Hydrometallurgy 84 (2006) 43 53

www.elsevier.com/locate/hydromet

Process intensification of copper extraction using emulsion liquid

membranes: Experimental search for optimal conditions
Bina Sengupta , Ranjan Sengupta, N. Subrahmanyam
Chemical Engineering Department, The Maharaja Sayajirao University of Baroda, Vadodara 390 001, India
Received 13 January 2006; received in revised form 6 April 2006; accepted 18 April 2006
Available online 22 June 2006

Abstract
Emulsion liquid membranes (ELMs) can contribute to process intensification of copper extraction, by significantly reducing the
solvent and carrier requirements in comparison with conventional solvent extraction. This investigation reports the extraction of
copper into emulsion liquid membranes using LIX 84 as carrier. The influence of four emulsion composition variables, namely the
internal phase volume fraction (), surfactant concentration (Wsurf), internal phase stripping acid concentration (Cio) and the carrier
concentration (Cc) as well as three process parameters pH, initial solute concentration (Ceo) and treat ratio (TR) on the rates of
extraction of copper, was studied. The emulsions used were characterized on the basis of internal drop size distribution and
viscosity to set a benchmark for the commercial application of this technology.
It was found that extraction was favorable above pH 2, extraction rates pass through maxima with increase in carrier
concentration and treat ratio. Increase in stripping capacities either by increase of or increase in Cio enhanced the extraction rates.
Effect of variables on emulsion swelling were investigated; data suggest that entrainment swelling of emulsion was predominant.
Swelling was observed to be serious only after 30 min of contact between the emulsion and the feed phases. Optimal conditions for
the successful implementation of ELM extraction of copper on commercial scale are suggested.
2006 Elsevier B.V. All rights reserved.
Keywords: Copper extraction; Emulsion liquid membranes; LIX 84; Rates; Emulsion composition; Emulsion swelling

1. Introduction
The global demand for refined copper is approximately 13 million tons per annum. International Copper
Study Group estimates that 13% of the refined copper
production from ores is by Solvent Extraction ElectroWinning (SX-EW) Technology. This technology
Corresponding author. Fax: +91 0265 2423898.
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 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2006.04.002

accounts for an even larger market share of refined

copper production from scrap and tailings.
Copper solvent extraction is well known and has
been in commercial practice since 1968. General Mills
Chemicals pioneered the solvent extraction technique
for copper recovery in 1960s, with the identification of
oxime copper solvent extraction reagents. This led to the
introduction of the extractant LIX 63 and, subsequently, the family of LIX reagents (now produced by
Cognis), SME reagents (Shell) and Acorga (ICI).
Kordosky (2000) has vividly described the evolution
and applications of copper solvent extraction reagents.

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B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

The versatility of solvent extraction of copper stems

from the ability to manipulate operating parameters to
handle a wide range of leach solution concentrations.
Readett et al. (2003) have reported various processing
schemes for copper solvent extraction plant that was
managed to counter varying leach solution concentrations. When copper tenor in leach solution was high
(4.5 g/L), extraction with a solvent containing LIX
984N (14% v/v) using a battery of two extraction
stages and one stripping stage resulted in 85% copper
recovery. Decline in the copper tenor (1.752.84 g/L)
necessitated one additional extraction stage to achieve
80% copper recovery. Furthermore, when copper tenor
was quite low (0.290.77 g/L), only 40% recovery
was obtained with a solvent containing LIX 984 N
(2.5% v/v) using a battery of two parallel extraction
stages and one stripping stage. For all these extractions, the solvent to feed phase ratio was one. This
data indicates that the process not only demands a
large inventory of solvent it also requires many
extraction stages. The overall success of the solvent
extraction technology would largely depend on the
ability to keep the operating costs on the lower side
and ensuring safe operations. Both these issues could
be addressed by process intensification using emulsion
liquid membranes (ELMs) that would substantially
reduce the inventory of the solvent.
ELMs invented by Li (1968) have been widely
used for water treatment including the removal of
metal cations and anions from aqueous streams.
ELMs for copper extraction are prepared by forming
a water in oil (W/O) emulsion, the external oil phase
of the emulsion contains the copper extractant, while
the aqueous internal phase of the emulsion contains a
stripping acid that could strip the copper from the
extractant. Such emulsions when dispersed in the feed
phase containing copper ions break up into small
globules of about 0.5 to 3 mm in diameter. Within
each globule exists a multitude of tiny droplets (about
110 m size) containing the aqueous stripping
phase.
The copper ions present in the feed phase react with
the extractant (HRorg.) present in the oil phase of the
emulsion at the interface between the emulsion globule
and the feed. The chemical reaction that takes place at
the interface can be described by:

2HRorg Cu2
aq CuR2org 2Haq

The resulting copper complex (CuR2org) diffuses

through the oil membrane phase of the emulsion and on
contact with the internal stripping phase of the emulsion

copper gets stripped from the extractant as per the

following chemical reaction:
2
2H
inner R2 CuCuinner 2HRorg

The stripped ion is effectively encapsulated within

the emulsion globules, while the extractant stripped of
copper shuttles back to scavenge more copper ions from
the feed phase to deposit in the internal stripping phase
of the emulsion. Due to its role as a facilitating agent for
the transport of copper from the feed phase to the
internal stripping phase of the emulsion, the extractant is
also called carrier.
ELM extraction processes are extremely rapid due
to the large interfacial area produced by the dispersion
of emulsion globules in the feed phase and also
because extraction and stripping takes place simultaneously. In addition to these features, the extraction can
be made very selective with appropriate choice of
extractants. Furthermore, the encapsulation of copper
within the internal stripping phase of the emulsion
results in large volume reduction and concentration of
copper. This makes ELM process particularly suitable
when the concentration of the copper in the feed stream
is quite low, since under such conditions conventional
solvent extraction being an equilibrium limited process
becomes uneconomical.
Realizing the potential for commercialization of
copper extraction from acidic streams using ELMs
considerable attention has been focused towards
development of this technique for copper extraction.
Frankenfeld and Li (1977), Kitagawa et al. (1977)
and Lee et al. (1978) were among the earliest
investigators to report the extraction of copper using
LIX reagents. With the exception of Strzelbicki and
Charewicz (1980), who used D2EHPA as carrier,
almost all previous investigators used chelating
extractants as carriers. The earliest investigators used
LIX 63 that did not extract copper at pH less than
3.3; Volkel et al. (1980), Marr and Kopp (1982) and
Frankenfeld et al. (1981) used ELMs containing LIX
64N to extract copper from aqueous streams.
Teramoto et al. (1983) used SME 529, while Bart
et al. (1988) used P 5050 (Acorga) as carrier for
copper extraction into ELMs.
Most of these extractants are now phased out and
new types of copper extractants are available. In recent
past, Chakravarti et al. (2000) separated copper using
LIX 84 and LIX 622 as carrier in ELMs, while Wright et
al. (1995) have reported pilot plant studies of copper
extraction using ELMs containing Acorga M5640 as
carrier. Sengupta et al. (2006) have recently reported

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

copper extraction into ELMs containing LIX 984N-C as

carrier.
Merigold (1996) has shown that, for leach solutions
that are relatively low in copper and high in pH, LIX 84
would be the best choice of extractant among the LIX
reagents because of its better copper transfer capacity in
comparison with LIX 984 and LIX 973. This is true in
spite of the fact that LIX 84 has the lowest maximum
loading capacity among these three extractants. Thus,
LIX 84 appears to be very well suited to remove copper
from waste streams and dilute heap leach solutions
when the pH of solution is typically above 1.8 (Cognis
MCT Redbook, 1997). This aspect of LIX 84 makes it
all the more attractive for use as a carrier in ELMs since
the loading and stripping operations occur simultaneously in ELMs and there is hardly any control on
these phenomena. An extractant with better transfer
capacity would lead to rapid shuttling of the carrier
between the feed phase and the inner stripping phase
leading to rapid copper transport. However, in case of
highly acidic leach solutions with pH 1, the performance of LIX 84 is poor and, in such cases, it would be
necessary to use the more strongly extracting copper
extractant such as LIX 984 N-C as carrier (Sengupta et
al., 2006).
Previous investigators have usually reported the
influence of two or three variables on the extraction
behavior, from which it is difficult to infer about the
overall dynamics of the extraction process. Furthermore,
very few investigators have reported the characteristics
of emulsions used that could serve as benchmark to
arrive at appropriate emulsion formulations that is
necessary to ensure reproducibility of results. The
second aspect is particularly important in view of the
fact that emulsions are transient entities.
The scope of the present work was to study the effect
of various emulsion preparation parameters and process
variables on extraction of copper into ELMs using LIX
84 as carrier. The ELMs used were appropriately
characterized to set a benchmark for commercial
applications. Experiments were carried out to search
the optimal combination of emulsion and process
parameters that yield the best results and factors
affecting emulsion swelling were also investigated.
2. Materials and reagents
The copper extractant LIX 84 (Cognis Inc.) a mixture
of predominantly 2-hydroxy-5-nonyl-acetophenone
oxime with a small amount of 5-dodecyl salicylaldoxime in a high flash point diluent was used as the carrier.
Kerosene (Indian Oil Corp. Ltd.) having boiling range

45

152C271C containing n-paraffins (27%), naphthenes (56%), aromatics (16%) and olefins (1%) having
density (15) of 821.3 kg/m3 was used as the membrane
material. Span 80 (Sorbitan mono-oleate), supplied by
S.D. Fine Chemicals, was the emulsifier. The carrier,
kerosene and the emulsifier were used directly as
received from the manufacturer. All other reagents
used were of AR grade.
3. Experimental
The W/O emulsions were formulated by blending
kerosene, containing the requisite amount of carrier
(LIX 84) and emulsifier (Span 80), with the internal
stripping phase, sulfuric acid, using a high-speed
blender at 12,000 rpm. The resulting milky white W/O
emulsion was cured for 30 min prior to dispersion in the
feed phase.
Extraction was carried out at 30 C in a four baffled
batch extractor 0.105 m in diameter equipped with a six
bladed disk turbine agitator having disk diameter
0.038 m. The copper feed solutions were prepared
synthetically by dissolving CuSO4 5H2O in deionised
water. The pH of the feed was adjusted using H2SO4 or
Na2CO3. Requisite amount of the emulsion was added
to the feed phase by mild agitation so as to maintain the
required treat ratio (ratio of volume of emulsion to feed).
Samples from the feed phase were withdrawn at definite
time intervals and analyzed for copper concentration
using AAS (Chemito AA 203) at 324.8 nm. On
completion of the extraction run, the two phases were
separated and the final volume of the emulsion was
noted to get an estimate of swelling of the emulsion due
to water transport. Extraction data are presented as plots
of the ratio of instantaneous copper concentration to
initial copper concentration (Ce/Ceo) versus time.
The nature of the W/O emulsion has an important
bearing on the overall extraction performance hence it is
necessary to characterize the emulsion used. The
emulsions were characterized by measurement of
viscosity, interfacial tension and internal drop size
distribution. Brookfield cone and plate Rheometer
model (LVDV III + CP) was used to determine the
viscosity of the emulsions at different shear rates using
cone spindle CPE 52. The interfacial tensions between
the emulsion and feed solutions were measured using a
Du-Nuoy tensiometer.
The internal drop sizes of the emulsion were
measured microscopically using Olympus microscope
model BH-2 attached with an Olympus photo micrographic system model PM-10 AD at a magnification of
1500 . The emulsion was diluted with kerosene and

46

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

more than 500 droplets were counted per slide. In order

to ensure greater accuracy, two slides were prepared for
each emulsion. Based on the total data of more than
1000 droplets, the Sauter mean diameter was calculated
for each case.
Dispersed emulsion globule sizes were determined
by photographing the dispersion using a Nikon F60
camera fitted with a 35105 mm microlens and a
Nikon SB-80 DX digital flash synchronized up to
125 frames/s. Exposures were taken using an aperture
of 11 and a shutter speed of 90 frames/s at definite
intervals of time covering the entire history from initial
dispersion to final settling of emulsion globules. The
emulsion globule sizes were measured using image
analysis techniques.
4. Results and discussion
A number of variables affect the extraction behaviour
of copper into ELMs. These variables may be broadly
classified as emulsion composition variables and
process variables. Emulsion composition variables
influence the inherent nature of the extracting emulsion
and can also change the morphology of the emulsion.
These variables include the internal phase volume
fraction (), surfactant concentration (Wsurf), internal
phase stripping acid concentration (Cio) and the carrier
concentration (Cc). The process variables on the other
hand are related to the process conditions they include
the extraction pH, initial copper concentration (Ceo) and
the treat ratio (TR). The range of these variables studied
in this work is reported in Table 1.
In order to assess the influence of different variables
on extraction, it is necessary to ensure that the emulsion
is adequately dispersed in the feed by agitation.
Preliminary investigations to establish the stirring
speed were made by dispersing an emulsion (having
= 0.5, Wsurf = 3% wt of oil phase, Cio = 1 M and
Cc = 10% v/v of oil phase) in the feed phase containing
500 mg/L copper at pH 2 maintaining a treat ratio 1:6.
It is well known that the rate of stirring affects the
emulsion globule size distribution. Higher stirring
speeds lead to formation of smaller sized emulsion
globules, increasing the interfacial area between the
emulsion globules and feed, resulting in increased
extraction rates. But at the same time, this also causes
the emulsion to swell rapidly due to an increase in the
rate of water transport into the emulsion. Since emulsion
swelling is detrimental to the extraction process and
could rupture the emulsion globules, it is all the more
important to select an optimal stirring speed wherein the
swelling is less while the extraction rates are large.

Pilot experiments revealed that up to stirring speed of

150 rpm the emulsion was not properly dispersed in the
feed phase and a thin film of emulsion covered the
surface of the continuous feed phase. Increasing the
stirring speed to 160 rpm resulted in a fine dispersion of
the emulsion; further increasing the stirring speed to
190 rpm resulted in a very fine dispersion of the
emulsion. Although the copper extraction rates were
more at 190 rpm but the extent of emulsion swelling was
also much larger, hence all other experimental runs were
carried out at 160 rpm.
4.1. Effect of emulsion composition variables
4.1.1. Effect of internal phase volume fraction ()
The internal phase volume fraction of the emulsion
has a profound influence on extraction using ELMs.
Change in not only leads to a change in all emulsion
properties, but also results in an increase in the capacity
of the emulsion to extract the solute. An increase in
shifts the internal drop size distribution towards larger
sizes as shown in Fig. 1. The increase in emulsion
viscosity () and the internal drop
by
Psize 3(represented
P
the Sauter mean diameter d32
ni di = ni di2 ) with
an increase in is shown in Table 2. In all the
experimental runs, the emulsion viscosities measured
showed shear thinning nature, the rheological behavior
could be explained by power law model that gave a fit
better than 99.5% in all cases.
Fig. 2 shows that, as is varied from 0.4 to 0.6, while
maintaining all other parameters constant at feed phase
pH 2, there is an increase in the rates of extraction. This

Table 1
Range of parametric variations studied
Variants Cio
(M)

Wsurf

(%, wt)

Wsurf
Cio
Cc

1
3, 4.7
1,
3
1.5, 2
1.5
3

pH

1.5

Ceo

TR

1.5

Cc
(%, v/v)

TR

Ceo
pH
(mg/L)

1:6

500

1:6
1:6

500
500

2
2

500

0.5

5, 7.5, 10, 1:6

15, 20
10
1:6

500

0.5

10

1, 2,
5
2

0.5

10

0.4, 0.5, 10
0.6
0.5
10
0.5
10
0.5

Stirring speed (N) = 160 rpm

1:6

500,
1033,
1900
1:4, 500
1:6,
1:10

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

50

30

= 0.4
= 0.5
= 0.6

0.8
Ce /C eo

= 0.4
= 0.5
= 0.6

40
% Frequency

47

0.6
0.4
0.2

20

0
10

0.652 1.304 2.608 3.192 5.216

Droplet size, m

6.52

7.824

Fig. 1. Variation of internal drop size distribution with (Wsurf =

3% wt, Cio = 1.5 M, Cc = 10% v/v).

increase is not significant when changes from 0.4 to

0.5, but is substantial when increases from 0.5 to 0.6.
The increase in extraction rates with an increase in is
attributed to the fact that, when is large, the emulsion
globules are more densely packed with the internal
stripping phase droplets. This results in a decrease of the
diffusion path length for the copperoxime complex
within the emulsion globule prior to getting stripped.
Hence, an increase in is analogous to formation of
thinner membranes.
The initial higher rate of extraction (up to 15 min)
observed for the case of emulsion having (0.4) as
compared to (0.5) is attributed to the very large
number of tiny inner phase droplets existing in
emulsions having (0.4) as seen in Fig. 1. The
convergence of all three curves in Fig. 2 at the end of the
run time (60 min) indicates that the same overall extent
of extraction took place in all three cases. This is
understandable because the stripping phase capacities in
all cases were much greater than the stoichiometric
requirement.
Extraction rates into ELMs could be enhanced by
either increasing that leads to reduction of the
diffusion path length within the globules or increasing
stirring speed (N) that causes an increase in the
interfacial area due to formation of smaller globules. A
trade off between these variables is seen in Fig. 3. The
Table 2
Effect of internal phase volume fraction () on viscosity and internal
drop size of emulsion

Viscosity at 38.6 s 1 (cp)

Internal drop size d32 (m)

0.4
0.5
0.6

65.74
65.74
116.6

3.18
3.38
4.58

10

20
30
40
Time in minutes

50

60

Fig. 2. Effect of internal phase volume fraction () on rate of copper

extraction (Wsurf = 3% wt, Cio = 1 M, Cc = 10% v/v, pH = 2, Ceo =
500 mg/L, TR = 1:6).

extraction pattern for two cases, one for ELMs with

(0.6) dispersed at 160 rpm and the other for ELMs with
(0.5) dispersed at 190 rpm keeping all other
parameters constant, turn out to be identical. This
shows that it is possible to tailor ELMs to achieve a
desired performance level using different variables.
4.1.2. Effect of surfactant concentration (Wsurf )
Influence of surfactant concentration in the oil phase
of the emulsion on the extraction rates was investigated
at two concentration levels with 3% (wt) and 4.7% (wt)
Span80. Emulsion with 2% (wt) Span 80 was not stable
for the total duration of run time (60 min).
Increasing the surfactant concentration from 3% to
4.7% resulted in a decrease in the amount of copper
extracted as shown in Fig. 4. Mikucki and Osseo-Asare
(1986) also observed similar behavior for copper
extraction using ELMs containing LIX 65 N-LIX 63
mixtures with variation in surfactant concentration. The
decrease in rates could be attributed to a number of
possible factors caused by high interfacial occupancy of
the surfactant that includes decrease in rate of copper
complexation at the membrane phasefeed phase
interface, increase in interfacial viscosity and decrease
1
N = 190 rpm, = 0.5
N = 160 rpm, = 0.6

0.8
Ce/C eo

0.6
0.4
0.2
0

10

20
30
40
Time in minutes

50

60

Fig. 3. Trade off between stirring speed (N) and (Wsurf = 3% wt,
Cio = 1 M, Cc = 10% v/v, pH = 2, Ceo = 500 mg/L, TR = 1:6).

48

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

1
Wsurf = 3 %
Wsurf = 4.7 %

C e /C eo

0.8
0.6
0.4
0.2
0

10

20
30
40
Time in minutes

50

60

Fig. 4. Effect of surfactant concentration (Wsurf) on rate of copper

extraction ( = 0.5, Cio = 1 M, Cc = 10% v/v, pH = 2, Ceo = 500 mg/L,
TR = 1:6).

in movement of inner droplets within the emulsion

globule.
4.1.3. Effect of internal phase stripping acid concentration (Cio )
The capacity of the emulsion to extract solute is
limited by the internal phase stripping acid concentration. Fig. 5 shows that there is a substantial increase in
extraction rates with an increase in internal phase acid
concentration from 1 M to 2 M. These extraction curves
were obtained for otherwise identical operating conditions; all the extraction curves converge at 60 min
duration indicating that the total extent of extraction was
same for all three cases.
The difference in the observed rates of extraction is
attributed to a difference in the rates of stripping using
different acid concentration in the inner stripping phase
of the W/O emulsion. Whewell and Hanson (1981)
reported there exists a first order dependence on the acid
concentration and on the organic phase copper concentration for stripping of copper from copperhydroxime
complexes. Volkel et al. (1980) in their investigation of
copper removal using LIX 64 N however did not

observe any effect of the stripping phase concentration

in the initial period of the run. In recent years, Jena et al.
(2002) have provided data for single stage stripping
efficiencies of copper from loaded organic phase
containing LIX 84 as extractant. Their data indicates
that the stripping efficiency increases with increasing
acid concentration, ranging from 83.3% for 1 M to
95.3% for 2 M.
Another reason for decrease in extraction rates at
lower stripping acid concentration stems from the fact
that when the stripping acid concentration in the
emulsion is low, the diffusing oxime copper complex
requires to penetrate deeper within the emulsion globule
to get stripped, since the inner stripping phase droplets
close to the surface of the globule get quickly exhausted.
Such enhancement of the diffusion path length causes a
decline in the extraction rates.
4.1.4. Effect of carrier concentration (Cc )
Carrier concentration plays a vital role in the overall
extraction behaviour of an ELM system. Fig. 6 shows
the effect of carrier concentration on extraction
behaviour. Increasing the carrier concentration in the
oil phase of the emulsion from 5% (v/v) to 10% (v/v)
leads to a progressive increase in removal of copper
from feed, but a further increase in carrier concentration
to 15% v/v and 20% v/v results in a decrease in the rates
of extraction as well as in overall extent of extraction.
This extraction behavior is attributed to the surfaceactive nature of oximes and the rheological behavior of
the emulsion. Oximes have a tendency to aggregate at
high concentrations. Consequently, the extraction pattern is influenced by this tendency. Whewell and
Hanson (1981) observed that the oxime aggregates
have less surface activity than monomers and tend to
stay away from the surface. Such behaviour results in
non-availability of the oxime for chelation at the
membrane feed interface when oxime concentration is
high. It also causes an increase in interfacial tension ()

1
Cio = 1 M
Cio = 1.5 M
Cio = 2 M

0.6
0.4
0.2

Cc = 5 %
Cc = 7.5 %
Cc = 10 %
Cc = 15 %
Cc = 20 %

0.8
Ce /Ceo

Ce/C eo

0.8

0.6
0.4
0.2

10

20
30
40
Time in minutes

50

60

Fig. 5. Effect of internal phase stripping acid concentration (Cio) on

rate of copper extraction ( = 0.5, Wsurf = 3% wt, Cc = 10% v/v, pH = 2,
Ceo = 500 mg/L, TR = 1:6).

10

20
30
40
Time in minutes

50

60

Fig. 6. Effect of carrier concentration (Cc) on rate of copper extraction

( = 0.5, Wsurf = 3% wt, Cio = 1.5 M, pH = 2, Ceo = 500 mg/L, TR = 1:6).

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

12

49

4.2. Effect of process variables

, mN/m

10
8
6
4
2
0

10
% LIX 84

15

20

Fig. 7. Variation of interfacial tension () between emulsion and feed

phase with carrier concentration (Cc) ( = 0.5, Wsurf = 3% wt,
Cio = 1.5 M, Cc = 10% v/v, pH = 2, Ceo = 500 mg/L).

between the emulsion and feed phase as seen in Fig. 7.

Increased interfacial tension leads to an increase in
emulsion globule size causing a decline in the surface
area that results in lowering of extraction rates.
Increase in emulsion viscosity affects the dispersion
behavior of the emulsion. It results in the formation of
large sized globules that causes a decline in the
interfacial areas. Teramoto et al. (1983) have reported
an increase in viscosity of emulsion with an increase in
the extractant SME 529 concentration leading to larger
globule diameters. Fig. 8 shows the influence of LIX 84
concentration on the viscosity of the emulsion. It is seen
that the viscosity of the emulsion takes a dip at 10% (v/
v) LIX 84 concentration, which corresponds with the
maximum copper extraction rates as seen from Fig. 6.
Lower emulsion viscosity favors finer emulsion dispersion in the feed phase thereby increasing the external
mass transfer area under otherwise identical operating
conditions. It appears that the low emulsion viscosity
with 10% (v/v) LIX 84 concentration compensates the
increase in interfacial tension to give dispersion with
large interfacial areas resulting in greater rates of
extraction.

4.2.1. Effect of pH
The pH of the feed phase has profound influence on
the extraction behaviour. It is well known that ketoximes, which is the principal constituent of LIX 84, are
moderately strong copper extractants. Reported pH
isotherms of LIX 84 (Cognis MCT Redbook 1997)
suggest that copper is strongly extracted at pH 2. The
presence of small amount of salicylaldoxime in LIX 84
that are strong copper extractants even at more acidic
conditions than pH 2 does not significantly influence the
extraction performance at lower pH values as seen in
Fig. 9. At pH 1, the maximum extent of copper recovery
was just 28%, while at pH 2 and pH 5 quantitative
copper recovery were obtained, but extraction rates were
significantly larger at pH 5 in comparison with pH 2.
4.2.2. Effect of initial feed concentration (Ceo )
The effect of feed phase copper concentration is
complementary to the internal phase stripping acid
concentration. When Ceo is low, most of the solute
diffusing within the emulsion globule is stripped by the
internal stripping phase droplets, which are situated in
the peripheral regions of the emulsion globule. When
Ceo increases, the peripheral droplets get rapidly
exhausted, necessitating the solute to permeate deeper
within the globule prior to getting stripped. Therefore,
an increase in Ceo also corresponds to an increase in
diffusional path lengths.
ELMs are usually designed to operate with feed
concentrations that are generally less than 1000 mg/L.
The efficacy of ELMs to handle widely varying feed
concentrations using emulsions having the same
extraction capacities was investigated by changing the
initial feed concentration in the range of 497 mg/L to
1900 mg/L. Stripping acid concentration of 2 M was
used to formulate these emulsions and higher Cio (2 M)

120

1
0.8

80
60

38.4 (1/s)
57.6 (1/s)
76.8 (1/s)
96.0 (1/s)
115.2 (1/s)

40
20
0

10
15
% LIX 84

20

25

Fig. 8. Effect of carrier concentration (Cc) on viscosity of emulsion ()

at different shear rates ( = 0.5, Wsurf = 3% wt, Cio = 1.5 M).

Ce /Ceo

, mPa.s

100

0.6

pH = 1
pH = 2
pH = 5

0.4
0.2
0

10

20
30
40
Time in minutes

50

60

Fig. 9. Effect of feed pH on rate of copper extraction ( = 0.5,

Wsurf = 3% wt, Cio = 1.5 M, Cc = 10% v/v, Ceo = 500 mg/L, TR = 1:6).

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

was chosen to provide ELMs with larger capacity for

extraction in order to handle high feed concentrations.
Fig. 10 presents the data of these extraction runs,
although it appears from the figure that the extraction
rate for the case of Ceo (1900 mg/L) is much lower in
comparison with Ceo (497 mg/L), but such interpretation
is deceptive in view of varying feed concentrations.
When Ceo was 497 mg/L, about 484 mg/L copper was
extracted from the feed in a 30 min run duration. This
same amount of copper was extracted in about 21 min
when Ceo was 1033 mg/L and in only 15 min when Ceo
was 1900 mg/L. Thus, by increasing the initial feed
concentration by almost four times, we observe that the
rates of extraction double while keeping all other
conditions identical. The rate of extraction and the
dC
0:5
initial copper concentration are related as e ~Ceo
.
dt

4.2.3. Effect of treat ratio (TR)

Treat ratio (TR) is the ratio of the emulsion phase to
the feed phase; it is a measure of the emulsion holdup in
the system. Increase in treat ratio results in an increase of
the emulsion phase holdup and simultaneously an
increase in the extraction capacity of the emulsion. It
also results in an increase in the amount of carrier and
overall surface area for mass transfer in the system. An
increase in treat ratio is expected to increase both the
rate and extent of extraction.
Fig. 11 shows the effect of treat ratio on extraction
behaviour for three cases. When the emulsion phase
holdup was low, corresponding to TR (1:10), the rate of
extraction was the least. Increasing emulsion holdup to
TR (1:6) substantially increased the rate as well as the
total extent of extraction but further increase in emulsion
holdup to TR (1:4) showed a decline in the rates as well
as extent of extraction. Many reasons could be attributed
to this behavior; increase in emulsion holdup results in
formation of larger globules and also shifts the globule
size distribution to the higher end of the spectrum.
1
Ceo = ~500 mg/L
Ceo = 1033 mg/L
Ceo = 1900 mg/L

Ce /C eo

0.8
0.6
0.4
0.2
0

10

20
30
40
Time in minutes

50

60

Fig. 10. Effect of initial copper concentration (Ceo) on rate of copper

extraction ( = 0.5, Wsurf = 3% wt, Cio = 2 M, Cc = 10% v/v, pH = 2,
TR = 1:6).

T R = 1:4
T R = 1:6

0.8
Ce /C eo

50

T R = 1:10

0.6
0.4
0.2
0

10

20
30
40
Time in minutes

50

60

Fig. 11. Effect of treat ratio (TR) on rate of copper extraction ( = 0.5,
Wsurf = 3% wt, Cio = 1.5 M, Cc = 10% v/v, pH = 2, Ceo = 500 mg/L).

Larger globule sizes lead to a decrease in external mass

transfer areas that is in many cases a rate-limiting step.
Furthermore, larger sized globules also increase the
effective diffusion path lengths within the globule that
results in a decline in extraction rates. An increase in
emulsion hold-up enhances globuleglobule interactions that lead to phenomena of globule breakage,
globule coalescence, redispersion, etc., which result in
release of the encapsulated copper back to the feed
phase.
4.3. Features of emulsion swelling and optimal
operating conditions
Issues concerning stability of emulsions have always
been a matter of concern and it has hindered the
prospects of commercialization of ELMs for long.
Retaining the integrity of the emulsion globule during
operation is the key to the success of ELM technology.
Rupture of emulsion globules leads to dumping of the
entrapped solute in the feed phase and changes the
operating conditions by changing the pH of the feed
phase. The main cause for emulsion rupture is excessive
emulsion swelling.
Swelling is detrimental for ELM extractions not only
because it dilutes the internal stripping phase and the
solute that has concentrated in the internal droplets
within the globules, but also because it changes the
rheological behavior of the emulsion. Increase of
internal droplet size of the W/O emulsion caused by
swelling modifies the emulsion morphology and
triggers a chain of sequence (enhanced mobility,
coalescence, Ostwald ripening, etc.) that ultimately
cause globule rupture. Increase in due to swelling
increases the emulsion viscosity that results in poor
dispersion behavior as time of contact between the
emulsion and feed phase increases, necessitating an
increase in the stirring speeds to keep the emulsion in

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

10 min
30 min
40 min
50 min
60 min

% Frequency

40
30
20
10
0

0.5

1
1.5
Globule size (mm)

Fig. 12. Variation of globule size distribution with time ( = 0.5,

Wsurf = 3% wt, Cio = 1.5 M, Cc = 10% v/v, pH = 2, Ceo = 500 mg/L,
TR = 1:6).

properly dispersed state as observed by Martin and

Davies (1977) and Volkel et al. (1980).
Swelling is driven by the osmotic pressure difference
between the feed phase and the internal droplet phase.
Two mechanisms are suggested for osmotic swelling
(Gu et al., 1992), one involves hydration of surfactant
molecule at the feedglobule interface, its transport to
internal droplet phase and dehydration over there. The
second involves transport of water by reversed micelles.
Swelling also occurs due to entrainment of feed phase
into the emulsion due to repeated coalescence and
redispersion of emulsion globules. Evidence supporting
entrainment swelling is the rapid increase of swelling
with increasing stirring speeds (Ding and Xie, 1991).
Although swelling is unavoidable, manipulating the
different variables can minimize it.
Measurement of the volume of the emulsion at the
end of the experimental run gave a measure of swelling.
The ratio of change in emulsion volume (Vem) to that
of the original emulsion volume (Vem0) gave the percent
swelling (S) as S = [(Vem / Vem0) 100]. The parametric
variations that induced significant swelling were stirring
speed (N) and treat ratio (TR). Increasing N from 160 to
190 rpm increased swelling from 40% to 58%. While
TR (1:10) recorded swelling of 30%, TR (1:6) gave 40%
and TR (1:4) gave 68% emulsion swelling at the end of
the run. For all other variations, swelling was of the
order of 40% except when was 0.6; in this particular
case, swelling was only 25%. Change in the stripping
phase concentration from 1.5 M to 2 M acid did not have
any marked effect on the swelling. In both cases, about

0.8

0.8

0.6

d 32
Ce/Ceo

0.4
0.2
0

0.6
0.4

Ce /Ceo

50

40% swelling was recorded. Hence, osmotic swelling

does not appear to be the dominant mechanism for
emulsion swelling in the experiments performed.
It is evident from the data that maximum swelling
occurred in situations involving intense dropdrop
interactions such as high stirring speed and high treat
ratio. Both these situations warrant comparatively larger
number density of emulsion globules in the feed phase.
Low swelling observed when was 0.6 is attributed to
high viscosity of the emulsion that favors formation of
large sized globules thereby decreasing the number
density of emulsion globules in the system. These
situations suggest entrainment swelling is the root cause
for emulsion swelling in the experimental runs.
It was observed that, in the first 30 min of the run,
just 5% swelling took place. In this time span, over
80% of the copper gets extracted. This behavior has an
important bearing on deciding the contact time of
emulsion with the feed phase in plant scale operations.
The influence of contact time on globule size
distribution is shown in Fig. 12 for an emulsion
(having = 0.5, Wsurf = 3% wt, Cio = 1.5 M and
Cc = 10% v/v) dispersed in feed phase containing
500 mg/L of copper at pH 2 and treat ratio 1:6. It is
observed that the globule size distribution changes
widely with time; there is considerable redistribution of
sizes up to 40 min; thereafter, the actual swelling takes
place as indicated by the flattening of the curve and its
shift towards the larger drop sizes. In Fig. 13, we
observe that the Sauter mean diameter (d32) initially
shows a small but progressive enlargement with time,
but after 40 min of contact there is sharp increase in
d32 that occurs primarily due to the emergence of large
sized globules in the distribution.
The optimal operating conditions that can be
suggested from the results of this investigation are the
following: = 0.50.6, Wsurf = 3% (wt), Cio = 1.5 M

d 32 (mm)

60

51

0.2
0

20

40
60
Time in minutes

0
80

Fig. 13. Variation of Sauter mean diameter (d32) of emulsion globule

with time ( = 0.5, Wsurf = 3% wt, Cio = 1.5 M, Cc = 10% v/v, pH = 2,
Ceo = 500 mg/L, TR = 1:6).

52

B. Sengupta et al. / Hydrometallurgy 84 (2006) 4353

2 M, Cc = 10% (v/v) LIX 84, pH 2 or greater and treat

ratio 1:6. The results are specific to Span 80 as
surfactant. In case of low feed copper concentration,
use of 1.5 M stripping acid would suffice but at higher
copper concentration 2 M stripping acid with a of 0.6
would be advantageous. In order to restrict swelling, it
will be desirable to avoid emulsion contact with the feed
phase for more than 30 to 40 min.
5. Conclusions
Process intensification using ELMs is an effective
alternative to handle situations when copper concentration in the feed is low, like low copper tenor leach
liquors or mine run waters. This investigation reveals
that the rates of extraction increased with an increase in
the feed copper concentration, the volume fraction of
internal phase and the internal phase stripping acid
concentration. It was found that, with an increase in treat
ratio of emulsion to feed, the extraction rate increases
and then declines, suggesting a maxima at a treat ratio
(1:6). LIX 84 (10% v/v) in the membrane phase was
found optimal for use in ELMs. A feed phase around pH
2 was congenial for extraction while extraction
performance was poor at pH 1.
Commercialization of ELM technique for copper
extraction has not taken place because the stability of the
ELMs has been suspect. In these experiments, the
emulsions used were very stable throughout the duration
of the experimental run. Emulsion swelling was about
40% in most cases. High stirring speed (190 rpm) and
high treat ratio (1:4) caused large swelling 58% and
68%, respectively, while high value of (0.6) led to a
reduction in swelling suggesting that swelling occurred
mostly due to entrainment of feed phase droplets in the
emulsion. Swelling was observed to be serious only
after 30 min of contact with feed phase; the change in
globule size distribution and sharp increase in the Sauter
mean diameter after 40 min contact consolidates this
observation.
Frankenfeld et al. (1981) had estimated that ELM
extraction of copper turns out to be 40% cheaper
than solvent extraction. Although it is not possible to
directly estimate the economics of operating continuous plant from batch experimental data reported in
this work but nevertheless substantial savings could
be achieved in terms of reduced solvent and
extractant use, despite incorporating steps of emulsion
preparation and emulsion breakage. The results of
this investigation should encourage and give impetus
for process intensification of copper extraction using
ELMs.

Acknowledgements
We would like to thank AICTE, R&D Scheme F. No.
8021/RID/NPROJ/R&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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