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 b s t r a c t 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 synergistic solvent extraction (SSX) system consisting of Versatic 10 and LIX 63 has been developed to sep-
arate copper from iron in high chloride concentration solutions and to transfer the extracted copper to a sul-
phate 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 electro-
lyte 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 CuCl
2
, 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 re-
extracted 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 smelt-
ing and leaching with other media such as sulphuric acid. Howev-
er, 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 commer-
cially 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 cop-
per over iron. So far no solvent extraction systems are available on
a commercial scale to recover copper effectively from chloride so-
lutions 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 chlo-
ride 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 extrac-
tion capacity and high selectivity for copper in chloride solutions
was developed and patented (Dalton et al., 1982). However,
CLX50 also transferred chloride to the electrowinning step, result-
ing in the unfavourable copper powder product (Atmore et al.,
1984). This reagent was abandoned and has never been commer-
cialised. 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 che-
lating 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 ef-
ciently extracted copper from chloride solutions. However, in strip-
ping 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 re-
agent such as Kelex 100 and LIX26 to transfer copper from chlo-
ride 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 cop-
per 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
Hydrometallurgy 113114 (2012) 155159
Corresponding author.
E-mail address: chu.cheng@csiro.au (C.Y. Cheng).
0304-386X/$ see front matter. Crown Copyright 2011 Published by Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.12.016
Contents lists available at SciVerse ScienceDirect
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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 recov-
ery of copper, from chloride solutions has not been established.
Copper hydroxyl-chloride and cuprous hydroxyl-chloride precipita-
tions have been proposed (Krebs et al., 2007). However, these in-
termediate 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). Howev-
er, it suffers disadvantages including small throughput and compli-
cated 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 de-
velopment and application of the novel SSX systemfor 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 re-
sultant 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 Aus-
tralia and LIX63 by Cognis Australia (now part of BASF). The compo-
sition of the LIX63 was reported by Cognis to be 70% active
component (5,8-diethyl-7-hydroxy-6-dodecanone oxime) in a dilu-
ent. 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
All tests were carried out in 0.5 L or 1.0 L stainless steel rectangu-
lar boxes immersed in a temperature controlled water bath. The solu-
tion temperature was maintained at 401 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.
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 mea-
sured 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.
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 ad-
just 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 solu-
tion containing 53 g/L Cu and 180 g/L H
2
SO
4
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 inde-
pendent 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 MHCl, 350 g/L CaCl
2
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 con-
taining 350 g/L CaCl
2
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
withb1 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
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
0.0 0.1 0.2 0.3 0.4 0.5 0.6
HCl concentration (M)
E
x
t
r
a
c
t
i
o
n

(
)
Cu
Fe
Al
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
Fig. 1. Effect of HCl concentration on metal extraction with the SSX systemconsisting 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 CaCl
2
at an A/O ratio of 1:2 and
40 C.
156 Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159
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 con-
trolled 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 subse-
quent 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 contain-
ing 53 g/L Cu and 180 g/L H
2
SO
4
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, indi-
cating 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 ex-
traction and electrowinning, and iron hydrolysis would have the fol-
lowing main features:
Hydrochloric acid leaching provides faster leaching kinetics and
higher copper recovery compared with sulphuric acid leaching;
Copper is readily separated from iron in the high chloride concen-
tration 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
CaCl
2
;
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 ad-
justment 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 CaCl
2
for leaching and to obtain an environ-
mentally 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 CuCl
2
and HFeCl
4
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 CuCl
2
and HFeCl
4
, 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
Table 2
Scrubbing iron from the loaded organic solution with a scrub solution containing
350 g/L CaCl
2
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 6.796 0.324
1 2.218 6.026 1.299 0.014 11.33 95.81
2 1.855 6.072 0.118 b0.001 10.66 >99.8
3 1.483 5.444 0.018 b0.001 19.89 >99.9
4 1.244 5.183 b0.001 b0.001 23.74 >99.9
0 1 2 3 4 5
Scrubbing stage
S
c
r
u
b
b
i
n
g

(
)
Cu
Fe
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
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
CaCl
2
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).
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
Cu concentration (g/L) Cl concentration (g/L) Scrubbing (%)
In aq. soln. In org. soln. In aq. soln. In org. soln. Cu Cl
6.550 8.815
3.04 0.554 6.119 15.97 0.321 6.58 96.36
3.53 0.090 6.508 18.37 0.144 0.65 98.37
4.03 0.014 6.500 18.58 0.039 0.75 99.55
pH
S
c
r
u
b
b
i
n
g

(
)
Cu
Cl
0.0
10.0
20.0
30.0
40.0
50.0
60.0
70.0
80.0
90.0
100.0
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5
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.
157 Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159
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).
CuCl
2
SSX SSXCuCl
2
1
HFeCl
4
SSX SSX HFeCl
4
2
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 aque-
ous 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 SSXCuCl
2
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
SSX
2
Cu
2
Eq. (4) and release hydrogen ions to the aqueous solution.
In Fig. 3, it can be seen that copper was scrubbed from the organic so-
lution at lowpH 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 elec-
trowinning, which is an important feature of this system.
SSXCuCl
2
SSX Cu
2
2Cl

3
SSX Cu
2
SSX
2
Cu
2
2H

4
6. Conclusions
A novel SSX system consisting of Versatic 10 and LIX 63 has been
developed to separate copper from iron in high chloride concentra-
tion 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 CaCl
2
and 0.2 M HCl after two successive scrub-
bing stages with only 1 mg/L Fe(III) remaining in the organic solu-
tion. Over 99.5% of the co-extracted chloride was scrubbed with
water at pH 4, with only 39 mg/L remaining in the scrubbed organ-
ic 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 CuCl
2
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 Flag-
ship and Parker CRC for Integrated Hydrometallurgy Solutions is
gratefully acknowledged.
Table 4
Copper stripping kinetics.
Time (min) 0.0 0.5 1.0 2.0 3.0 5.0 10.0
Cu strip (%) 0.0 15.1 59.8 81.4 93.7 97.5 98.3
Advanced
electrolyte
Leach
solution
Stripped organic
Loaded
organic
HCl/CaCl
2
recycle
Cu cathodes
Raffinate
Scrubbed
organic
Bleed
Cu EW
Spent
electrolyte
Copper ores
Chloride leaching Iron hydrolysis
Iron oxide
Extraction Fe Scrubbing Stripping
Cl Scrubbing
Water
To leaching
Lime boiling
NH
3
Lime
CaCl
2
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.
Table 5
Copper, iron and chloride mole concentrations in the organic solution.
In organic solution (g/L) In organic solution (mol/L) Cl
calc.
(mol/L)
[Cl
calc.
]/
[Cl]
Cu Fe Cl Cu Fe Cl
6.55 0.82 8.82 0.103 0.015 0.249 0.265 1.07
158 Z. Zhu et al. / Hydrometallurgy 113114 (2012) 155159
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