chem. Eng. J.,
2003; 95, 199–204.
[16] J. Luan, A. Plaisier. J. Membr. Sci., 2004; 229, 235–239.
Symbols [17] J. Yuanli, W. Fuan, K.D. Hyun, L. Mee Sook. J. Membr. Sci.,
2001; 191, 215–223.
[18] L. Sang Cheol. Chem. Eng. J., 2000; 79, 61–67.
(HR)2 D2EHPA dimer [19] C.I. Sainz-Dıaz, H. Klocker, R. Marr, H.J. Bart. Hydrometal-
ZnR2 (HR) Zinc–carrier complex lurgy, 1996; 42, 1–11.
[20] K. Ganesh prasad, S. Venkatesan, K.M. Meera Sheriffa
CuR2 (HR) Copper–carrier complex Begum, N. Anantharaman. Chem. Eng. Technol., 2007; 30(9),
C/Co Dimensionless concentration of metal Ions 1212–1220.
[21] W.C. Babcock, R.W. Baker, E.D. Lachapelle, K.L. Smith.
J. Membr. Sci., 1980; 7, 89–100.
[22] S.B. Kunungo, R. Muhapatra. J. Membr. Sci., 1995; 105,
REFERENCES 227–235.
[23] M. Kobya, N. Topcu, N. Demircioğlu. J. Membr. Sci., 1997;
[1] IPCS International Programme on Chemical Safety, Environ- 130, 7–14.
mental Health Criteria 61, World Health Organization, Geneva, [24] Y. Wan, X. Zhang. J. Membr. Sci., 2002; 196, 185–201.
1988. [25] Y.S. Mok, W.K. Lee. Sep. Sci. Technol., 1994; 29(6),
[2] D.G. Josefina, D.S.M. Eduardo Rodriguez. Ind. Eng. Chem. 743–764.
Res., 1999; 38(6), 2182–2202. [26] A.V. Mukkolath, P.T. Gaderkar, K. Tiwari. Chem. Ind., 1990;
[3] R.P. Borwankar, D.T. Wasan, N.L. Li. In Metals Speciation, 19 March, 192–193.
Separation and Recovery (Eds.: J.W. Patterson, R. Passino), [27] J. Yan, R. Pal. J. Membr. Sci., 2001; 190, 79–91.
Lewis publishers Inc.: Chelsea, MA 48118, 1987; pp. [28] Walstra. Chem. Eng. Sci., 1993; 48, 333–349.
pp.289–305. [29] I.P. Clausse, L. Komunjer. Colloids Surf., A, 1999; 152,
[4] B. Raghuraman, N. Tirmizi, J. Wiencek. Environ. Sci. Tech- 23–29.
nol., 1994; 28, 1090–1102. [30] M.F. Bobin, V. Michel, M.C. Martini. Colloids Surf., A, 1999;
[5] G.M. Ritcey, A.W. Ashbrook. Part I, Solvent Extraction: 152, 53–58.
Principles and Applications to Process Metallurgy, Elsevier [31] Z. Ren, W. Zhang, H. Meng, Y.M. Liu, Y. Dai. J. Chem. Eng.
Scientific Co., Amsterdam, 1984; pp.1–40. Data, 2007; 52(2), 438–441.
[6] L.L. Taviarides, J.H. Bae, C.K. Lee. Sep. Sci. Technol., 1987; [32] D.D. Pereira, S.D. Ferreira Rocha, M. Borges Mansu. Sep.
22(2&3), 581–617. Purif. Technol., 2007; 53, 89–96.
[7] A.K. Chakravarti, S.B. Chowdhury, D.C. Mukherjee. Colloids [33] M.T.A. Reis, J.M.R. Carvalho. Extraction equilibrium of
Surf., A, Physicochem. Eng. Asp., 2000; 166(1–3), 7–25. zinc from zinc sulphate solutions with Bis(2-ethylhexyl)
[8] N.N. Li, R.P. Cahn, D. Naden, R.W.M. Lai. Hydro thiophosphoric acid, Ind. Eng. Chem. Res.,, 2003; 42(17),
metallurgy, 1983; 9, 277–305. 4077–4083.
[9] C.W.A. Strzelbichki, A. Mackiewiez. Sep. Sci. Technol., 1984; [34] T. Ohtake, T. Hano, K. Takagi, F. Nakashio. Analysis of
19(4 &5), 321–336. water entrainment into dispersed w/o emulsion drops, J. Chem.
[10] M. Raffaele, D. Enrico, P. Giuseppe. Sep. Sci. Technol., 1989; Eng. Jpn.,, 1988; 21, 272–276.
24(12, 13), 1015–1032.
[11] J. Draxler, R. Marr. In Solvent Extraction 1990: Proceedings
of the International Solvent Extraction Conference (ISEC

 2008 Curtin University of Technology and John Wiley & Sons, Ltd. Asia-Pac. J. Chem. Eng. 2008; 3: 387–399
DOI: 10.1002/apj