Hydrometallurgy 81 (2006) 67 – 73

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Technical note
Copper extraction into emulsion liquid membranes using
LIX 984N-C®☆
Bina Sengupta ⁎, R. Sengupta, N. Subrahmanyam
Chemical Engineering Department, Faculty of Technology and Engineering, The Maharaja Sayajirao University of Baroda,
Vadodara, 390 001, Gujarat, India
Received 13 July 2005; received in revised form 8 October 2005; accepted 20 October 2005
Available online 13 December 2005

Abstract

The extraction of copper from aqueous sulfate media into ELMs using the extractant LIX 984N-C was studied. Appropriately
characterized emulsions on the basis of viscosity and internal drop sizes were used to study the effect of different parameters on
extraction. The effects of stirring speed, surfactant concentration, pH of the external continuous phase, carrier concentration,
internal phase stripping acid concentration and initial copper concentration are reported. These results show that LIX 984N-C
efficiently extracts copper at low pH values typical of leach solutions. It was found that LIX 984N-C could extract up to 80%
copper from aqueous solutions at pH value of 1. Performance of LIX 984N-C was also compared with LIX 84 and LIX 84-I at
different pH values. Results indicate that LIX 984N-C could open up new avenues for extraction of copper into ELMs, not only
from dilute solutions, but also from sulfuric acid leach solutions.
© 2005 Elsevier B.V. All rights reserved.

Keywords: LIX 984; Copper extraction; Emulsion liquid membrane

1. Introduction effluent streams. This practice is becoming unpopular

There is general concern to minimize the discharge
of hazardous metals in liquid effluent streams. Aqueous
streams contaminated with heavy metal ions are fre-
quently encountered from various industrial processes
such as mining and smelting, metal plating, and metal
finishing also during attempts to remediate soil loaded
with heavy metals. Precipitation technique is most com-
monly used for the removal of metal species from
☆
LIX is a registered trademark of the Cognis Group.
⁎ Corresponding author. Fax: +91 265 242 3898.
E-mail addresses: bina_msu@yahoo.co.in (B. Sengupta),
ranjan_msu@yahoo.co.in (R. Sengupta),
nsmanyambaroda@yahoo.com (N. Subrahmanyam).
0304-386X/$ - see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2005.10.002
because the products obtained are not always of re-
quired quality and the process produces a sludge that
has to be disposed in a landfill. Solvent extraction is
another widely used technique, but it requires large
inventory of organic solvent and the metal extractant
and becomes inefficient when the metal ion concentra-
tion in the effluent stream is low.
Emulsion liquid membranes (ELMs) first invented by
Li (1968) offers a promising technology for the separa-
tion of heavy metal ions from aqueous effluent streams.
ELMs remove the equilibrium limitations of solvent
extraction by combining extraction and stripping in a
single operation, thereby achieving reduction of metal
concentration in the feed stream to very low levels.
Furthermore, they reduce the inventory of the organic
68 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73
solvent and metal extractant substantially. ELMs have
been used to treat aqueous streams contaminated with
heavy metals like copper, zinc, cadmium, chromium,
etc. (Frankenfeld and Li, 1977; Gu et al., 1992; Marr
and Kopp, 1982; Winston Ho and Li, 1996).
ELMs for metal extraction are made by forming a
water in oil (W/O) emulsion, stabilized by a surfactant,
the W/O emulsion contains the metal extractant (carrier)
in the oil phase and the stripping acid in the internal
aqueous receiving phase. This emulsion is then dis-
persed by mild agitation into a feed phase containing
the metal to be extracted. After extraction, the loaded
emulsion is separated from the feed stream, demulsifi-
cation yields an oil phase that can be recycled. Electro-
plating or crystallization could subsequently recover the
heavy metal concentrated in the receiving phase.
Removal of copper as Cu2+ ions from aqueous
streams using ELMs has been an area of interest ever
since ELMs were invented. Most investigators (Kita-
gawa et al., 1977; Mikucki and Osseo-Asare, 1986;
Martin and Davies, 1977; Volkel et al., 1980) preferred
using chelating extractants, such as LIX 63, LIX 64N,
LIX 65, SME 529®, etc., because of their immiscibility
with water. Economic evaluation by Frankenfeld et al.
(1981) showed that ELM extraction of copper using
LIX 64N turns out to be 40% cheaper than solvent
extraction.
Earlier used copper extractants LIX 63, LIX 65, etc.
are no longer commercially available. Hu and Wiencek
(1998) and Chakravarti et al. (2000) investigated copper
extraction into ELMs using the widely used extractant
LIX 84 as carrier but literature on the extraction of Cu2+
using ELMs containing the new generation of extrac-
tants is scarce. In recent years, Cognis Inc. has intro-
duced new copper extractants such as LIX 860 and LIX
984 and their variants that show faster kinetics, easier
phase disengagement and strong extraction of copper
even at low pH values of 1 to 2. Data on extraction of
copper using these extractants are lacking. LIX 984 is
particularly attractive for ELM extraction of copper
since it combines the most desirable features of its
components. The extractive strength and fast kinetics
of salicylaldoximes are combined with proven excellent
physical performance and stability of ketoximes.
In the present work, the extraction of copper from
aqueous sulfate media into ELMs using extractant LIX
984N-C as carrier is reported. The results present an
overall idea of the optimal operating conditions for
copper extraction into ELMs. Further, the results are
compared with those obtained for copper extraction into
ELMs using the extractants LIX 84 and LIX 84-I at
various pH conditions.
2. Materials
The copper extractant LIX 984N-C, supplied by
Cognis Ireland, is an equi-volume mixture of LIX
860N-IC (5-nonyl salicylaldoxime) and LIX 84I-C (2-
hydroxy-5-nonyl-acetophenone-oxime) in a high flash
point hydrocarbon diluent. Kerosene, supplied by Indi-
an Oil Corporation Ltd., having boiling range of 152 °C
to 271 °C containing n-paraffins (27.08%), naphthenes
(55.92%), aromatics (16%) and olefins (1%) with a
density (ρ15) of 821.3 kg/m3, was used as the mem-
brane material. Emulsifier Span 80 (Sorbitan monoole-
ate) was supplied by S.D. Fine Chemicals. The
extractant, kerosene and emulsifier were used directly
as received from the manufacturer. All other chemicals
used were of A.R. grade.
3. Experimental
Experimental studies were carried out in the follow-
ing three stages.
3.1. Emulsion preparation
Water in oil emulsions were prepared by initially
blending the extractant LIX 984N-C and surfactant
Span 80 with kerosene to get the membrane phase. The
internal aqueous stripping phase (1.5 M H2SO4) was
added slowly to the oil phase with agitation of contents
at 12,000 rpm. The emulsions were prepared with equal
volumes of oil and the internal stripping phase.
3.2. Emulsion characterization
Emulsions were characterized by viscosity and inter-
nal drop size distribution. The viscosity of the emul-
sions were measured using Brookfield cone and plate
Rheometer, model LVDV III+CP, at different shear
rates. Internal drop size of emulsions were measured
microscopically using Olympus microscope model BH-
2 attached with an Olympus photo micrographic system
model PM-10AD.
3.3. Copper extraction into ELMs
Copper extraction into ELM was performed in a
batch extractor at 30 °C. The extractor was a four-
baffled vessel 0.105 m in diameter equipped with a six
bladed turbine agitator. The copper feed solutions were
synthetically prepared by dissolving CuSO4·5H2O in
deionised water. The feed was adjusted to the required
pH using H2SO4 or Na2CO3. The emulsion (100 mL)
 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73
was added to the feed phase (600 mL) by mild agitation
thereby keeping a Treat ratio of 1:6. Samples of the feed
phase were withdrawn at definite time intervals and
analyzed for copper concentration using AAS, model
Chemito AA 203, at 324.8 nm.
4. Results and discussion
The performance of the extraction depends on the
nature of emulsion and the influence of various opera-
tional parameters as detailed below.
4.1. Emulsion characterization
Appropriate characterization of ELMs is necessary
to ensure reproducibility of results. The W/O emulsions
having internal phase volume fraction ϕ (0.5), surfac-
tant concentration Wsurf (3%) based on weight of oil
phase and internal phase sulfuric acid concentration Cio
(1.5 M) showed shear thinning behavior. The viscosities
increased with an increase in the carrier concentration
(Cc). Fig. 1 shows the effect of volume percent LIX
984N-C in the membrane phase on the viscosity at
different shear rates. The rheological behavior could
be explained by power law model that gave a fit of
99.6%. The internal drop sizes of the emulsion were
measured at 1500× magnification and the Sauter mean
diameter, d32, turned out to be 3.424 μm.
4.2. Effect of parametric variations on copper extraction
When the W/O emulsion is dispersed in the feed
phase, the emulsion breaks up into numerous tiny glo-
Fig. 1. Effect of LIX 984N-C on emulsion viscosity at various shear rates.
69
bules to generate a huge surface for reaction and mass
transfer. The reaction that takes place at the interface of
the emulsion globule and the continuous feed phase can
be described by:
þ
2HRorg þ Cu2þ
aq: ⇆CuR2org þ 2Haq :
where HR represents the carrier, and aq. and org. are the
aqueous and organic phases.
The metal complex ‘CuR2’ diffuses within the or-
ganic membrane phase to the inner stripping phase of
the emulsion where the Cu2+ ion gets stripped from the
carrier as per the following chemical reaction
2Hþ
inner þ R2 Cu⇆Cuinner þ 2RHorg :
2þ
The liberated carrier is free to shuttle back to the
external interface to scavenge more Cu2+ ions, while the
stripped ion is effectively encapsulated in the internal
phase of the emulsion.
In all experimental runs, the internal phase volume
fraction of the extracting emulsion was retained at ϕ
(0.5) and the Treat ratio was maintained (1:6). Other
operating parameters, except when varied to study their
effect, were carrier LIX 984N-C concentration, Cc (10%
vol.), copper concentration in the external phase, Ceo
(∼ 500 mg/L), internal acid concentration, Cio, (1.5 M)
and initial feed pH was 2. The amount extracted at any
time was expressed as ratio of the instantaneous con-
centration to initial concentration of copper Ce/Ceo.
4.2.1. Effect of stirring speed
Stirring speed, N, directly influences extraction be-
haviour. Since globule size distribution gets affected by
70 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73
stirring rates, higher stirring rates lead to formation of
smaller sized globules, thereby increasing the interfacial
area between continuous phase and the membrane
phase, leading to an increase in the rates of mass trans-
fer. Higher stirring speeds can also lead to more swell-
ing and globule rupture. Appropriate stirring speed
needs to be selected for optimal performance of ELMs.
Preliminary studies showed that a stirring speed of
150 rpm was necessary to keep the emulsion in a dis-
persed state but even then a film of emulsion remained
on the surface of the feed phase. Increasing N to 160 rpm
resulted in elimination of the surface film while gener-
ating a dispersion having spherical shaped globules.
Further increasing N to 190 rpm resulted in smaller
size globules with larger initial rates of extraction and
considerable increase in emulsion swelling. In view of
enhanced swelling at 190 rpm, the stirring speed of 160
rpm was chosen for all further investigations.
The dispersion was photographed at definite time
intervals and the globule sizes were measured using
imaging software. The globule size distribution after
10 min of dispersion that corresponds to almost 80%
extraction is shown in Fig. 2. The Sauter mean diameter
for this distribution was 0.678 mm.
4.2.2. Effect of surfactant concentration
Surfactant concentration has an important bearing on
the stability of the emulsion. Too little surfactant ren-
ders the membrane weak, while an increase in surfactant
concentration leads to larger diffusional resistance.
Experiments were performed with surfactant concentra-
tions ranging from 1% to 4.7% by weight based on the
oil phase. It was observed that, when the surfactant
concentration was 1%, there was severe membrane rup-
ture, but increasing the surfactant concentration to 3%
Fig. 2. ELM globule size distribution at 160 rpm.
resulted in a stable membrane throughout the duration
of the experiment with negligible leakage at stirring
speed of 160 rpm. Further increasing the surfactant
concentration to 4.7% gave similar extraction rates but
there was significant swelling of emulsion. Hence, sur-
factant concentration of 3% was chosen for all further
studies.
4.2.3. Effect of pH
The pH of the continuous phase has a profound
influence on the extraction behaviour. The ketoximes,
LIX 84, are only moderately strong copper extractants
and are most useful above pH 1.6 to 1.8 (Redbook,
1997). pH isotherms of LIX 84 suggest that copper
can be strongly extracted at pH 2. Salicylaldoximes
(LIX 860), on the other hand, are very strong copper
extractants that extract substantial amounts of copper
even at pH 1. Since it is difficult to strip copper from
salicylaldoximes, they are most often used in combina-
tion with an equilibrium modifier or with a ketoxime, so
that copper may be effectively stripped. Due to the
presence of equal amount of salicylaldoxime and ketox-
ime, LIX 984N-C is expected to be a strong copper
extractant even at low pH values.
To test the efficiency of extraction using LIX 984N-
C and to compare the ELM performance with LIX 84,
extractions were performed at pH values of 1, 2 and 5.
The results obtained are presented in Fig. 3. It is seen
that at pH 2 and pH 5 the extraction was quantitative
with LIX 984N-C, while at pH 1 almost 80% of the
initial copper was extracted.
Comparing the behaviour of LIX 984N-C with LIX
84, it was observed that at pH 5 the rates of extraction
were almost identical. At pH 2, the total amount of
copper extracted was almost the same, although the
 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73 71

Fig. 3. Effect of pH on extraction of copper from sulfate media.

initial rates using LIX 984N-C were more rapid than
those obtained using LIX 84. This behaviour could be
attributed to the presence of salicylaldoximes in LIX
984N-C. Furthermore, it was observed that with LIX 84
the rates of extraction at pH 2 were considerably slower
than that observed at pH 5. At pH 1, only 28 % copper
could be extracted with LIX 84.
Extraction of copper into ELMs with LIX 84-I at pH
5 gives a behaviour that is comparable with LIX 84 and
LIX 984N-C, although the extraction rates were mar-
ginally lower. However, at pH 2, ELMs containing LIX
84-I could extract only 60% copper in 60 min of contact
time in comparison with quantitative extraction of cop-
per by ELMs containing LIX 84.
4.2.4. Effect of carrier concentration
Carrier concentration, Cc, in the membrane phase
plays a vital role in the overall extraction behaviour of
ELM systems. To study this effect, the carrier concen-
tration in the ELMs was varied in the range of 5% to
10% by volume of membrane phase at external phase
pH 2, while maintaining all other emulsion and operat-
ing conditions constant. The results obtained are shown
in Fig. 4. It can be seen that an increase in Cc from 5%

Fig. 4. Effect of LIX 984N-C concentration on extraction of copper.

72 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73

Fig. 5. Effect of stripping acid concentration.

to 7.5% leads to an increase in initial rates. Further
increasing Cc to 10% does not show any change and
the final amount extracted in all cases remains the same
at sample time of 45 min. It is seen that there is some
evidence of emulsion breakage after 45 min when the
carrier concentration is 5%. The enhanced stability of
the emulsions containing higher concentrations of car-
rier could be attributed to their higher viscosities.
4.2.5. Effect of internal phase acid concentration
Two concentrations of stripping acid 1.5 M and 2 M
were studied. It was observed that for extraction of
copper at pH 2 the initial extraction rates with a strip-
ping acid concentration of 1.5 M were marginally great-
er than that obtained with 2 M acid concentration,
although the overall extent of extraction in both cases
were the same. Martin and Davies (1977) also observed
similar behavior for copper extraction into ELMs using
the chelating extractant SME 529. It is interesting to
note that for extractions carried out at pH 1 the stripping
acid concentration did not affect the rates of extraction
as seen in Fig. 5.
4.2.6. Effect of initial feed concentration
The effect of copper concentration in the feed phase
was investigated at feed concentrations of 497 mg/L

Fig. 6. Effect of initial copper concentration.

 B. Sengupta et al. / Hydrometallurgy 81 (2006) 67–73
and 1900 mg/L using two ELM systems—one contain-
ing LIX 984N-C as carrier and the other with LIX 84 as
carrier. The extractions were performed at pH 2 with
stripping acid concentration 2 M. The results are pre-
sented in Fig. 6. It can be seen that for ELMs containing
LIX 84 there exists a wide gap between the extraction
curves obtained for the two feed concentrations, while
for ELMs containing LIX 984N-C the extraction per-
formance did not decline in spite of a fourfold increase
in the feed concentration. This difference in extraction
behaviour stems from the nature of extractant and the
concentration of oxime present in the extractant. Since
LIX 984N-C is a more concentrated oxime and also
contains more strongly copper-extracting salicylaldox-
imes, it gives consistent extraction performance in
ELMs over a wide range of initial feed concentrations.
It is expected that such performance would be observed
for even higher initial concentrations provided there is
sufficient stripping acid to strip the solute extracted.
5. Conclusions
The results of this study demonstrate the effective-
ness of LIX 984N-C as an extractant for copper extrac-
tion into ELMs. Membranes with LIX 984N-C can be
used even at pH values as low as pH 1 to achieve more
than 80% recovery of copper. ELMs containing LIX
984N-C could be used over wide range of solute con-
centrations with almost the same extent of copper re-
coveries in each case. Such expectations cannot be
fulfilled by predominantly ketoxime extractants such
as LIX 84 or LIX 84-I at low pH ranges or at high
solute concentrations. However, for dilute concentration
ranges and pH N 2, there is no significant difference
between the performance of ELMs containing LIX 84
and LIX 984N-C.
The ELM technique was originally developed for the
removal of copper and other heavy metals from waste
waters where the concentration of metals are quite low.
But due to the inherent instability of the emulsion, their
commercialization has been delayed. The results of this
investigation also show that adequately formulated
emulsions are sufficiently stable in carefully chosen
operating conditions for industrial utilization. The new
genre of strongly copper extracting reagents like LIX
984N-C opens up avenues for the use of ELMs for
extraction of copper not only from dilute solutions but
also from sulfuric acid leach solutions and at par with
the conventional solvent extraction technique.
73
Acknowledgements
We would like to thank AICTE, R&D Scheme F.
No.8021/RID/NPROJ/R and D-2/2002-03 for support
to carry out this work, Indian Oil Corporation Limited
for supply of kerosene and Cognis Inc. (Ireland) for
supply of samples of LIX reagents.
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