Hydrometallurgy 113114 (2012) 155159

Contents lists available at SciVerse ScienceDirect

Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

A synergistic solvent extraction system for separating copper from iron in high
chloride concentration solutions
Z. Zhu, W. Zhang, C.Y. Cheng
The Parker Centre, CSIRO Process Science and Engineering, CSIRO Minerals Down Under National Research Flagship, Australia

a r t i c l e

i n f o

Article history:
Received 2 November 2011
Received in revised form 22 December 2011
Accepted 22 December 2011
Available online 29 December 2011
Keywords:
Synergistic solvent extraction
LIX63
Versatic 10
Copper
Iron

a b s t r a c t
A synergistic solvent extraction (SSX) system consisting of Versatic 10 and LIX 63 has been developed to separate copper from iron in high chloride concentration solutions and to transfer the extracted copper to a sulphate solution for recovery by conventional electrowinning. The SSX system is able to selectively extract
copper over iron and other impurity metals from chloride solutions in extraction stages. The co-extracted
iron and chloride in the loaded organic solution are scrubbed in two separate scrub circuits. A spent electrolyte is used to strip the copper from the scrubbed organic solution for conventional copper electrowinning. A
process ow sheet from leaching with chloride solutions to copper conventional electrowinning is proposed.
It is proposed that in high chloride concentration solutions, copper exists as neutral molecule of CuCl2, which
forms complexes with the organic components of the SSX system via a solvating mechanism. After scrubbing
the chloride from the organic system with water at an appropriate pH, the copper is proposed to be reextracted via a cation exchange mechanism by the same organic system.
Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.

1. Introduction
Copper chloride hydrometallurgy was a hot research topic in
the 1970s and 1980s due to the higher copper leaching kinetics
and recovery and less environmental concern compared to smelting and leaching with other media such as sulphuric acid. However, the electrowinning of copper from chloride solutions was very
problematic due to the difculties in cell design and the handling
of a copper powder product. It was also found that the commercially used aromatic hydroxyoxime extractants to extract copper
from sulfate solutions, such as LIX 984N and Acorga M5640, were
not suitable to extract copper from chloride solutions due to
their low extraction capability and small separation factors of copper over iron. So far no solvent extraction systems are available on
a commercial scale to recover copper effectively from chloride solutions and to transfer it to sulfate solutions for electrowinning.
To overcome this problem, an aromatic hydroxyoxime reagent
LIX64N was used to extract copper from chloride leach solutions,
but failed due to its low loading capacity and the transfer of chloride to the electrolyte (Paynter, 1973). As a result, electrowinning
of copper from chloride solutions had to be undertaken, resulting
in copper powder product which is difcult to be marketed. A
new extractant called ACORGA DS5443 or CLX50 with high extraction capacity and high selectivity for copper in chloride solutions

Corresponding author.
E-mail address: chu.cheng@csiro.au (C.Y. Cheng).

was developed and patented (Dalton et al., 1982). However,

CLX50 also transferred chloride to the electrowinning step, resulting in the unfavourable copper powder product (Atmore et al.,
1984). This reagent was abandoned and has never been commercialised. Methods to extract copper from chloride solutions and to
transfer it to sulphate solutions for electrowinning were explored
by a number of researchers. Mixed extractants consisting of a chelating reagent, LIX54, and a basic extractant, tri-alkylamine such as
Alamine 336 were tested (Kyuchoukov and Szymanowski, 2000;
Kyuchoukov et al., 2000; Ryszard and Jan, 2001). This mixture efciently extracted copper from chloride solutions. However, in stripping with sulphuric acid, the amine was protonated to form
hydrosulphate and therefore, the organic system could not be
recycled to the extraction step without prior conditioning with
chloride solution. Although a combination of LIX54 with Acorga
CLX50 showed improvement during the copper stripping step
with sulphuric acid compared to the above mentioned mixture,
the same drawback existed due to the formation of hydrosulphate
in the organic phase. Kyuchoukov and Szymanowski (2000) and
Kyuchoukov et al. (2000) reported the use of a bi-functional reagent such as Kelex 100 and LIX26 to transfer copper from chloride to sulphate solutions for electrowinning. However, these
reagents extract iron(III) more strongly than copper and cannot
be used for the separation of copper from iron(III).
Until recently, most commercialised leaching processes for copper sulphide ores were carried out in sulphate systems. After the
recovery of copper from the leach solutions, large volumes of
waste solutions containing a large amount of sulphate salts are

0304-386X/$ see front matter. Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.12.016

156

Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159

discharged, resulting in environmental pollution. To overcome this

drawback, the development of leaching processes with hydrochloric
acid and chloride salts has made great progress for the treatment of
copper, zinc, nickel and cobalt containing ores (Harris and White,
2008; Harris et al., 2003, 2004; Krebs et al., 2007; Kyung-Ho et
al., 2006). More than 90% of copper can be leached by hydrochloric
acid and chloride salts at atmospheric pressure. Another advantage
of hydrochloric acid and chloride salts leaching is that they can be
recycled by pyrohydrolysis of iron as commonly practised in the
steel making industry. However, the efcient separation and recovery of copper, from chloride solutions has not been established.
Copper hydroxyl-chloride and cuprous hydroxyl-chloride precipitations have been proposed (Krebs et al., 2007). However, these intermediate products have to be treated in extra processes to
recover copper as pure metal. Ion exchange technology has been
proposed in process ow sheets (Harris and White, 2008). However, it suffers disadvantages including small throughput and complicated operation.
A novel SSX systems has been developed to separate and recover
cobalt and zinc from leach solutions (Cheng, 2006; Cheng and
Urbani, 2005; Cheng et al., 2010). This paper presents the further development and application of the novel SSX system for the separation,
purication and recovery of copper from chloride leach solutions.
2. Experimental
2.1. Aqueous and organic solutions
The synthetic leach solution was prepared by dissolving AR or
technical grade sulphates of copper, iron(III), aluminium and calcium
chlorides in distilled water. The metal concentrations in the synthetic
leach solution were determined by Inductively Coupled Plasma
Atomic Emission Spectrometry (ICP-AES). The composition of the resultant feed solution is shown in Table 1.
The reagent Versatic 10 acid (neodecanoic acid) and the diluent
Shellsol D70 (100% aliphatic) were provided by Shell Chemicals Australia and LIX63 by Cognis Australia (now part of BASF). The composition of the LIX63 was reported by Cognis to be 70% active
component (5,8-diethyl-7-hydroxy-6-dodecanone oxime) in a diluent. The actual concentration of the oxime in LIX63 was only 54%
(Barnard and Urbani, 2007). For consistency, 70% oxime in the
LIX63 was used as a nominal concentration in the current paper. All
reagents were used as received.
2.2. Batch test procedures

2.2.2. Scrubbing pH isotherms

The loaded organic solution and a selected scrub solution were
mixed at an A/O ratio of 1:4 for iron scrubbing and 1:2 for chloride
scrubbing and 40 C. 6 M HCl or 10% NaOH solution was used to adjust the pH during testing. Solution mixture samples were taken at
0.5 pH intervals for assay.
2.2.3. Stripping kinetics
The loaded organic solution was stripped with the aqueous solution containing 53 g/L Cu and 180 g/L H2SO4 at an O/A ratio of 4:1
and 40 C. Timing started immediately when the strip solution was
added to the loaded organic solution. Solution mixture samples
were taken at 0.5, 1, 2, 3, 5 and 10 min for assay.
3. Results and discussions
3.1. Metal extraction acidity isotherms
In Fig. 1, it can be seen that the extraction of copper was independent of the solution acidity between 0.1 and 0.5 M HCl with a
constant value. However, the extraction of iron was slightly acidity
dependent, showing an increasing trend when the solution acidity
increased. This suggests that the iron can be scrubbed by a low
acidity solution, e.g. 0.2 M HCl solution. Due to the high chloride
concentration in the scrub solution, copper remained in the loaded
organic solution.
With 0.1 M HCl, 350 g/L CaCl2 at an A/O ratio of 1:2 and 40 C, over
95% Cu but only 14% Fe were extracted by the SSX system consisting
of 0.3 M LIX 63 and 0.33 M Versatic 10 in Shellsol D70 after a single
contact (Fig. 1). The extraction of aluminium was negligible. This
clearly shows that the SSX system can be used to separate copper
from other metals, including Fe(III), in chloride solutions with a few
extraction stages.
3.2. Iron scrubbing
The co-extracted iron was scrubbed with a scrub solution containing 350 g/L CaCl2 and 0.2 M HCl. A total of 4 batch scrubbing
tests were successively conducted at an A/O ratio of 1:4 and
40 C. This means that the same organic solution was mixed with
fresh scrub solution 4 times. As shown in Table 2 and Fig. 2, after
the rst two scrubbing stages, over 99.8% Fe(III) was scrubbed
with b 1 mg/L Fe(III) left in the organic solution. About 11% Cu was
also scrubbed in each of the rst two scrubbing stages. In a
counter-current operation, it would be expected that all the

All tests were carried out in 0.5 L or 1.0 L stainless steel rectangular boxes immersed in a temperature controlled water bath. The solution temperature was maintained at 40 1 C during testing. Eurostar
digital overhead stirrers and 30 mm (for 0.5 L box) or 40 mm (for
1.0 L box) diameter impellers were used for mixing.

90.0
80.0

Extraction ( )

2.2.1. Extraction acidity isotherms

To determine metal extraction acidity isotherms, the acidity of the
aqueous solution was adjusted by adding concentrated HCl and measured by titration with standard NaOH solution. The organic solution
was mixed with the synthetic solution at a particular A/O ratio and
40 C. The solution mixture (20 mL) was sampled at different acidities
for assay by ICP-AES. The system was allowed to equilibrate at each
acidity point before sampling.

100.0

Cu

70.0

Fe

60.0
Al

50.0
40.0
30.0
20.0
10.0
0.0
0.0

0.1

0.2

0.3

0.4

0.5

0.6

HCl concentration (M)

Table 1
Chemical composition of the synthetic leach solution.
Element

Cu

Fe(III)

Al

Ca

Cl

Concentration (g/L)

14.2

4.74

2.07

126

224

Fig. 1. Effect of HCl concentration on metal extraction with the SSX system consisting of
0.3 M LIX 63 and 0.33 M Versatic 10 in Shellsol D70 and the synthetic aqueous solution
containing 14 g/L Cu, 4.7 g/L Fe(III), 2 g/L Al and 350 g/L CaCl2 at an A/O ratio of 1:2 and
40 C.

Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159

Table 2
Scrubbing iron from the loaded organic solution with a scrub solution containing
350 g/L CaCl2 and 0.2 M HCl at an A/O ratio of 1:4 and 40 C.
Scrub
stage

Cu concentration (g/L)

Fe concentration (g/L)

Scrubbing (%)

In aq. soln.

In org. soln.

In aq. soln.

In org. soln.

Cu

Fe

0
1
2
3
4

2.218
1.855
1.483
1.244

6.796
6.026
6.072
5.444
5.183

1.299
0.118
0.018
b 0.001

0.324
0.014
b 0.001
b 0.001
b 0.001

11.33
10.66
19.89
23.74

95.81
>99.8
>99.9
>99.9

scrubbed copper would be extracted again by the organic solution

in the subsequent scrub stages.
3.3. Chloride scrubbing
The co-extracted chloride was scrubbed with water under controlled pH with 10% NaOH solution. The chloride scrubbing at pH
3.04, 3.53 and 4.03 and the chloride scrubbing pH isotherm are
shown in Table 3 and Fig. 3, respectively. At pH 4, over 99.5%
chloride was scrubbed with only 39 mg/L Cl left in the scrubbed
organic solution, while the scrub efciency of copper was only
0.75%. In a counter-current operation, the scrubbed copper
would be extracted again by the organic solution in the subsequent scrub stages.
3.4. Copper stripping kinetics
Copper stripping kinetic tests were conducted with the scrubbed
organic solution containing 3.78 g/L Cu using a strip solution containing 53 g/L Cu and 180 g/L H2SO4 at an O/A ratio of 4 and 40 C
(Table 4). After two minutes of stripping, over 81% Cu was stripped
and after three minutes of stripping, nearly 94% Cu was stripped, indicating fast stripping kinetics.
4. Process owsheet development
With the above solvent extraction circuit, copper can be separated
from iron in chloride solutions, transferred to sulphate solution and
recovered as pure copper cathodes by conventional electrowinning.
A proposed owsheet is shown in Fig. 4.
This process, consisting of chloride leaching, copper solvent extraction and electrowinning, and iron hydrolysis would have the following main features:
Hydrochloric acid leaching provides faster leaching kinetics and
higher copper recovery compared with sulphuric acid leaching;

Table 3
Scrubbing chloride from the loaded organic solution with water under different pH
values at an A/O ratio of 1:2 and 40 C.
Scrub
pH

3.04
3.53
4.03

Cu concentration (g/L)

Cl concentration (g/L)

Scrubbing (%)

In aq. soln.

In org. soln.

In aq. soln.

In org. soln.

Cu

Cl

0.554
0.090
0.014

6.550
6.119
6.508
6.500

15.97
18.37
18.58

8.815
0.321
0.144
0.039

6.58
0.65
0.75

96.36
98.37
99.55

Copper is readily separated from iron in the high chloride concentration solution by the novel SSX system;
Iron is readily scrubbed from the copper-loaded SSX system with a
weak acid (0.2 M HCl) solution containing high concentration of
CaCl2;
Chloride is scrubbed with water in a pH range of 3.54 and the pH is
adjusted by adding ammonia solution;
The ammonia is regenerated by lime boiling and recycled for pH adjustment in the chloride scrub stage;
Copper is readily stripped from the loaded SSX system to obtain
loaded strip liquor suitable for conventional electrowinning;
Part of the rafnate of the SSX circuit is subjected to iron hydrolysis
to regenerate HCl and CaCl2 for leaching and to obtain an environmentally friendly product of iron oxide;
Part of the rafnate is recycled to the leach process to form a closed
circuit.
5. Proposed extraction mechanism
It is well-known that copper and iron can form complexes
with chloride ions such as CuCl2 and HFeCl4 in acidic solutions
with high chloride concentrations (Jackson, 1986). When the SSX
system extracts copper and iron, it is most likely that they are
extracted as neutral molecules; this is indirectly supported by
the following calculation. In the current loaded organic solution,
the chloride concentration was 8.82 g/L, and that of copper and
iron, 6.55 g/L and 0.82 g/L, respectively (Table 5). The aluminium
extraction was negligible (Fig. 1). The total molar concentration
of copper calculated was 0.103 M and that of iron and chloride
0.015 M and 0.249 M, respectively. Based on the molecule formula
of CuCl2 and HFeCl4, 0.265 M Cl is required, resulting in
the calculated chloride to the measured chloride ratio of 1.07.
This is consistent with a chloride to copper mole ratio of 2:1
and a chloride to iron mole ratio of 4:1, and hence the extraction
100.0

100.0

90.0

90.0

80.0

70.0

Scrubbing ( )

80.0

Scrubbing ( )

157

Cu

60.0
Fe

50.0
40.0
30.0

50.0
40.0
30.0
20.0

10.0

10.0
0

Scrubbing stage
Fig. 2. Scrubbing iron from the loaded organic solution consisting of 0.3 M LIX 63
and 0.33 M Versatic 10 in Shellsol D70 with chloride solution contained 350 g/L
CaCl2 and 0.2 M HCl in 4 batch scrubbing stages at an A/O ratio of 1:4 and 40 C.
The loaded organic solution contained 6.80 g/L Cu and 0.32 g/L Fe(III).

Cl

60.0

20.0
0.0

Cu

70.0

0.0
0.5

1.0

1.5

2.0

2.5

3.0

3.5

4.0

4.5

pH
Fig. 3. Scrubbing chloride from the loaded organic solution consisting of 0.3 M LIX 63
and 0.33 M Versatic 10 in Shellsol D70 with water under different pH values at an A/
O ratio of 1:2 and 40 C. The loaded organic solution contained 6.55 g/L Cu and
8.82 g/L Cl.

158

Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159

Table 4
Copper stripping kinetics.

Table 5
Copper, iron and chloride mole concentrations in the organic solution.

Time (min)

0.0

0.5

1.0

2.0

3.0

5.0

10.0

In organic solution (g/L)

In organic solution (mol/L)

Cu strip (%)

0.0

15.1

59.8

81.4

93.7

97.5

98.3

Cu

Fe

Cl

Cu

Fe

Cl

6.55

0.82

8.82

0.103

0.015

0.249

mechanism of the SSX system for the extraction of copper and

iron in high chloride concentration solutions is suggested to be
solvating as shown in Eqs. (1) and (2).
CuCl2 SSX SSXCuCl2

HFeCl4 SSX SSX HFeCl4

where the bars denote organic species.

When the loaded organic solution was subjected to scrubbing
with water, the chloride concentration in the loaded scrub liquor
was low. For example, if the above mentioned loaded organic solution
was scrubbed at an A/O ratio of 1:1 and all chloride entered the aqueous solution, the maximum chloride concentration would be 8.8 g/L,
indicating a low chloride concentration compared with the chloride
concentration of 224 g/L in the feed solution (Table 1). Therefore,
the SSXCuCl2 complex would dissociate to release the chloride ions
and the copper ions Eq. (3). At an appropriate pH, the organic solution
would extract the cationic copper ions to form complexes such as
SSX2 Cu2 Eq. (4) and release hydrogen ions to the aqueous solution.
In Fig. 3, it can be seen that copper was scrubbed from the organic solution at low pH and extracted when the pH increased, indicating that
the extraction mechanism of the SSX system for copper became pH
dependent, which is indicative of a cation exchange mechanism
Eq. (4). Because of this change in mechanism, chloride can be released
from the copperchloride complex and the copper can be transferred
from a chloride medium to a sulphate medium for conventional electrowinning, which is an important feature of this system.
2

SSXCuCl2 SSX Cu
2

SSX Cu

2Cl

SSX2 Cu2 2H

Clcalc.
(mol/L)

[Clcalc.]/
[Cl]

0.265

1.07

6. Conclusions
A novel SSX system consisting of Versatic 10 and LIX 63 has been
developed to separate copper from iron in high chloride concentration solutions and transfer the copper into sulphate solutions, thereby
enabling conventional electrowinning.
With the organic system consisting of 0.3 M LIX 63 and 0.33 M
Versatic 10 in Shellsol D70, over 95% Cu but only 14% Fe(III) were
extracted at an A/O ratio of 1:2 and 40 C after a single contact.
Over 99% co-extracted Fe(III) was scrubbed using a scrub solution
containing 350 g/L CaCl2 and 0.2 M HCl after two successive scrubbing stages with only 1 mg/L Fe(III) remaining in the organic solution. Over 99.5% of the co-extracted chloride was scrubbed with
water at pH 4, with only 39 mg/L remaining in the scrubbed organic solution. The copper stripping kinetics was fast with nearly 94%
Cu being stripped after 3 minutes of mixing at 40 C using 180 g/L
sulphuric acid.
It is proposed that in high chloride concentration solutions, the
copper would form a complex containing CuCl2 with the SSX system
via a solvating mechanism. After scrubbing the chloride with water,
the copper is proposed to be re-extracted via a cation exchange
mechanism by the same organic system.

Acknowledgements
The authors would like to thank Dr Keith Barnard and Mr Yoko
Pranolo for reviewing this paper and providing valuable comments.
The support of the Minerals Down Under National Research Flagship and Parker CRC for Integrated Hydrometallurgy Solutions is
gratefully acknowledged.

Copper ores

HCl/CaCl2 recycle

Chloride leaching
Leach
solution

Iron hydrolysis

Bleed
Iron oxide

Raffinate

Stripped organic
Water

Scrubbed
organic

Loaded
organic

Extraction

Fe Scrubbing

Stripping

Cl Scrubbing
NH3
Lime

To leaching

CaCl2

Spent
electrolyte

Advanced
electrolyte

Cu EW

Lime boiling

Cu cathodes
Fig. 4. A schematic of a proposed process owsheet for the separation of copper from iron and the recovery of copper from chloride solutions by a synergistic solvent extraction
system and conventional electrowinning.

Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159

References
Atmore, M.G., Severs, K.J., Voyzey, R.B.G., 1984. Past, present and future of solvent extraction of copper. International conference of Mineral Processing and extractive metallurgy, October, 1984, China.
Barnard, K.R., Urbani, M.D., 2007. The effect of organic acids on LIX63 stability under
harsh strip conditions and isolation of a diketone degradation product. Hydrometallurgy 89, 4051.
Cheng, C.Y., 2006. Solvent extraction of nickel and cobalt with synergistic systems consisting of carboxylic acid and aliphatic hydroxyoxime. Hydrometallurgy 84,
109117.
Cheng, C.Y. and Urbani, M.D., 2005. Solvent extraction process for separation
cobalt and/or manganese from impurities in leach solutions. WO Patent No 2005/
073415 A1.
Cheng, C.Y., Zhang, W., Pranolo, Y., 2010. Separation of cobalt and zinc from manganese, magnesium and calcium using synergistic solvent extraction system consisting of Versatic 10 and LIX63. Solvent Extr. Ion Exch. 28, 604624.
Dalton, R.F., Price, R., Quan, P.M., Steward, D., 1982, Process for extraction of metal
values and novel metal extractants, Eur. Patent No 57,797.
Harris, G.B., White, C.W., 2008. Recent developments in the high-strength chloride
leaching of base metal sulphide ores. ALTA Copper 2008, Perth, WA, September
2008.

159

Harris, G.B., Magee, J., Valls, R., 2003. Beyond PAL: The Chesbar option, AAL. ALTA Nickel/
Cobalt 2003, Perth, Australia, May 2003.
Harris, G.B., Lakshmanan, V. I., and Sridhar, R., 2004. Process for the recovery of
value metals from material containing base metal oxides. US Patent No 2004/
0228783 A1.
Jackson, E., 1986. Hydrometallurgical Extractions and Reclamation. Ellis Harwood, Ltd.
Publisher.
Krebs, D., Hyvarinen, O., Dreisinger, D., 2007. Processing nickel sulphide ore or concentrates with sodium chloride. PCT WO 2007/039663 A1.
Kyuchoukov, G., Szymanowski, J., 2000. Extraction of copper(II) and zinc(II) from
chloride media with mixed reagents. J. Radioanal. Nucl. Chem. 246 (3),
675692.
Kyuchoukov, G., Zhivkova, S., Borowiak-Resterna, A., Szymanowski, J., 2000. Separation
of copper(II) and zinc(II) from chloride solutions with alkyl-8-hydroxyquinoline in
various stages of extraction: stripping. Ind. Eng. Chem. Res. 39, 38963900.
Kyung-Ho, P., Debasish, M., Reddy, B.R., 2006. A study on the acidied ferric chloride
leaching of a complex (CuNiCoFe) matte. Sep. Purif. Technol. 2006 (51),
332337.
Paynter, J.C., 1973. A review of copper hydrometallurgy. J. S. Afr. Inst. Min. Metall. 1973,
158170 November.
Ryszard, C., Jan, S., 2001. Copper extraction from chloride solution by solvating and
chelating extractants. Solvent Extr. Ion Exch. 19 (3), 441456.