Hydrometallurgy 137 (2013) 1317

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Hydrometallurgy
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Solvent extraction of copper from chloride solution I: Extraction isotherms

Jianming Lu , David Dreisinger
Department of Materials Engineering, University of British Columbia, 309-6350 Stores Road, Vancouver, BC, Canada, V6T 1Z4

a r t i c l e

i n f o

Article history:
Received 19 November 2012
Received in revised form 31 March 2013
Accepted 10 April 2013
Available online 17 April 2013
Keywords:
Copper
Chloride solution
Solvent extraction
Extraction isotherm

a b s t r a c t
This study was conducted as part of the development of a novel process for copper recovery from chalcopyrite by chloride leaching, simultaneous cuprous oxidation and cupric solvent extraction to transfer copper to
a conventional sulfate electrowinning circuit, and hematite precipitation to reject iron. Copper solvent extraction from chloride solution has been studied using four LIX extractants (LIX84-I, LIX612N-LV,
XI-04003 and LIX984N) from BASF with respect to copper extraction as a function of pH and A/O ratio, and
behavior of the impurities. At a pH below 0.5, the copper extraction increased quickly with increasing pH
while at a pH above 0.5, it increased only slightly with pH. The copper extraction in organic solution was virtually not affected by the impurities. The iron extraction in organic solution increased with decreasing A/O
ratio from 2:1 to 1:8 as the copper extraction decreased. Conversely, the Cu/Fe ratio in organic solution
increased as copper extraction increased. The extractions of silver and lead were 1 mg/L or lower under all
conditions tested. The other impurities (Zn, Ni, Cd, Cr, Hg, As and Sb) were virtually not loaded into the
organic solution. The optimum copper solvent extraction conditions in chloride solution were proposed.
Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.

1. Introduction
Ferric and/or cupric chloride leaching processes have been extensively studied to treat sulde concentrates of copper, lead, and zinc
(Dutrizac, 1992; Peters, 1977). Chloride leaching has the following
advantages over sulfate systems: (1) supporting high metal solubility,
(2) enhanced redox behavior, (3) increased rates of leaching, and
(4) the formation of predominantly elemental sulfur. In a chloride
system, both cuprous and cupric ions are stabilized through complexation with chloride ions. Copper can be efciently extracted into chloride solution from chalcopyrite and bornite and a copper extraction of
99% can be reached at a temperature below 100 C using a two-stage
countercurrent chloride leach circuit (Lu and Dreisinger, 2013).
Compared to the conventional sulfate system, one challenge for the
chloride system is to produce high quality copper since some impurities such as silver are not removed efciently from chloride solution,
and dendritic copper cathodes are produced by electrowinning from
chloride solution. Generally there are four processes to recover
copper from chloride solution: (1) the precipitation of CuCl at lower
temperature and reduction to Cu in the UBC-Cominco and the
Cymet processes (Dutrizac, 1992; Peters, 1977), (2) direct electrowinning of Cu from chloride solution (Moyes et al., 2000), (3) the precipitation of Cu2O and reduction to Cu with hydrogen (Hyvarinen and
Hamalainen, 2005), and (4) solvent extraction of copper to sulfate
system from chloride system and electrowinning of copper from

Corresponding author. Tel.: +1 604 822 1357; fax: +1 604 822 3619.
E-mail address: Jianming.Lu@ubc.ca (J. Lu).

sulfate media (Demarthe et al., 1976; Liddicoat and Dreisinger,

2007). The rst two methods normally result in impure copper
while the third one is generally suitable for the solution containing
a small amount of iron. The fourth one can generate high purity copper since the impurities are separated from copper by solvent extraction. In this process, the advantages of both chloride (leaching) and
sulfate (SX-EW) systems can be fully utilized and their disadvantages
can be avoided. The transfer of copper from a Cu(I) chloride solution
to a Cu(II) sulfate solution requires extraction with a hydroxyoxime
extractant as is used normally in the processing of sulfate-based
copper leach solution. The solvent extraction process for copper recovery involves simultaneous cuprous oxidation and cupric solvent
extraction:
4 CuCl 4 HRorg O2 2 CuR2 org 2 CuCl2 2H2 O

This process was rst proposed by Demarthe et al. (1976). Proof of

concept testing indicated that cuprous oxidationcupric solvent extraction using air or oxygen was feasible with minimum transfer of
impurities. However, reliable data on the kinetics and equilibrium
processes for copper extraction is required for process denition.
In this work, four LIX extractants (LIX84-I, LIX612N-LV,
XI-04003 and LIX984N) recommended by BASF (Cognis) have been
studied since these extractants have a high copper loading capacity
and high selectivity of copper over iron. The objective of this study
is to develop the equilibrium data for copper solvent extraction
from chloride solution for the selection of optimum solvent extraction
operating conditions

0304-386X/$ see front matter. Crown Copyright 2013 Published by Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.hydromet.2013.04.001

14

J. Lu, D. Dreisinger / Hydrometallurgy 137 (2013) 1317

point was determined using standard solutions with different concentrations of copper.

2. Experimental
2.1. Apparatus

3. Results and discussion

The tests for extraction isotherms were conducted in a 250-mL
glass reactor with three bafes and a well at its base to allow collection and pH measurement of aqueous solution (Fig. 1). The pH was
measured using an Orion Ross sure-ow pH electrode.
2.2. Experimental procedures
The A/O ratio was set at 2:1, 1:1, 1:2, 1:3, 1:4 and 1:8 for investigating extraction isotherms. The procedures for generating an extraction isotherm are as follows:
(1) Aqueous solution and organic solution are transferred to the
reactor.
(2) The aqueous and organic phases are vigorously mixed and the
pH is controlled by addition of NaOH. The pH is rst adjusted
close to a target value using 50% NaOH and then it is nely
tuned to the target value using 10% NaOH.
(3) When the reaction reaches the equilibrium, the stirring is
stopped. After the two phases are separated, the mixed solution
is transferred to a separatory funnel. The separated aqueous solution is ltered using Whatman No. 42 ltration paper to remove
entrained organic solution. The separated organic solution is
centrifuged to remove trapped minor aqueous solution.
(4) Loaded organic solution is stripped three times using 6 M HCl
solution with an A/O ratio of 1:1. All strip solutions are collected
and combined for chemical analysis.
2.3. Preparation of organic and aqueous solution
The organic solutions were prepared on a volume basis (40%
extractant and 60% Phillips 66 kerosene). The aqueous feed solution
for extraction isotherms was prepared using deionized water, reagent
grade cupric, calcium and ferric chlorides. The impurities (Zn, Ni, Pb,
Cd, Cr, Ag, Hg, Sb) were added as their chlorides while As was
added as sodium arsenite.
2.4. Chemical analysis
The concentrations of Cu and Fe were analyzed using atomic
adsorption. The other elements were analyzed using ICP. The free
acid titration was conducted with oxalate masking. 2 M potassium
oxalate was used to complex metal ions that would normally contribute
protons, via reaction with hydroxide ions in water. The titration end

In the cuprous oxidationcupric solvent extraction system (CuCl/

CuCl2FeCl2/FeCl3CaCl2), without addition of base and acid, the pH is
difcult or impossible to control in the A/O ratio range of 2:1 to 1:8.
For example, at an A/O ratio of 2:1, after oxidation and extraction of a
small part of copper, the pH rises to a high value (>1.0) since copper extraction easily reaches the full copper loading capacity of the organic
phase and the amount of H+ released due to Reaction 2 is much less
than that consumed due to Reaction 3. At an A/O ratio of 1:8, the pH
cannot be raised to 0.5 by the oxidation of Cu(I) and Fe(II) since copper
extraction is about one quarter of the full copper loading capacity of
the organic phase and the amount of H+ released due to Reaction 2 is
much larger than that consumed due to Reaction 3.

Cu aq 2HRorg CuR2 org 2H

2 Cu Fe

1=2 O2 2H 2 Cu

2
3

Fe

H2 O

Not only is Cu(I) oxidized but also some Fe(II) is oxidized. It is difcult to accurately predict the concentrations of Cu(II) and Fe(III)
under the conditions studied without very reliable equilibrium constants and activity coefcients of Cu(II)/Cu(I) and Fe(III)/Fe(II) chloride species. The extraction of Fe(III) into the organic phase can
affect the copper extraction especially at a high pH. Therefore it is
very difcult to develop copper extraction isotherms as a function
of pH and Cu concentration (A/O ratio). By careful selection of initial
CuCl2 and CaCl2 concentrations, the copper extraction data developed
in CuCl2 and CaCl2 system with addition of NaOH for pH control can
be applied in a simultaneous cuprous oxidation and cupric solvent
extraction process.
3.1. pH measurement
Copper extraction in organic solution is dependent on aqueous solution pH. The accurate measurement of aqueous solution pH is important to develop extraction isotherms. When aqueous solution
contains a signicant amount of copper and calcium chlorides, the activity coefcient of hydrogen ion is signicantly changed and the pH
measurement is affected.
To control the aqueous solution pH, the copper solvent extraction
was conducted by addition of NaOH solution into copper chloride solution. The extraction reaction is expressed as:
2HRorg CuCl2 2 NaOH CuR2 org 2 NaCl 2 H2 O

Baffle

Ti shaft

pH probe

Baffle

Teflon impeller
Fig. 1. A schematic diagram for glass reactor for metal extraction isotherms.

With increasing copper extraction, the CuCl2 concentration decreased and the NaCl concentration increased. At a constant H + concentration, the pH changed as copper was extracted into the organic
phase. Therefore the pH measurement with respect to H + concentration was conducted in solutions with a constant CaCl2 concentration
and different CuCl2 and NaCl concentrations. The initial aqueous solution composition was 1.25 M CuCl2 (~ 80 g/L Cu) and 1.8 M CaCl2. The
reason for selection of such an initial aqueous composition is based on
the following consideration: when half of the copper was extracted
into the organic phase, the ionic strength and the free chloride concentration were close to those in the cuprous oxidationcupric solvent extraction system (Reaction 1). Therefore the extraction
isotherm data developed can be used for the cuprous oxidation and
cupric solvent extraction system. In such a concentrated chloride solution, the major Cu(II) species are CuCl2(aq), CuCl3 and CuCl42
while the dominant Fe(II) species is FeCl + (Muir, 2002; Winand,
1991). The ionic strength and free chloride concentrations were

J. Lu, D. Dreisinger / Hydrometallurgy 137 (2013) 1317

SX
reaction

Initial
composition

Reaction 1 1.25 M CuCl +

2 M FeCl2 +
1.5 M CaCl2
Reaction 4 1.25 M CuCl2 +
1.8 M CaCl2

Composition
after extraction
of half Cu

[Cl-]/M
Ionic
Species
selected for strength/
calculation M

0.625 M CuCl2
+ 2 M FeCl2
+ 1.5 M CaCl2
0.625 M CuCl2 +
1.25 M NaCl + 1.8
M CaCl2

CuCl2
CuCl3
CuCl42
CuCl2
CuCl3
CuCl42

5.0
6.50
7.13
4.85
6.65
7.28

6.19
4.38
3.75
6.65
4.23
3.6

calculated based on the selection of CuCl2 (aq), CuCl3 and CuCl42 respectively as the sole species present and they are summarized in
Table 1. After the extraction of half of the copper, the ionic strength
and free chloride concentration for Reaction 1 are close to those for
Reaction 4.
The pH values measured at 40 C are summarized in Table 2. The
measured pH varied only slightly with changing CuCl2 and NaCl concentrations. There is a virtually linear relationship between pH and
free acid concentration, and the slope is 1.00. The HCl concentration
was rst determined by titration and HCl was added to adjust the
HCl concentration to the target value.
The concentrations of CuCl2 and CaCl2 were so high that the pH
was affected by the liquid junction potential between the lling solution of the reference electrode for the pH probe and the solution studied. The direct measurement of a junction potential is not possible. In
this study, the Henderson equation was used to estimate the liquid
junction potential (Ej). The liquid junction potential and the corresponding pH correction are summarized in Table 3.
As NaOH solution was added and copper was extracted, the aqueous solution was diluted due to addition of the solution and water
formed by Reaction 4. The extraction of 25, 50, 75 and 100% copper
resulted in around 4, 8, 12, and 16% dilution respectively. The liquid
junction potential recalculated considering the dilution factor was
around 7.0 mV for all solutions and the pH corrected for liquid junction potential was the pH measured plus 0.11.

Table 3
Liquid junction potential and corresponding pH correction as a function of HCl concentration at different compositions and 40 C.
HCl concentration/M
1.25 M CuCl2 and 1.8 M CaCl2
0.9375 M CuCl2, 0.675 M NaCl
and 1.8 M CaCl2
0.625 M CuCl2, 1.25 M NaCl
and 1.8 M CaCl2
0.3125 M CuCl2, 1.875 M NaCl
and 1.8 M CaCl2
2.49 M NaCl and 1.8 M CaCl2

H+ concentration/M

0.005 0.01 0.02 0.04 0.08

1.25 M CuCl2 and 1.8 M CaCl2

0.9375 M CuCl2, 0.675 M NaCl and 1.8 M CaCl2
0.625 M CuCl2, 1.25 M NaCl and 1.8 M CaCl2
0.3125 M CuCl2, 1.875 M NaCl and 1.8 M CaCl2
2.49 M NaCl and 1.8 M CaCl2a

1.20
1.18
1.16
1.14
1.09

0.90
0.88
0.85
0.84
0.80

0.60
0.58
0.56
0.54
0.49

0.31
0.27
0.26
0.24
0.19

0.01
0.01
0.02
0.03
0.06

a
Instead of 2.5 M NaCl, 2.49 M NaCl was used because the saturation concentration
of NaCl in 1.8 CaCl2 solution is 2.49 M.

0.01

0.02

0.04

0.08

7.0
0.11
7.7
0.12
8.3
0.13
8.8
0.14
9.3
0.15

6.8
0.11
7.5
0.12
8.1
0.13
8.7
0.14
9.2
0.15

6.4
0.10
7.1
0.12
7.8
0.13
8.4
0.14
8.9
0.14

5.7
0.09
6.5
0.10
7.2
0.12
7.8
0.13
8.4
0.13

20

LIX84-I
LIX612N-LV
XI-04003
LIX984N

15

10
0.0

0.5

1.0

1.5

Measured pH
Fig. 2. Copper extraction pH isotherm in chloride solution based on the analysis of the
aqueous and organic solutions at 40 C and A/O ratio of 1.

25

[Cu2+]org. / g L-1

Table 2
pH values as a function of HCl concentration at different compositions at 40 C.

0.005
7.1
0.11
7.7
0.12
8.3
0.13
8.9
0.14
9.4
0.15

25

3.2. Copper extraction pH isotherms

Four LIX extractants (LIX84-I, LIX612N-LV, XI-04003 and LIX984N)
from BASF were tested. LIX 84-I is based on ketoxime. LIX 984 N is a
50:50 mixture of LIX 860 N-I (C9 aldoxime) with LIX 84-I. XI04003 is
formulated with C12 aldoxime and LIX 612 N-LV is formulated with
C9 aldoxime. Both XI04003 and LIX612n-LV are formulated with a ketone as a modier to the same degree of modication. If properly formulated, they should give identical performance within the limits of
error of the experiment. When the feed aqueous solution and organic
solution were mixed, the aqueous solution pH decreased from 0.86 to
the values ranging between 0.3 and 0.6, which were dependent
on the A/O ratio and the type of organic extractant. A lower A/O ratio
resulted in a lower pH since more copper was extracted into the organic
phase and more acid was produced. A stronger extractant resulted in a
lower pH.

Ej/mV
pH
Ej/mV
pH
Ej/mV
pH
Ej/mV
pH
Ej/mV
pH

At pH 0.6 to 0.3, the copper extraction was only 2040% of

their full loading capacity. NaOH was added to adjust the pH to the
target value and the extraction reaction is expressed by Reaction 4.
The plot of copper extraction against pH is shown in Fig. 2. At a pH
below 0.5, the copper extraction increased quickly with increasing
pH. At a pH above 0.5, the copper extraction increased slowly with increasing pH, indicating that the copper extraction was close to the full
capacity of the extractant. The copper extraction calculated based on
the H + generated (shown in Fig. 3) was very close to that based on

[Cu2+]org. / g L-1

Table 1
Ionic strength and free chloride concentration after extraction of half the copper.

15

20

LIX84-I
LIX612N-LV
15

XI-04003
LIX984N

10
0.0

0.5

1.0

1.5

Measured pH
Fig. 3. Copper extraction pH isotherms in chloride solution based on the H+ generated
at 40 C and A/O ratio of 1.

16

J. Lu, D. Dreisinger / Hydrometallurgy 137 (2013) 1317

25

Table 4
Composition of aqueous feed solution (g/L).

[Cu2+]org. / g L-1

20

Cu

Fe

Zn

Pb

Ni

Cd

Cr

Hg

Ag

As

Sb

75.6

9.78

1.95

0.918

0.906

1.02

0.101

0.173

0.046

0.052

0.061

15

3.4. Behavior of impurities in copper solvent extraction

10

LIX84-I
LIX612N-LV
XI04003
LIX984N

0
0

20

40

60

80

[Cu2+]aq. / g L-1
Fig. 4. Copper extraction distribution isotherms from chloride solution based on the
analysis of the aqueous and organic solutions at 40 C and pH 0.50.

the analysis, indicating that the extraction reaction follows Reaction 4.

The copper extraction for XI04003 was 0.51.0% lower than that for
LIX612N-LV probably due to small differences in extractant reagent
concentrations and analysis.

The behavior of impurities is important to know. Fe, Zn, Ni, Pb, Ni,
Cd, Cr, Hg, Ag, As and Sb were added as impurities. The feed solution
composition is summarized in Table 4. Copper and iron extraction distribution isotherms are shown in Figs. 6 and 7 respectively. The copper
extraction was nearly not affected by the impurities by comparison of
Figs. 4 and 6. The iron concentration in the organic solution decreased
with increasing iron concentration in the aqueous solution (or decreasing A/O ratio from 2:1 to 1:8). At a higher A/O ratio, the organic solution
was loaded with more copper and therefore less iron was extracted into
the organic solution. To suppress the iron extraction in the organic solution, the copper concentration in the organic solution should be close to
its full loading capacity. The Cu/Fe ratios in the organic solution at different A/O ratios are summarized in Table 5. The Cu/Fe ratios decreased
with decreasing A/O ratios as the copper concentration decreased and
more iron was extracted. The selectivity of copper over iron is related
not only to the extractant own properties, but also to the pH and copper
extraction in organic solution. A lower pH and high copper extraction

3.3. Copper extraction distribution isotherms

25

20

[Cu2+]org. / g L-1

At a pH above 0.5, the copper extraction increased slowly with increasing pH. At a pH above 0.9, iron oxide or hydroxide began to precipitate from the solution with 20 g/L Fe as FeCl3, 1.25 M CuCl2 and
1.8 M CaCl2. For cuprous oxidationcupric solvent extraction, when
most of Cu(I) is oxidized to Cu(II), a small amount of iron exists in
the form of Fe(III) since in such a concentrated chloride medium,
the redox potential for Cu(II)/Cu(I) is close to that for Fe(III)/Fe(II).
To avoid the precipitation of iron oxide and obtain a higher copper
extraction, the pH should be controlled around 0.5. Therefore copper
extraction distribution isotherms were developed at pH 0.5 and they
are shown in Fig. 4. At a low copper concentration (below 10 g/L)
in aqueous solution, the copper extraction in the organic solution increased rapidly with increasing aqueous copper concentration. As
more copper was extracted into the organic solution, the copper concentration in the organic solution increased slowly with increasing
aqueous copper concentration. The copper extraction calculated
based on the H + generated (shown in Fig. 5) was very close to that
based on the analysis of the organic solution.

LIX84-I
LIX612N-LV
XI04003
LIX984N

10

0
0

20

40

60

80

[Cu2+]aq. / g L-1
Fig. 6. Copper extraction distribution isotherms at 40 C and pH 0.50.

25

0.6

LIX84-I
LIX612N-LV
XI04003
LIX984N

0.5

[Fe3+]org. / g L-1

20

[Cu2+]org. / g L-1

15

15

10

LIX84-I
LIX612N-LV
XI04003
LIX984N

20

40

[Cu2+]aq.

60

/g

0.3
0.2
0.1

0
0

0.4

80

L-1

0
4

[Fe3+]aq.
Fig. 5. Copper extraction distribution isotherms in chloride solution based on the H+
generated at 40 C and pH 0.50.

/g

10

L-1

Fig. 7. Iron extraction distribution isotherms in chloride solution at 40 C and pH 0.50.

J. Lu, D. Dreisinger / Hydrometallurgy 137 (2013) 1317

Table 5
[Cu]/[Fe] ratios in organic solution at different A/O ratios.
A/O ratio

2:1

1:1

1:2

1:4

1:8

LIX84-I
LIX612N-LV
XI-04003
LIX984N

225
285
295
266

218
272
285
253

178
201
226
191

90
94
94
54

23
20
20
16

result in a lower iron extraction. The extractions of silver and lead were
1 mg/L or lower for all ve extractants. The behavior of these impurities
in copper solvent extraction is probably related to the formation of their
chloro-complexes that are not extracted into hydroxyoxime organic
solution.
4. Conclusions
There is a virtually linear relationship between pH and free acid
concentration (0.0050.08 M) in CuCl2NaClCaCl2 solution and the
slope is 1.00. Considering the dilution due to the addition of NaOH
solution, the liquid junction potential estimated using Henderson's
equation is around 7 mV for all solutions and the corrected pH is
the measured value plus 0.11.
At a pH below 0.5, the copper extraction increased quickly with
increasing pH while at a pH above 0.5, it only increased slowly with
increasing pH. At an aqueous copper concentration below 10 g/L, the
copper extraction increased quickly with increasing aqueous copper
concentration while at an aqueous copper concentration above 10 g/L,
the copper extraction increased slowly with increasing aqueous copper
concentration. The loading capacity order of copper for four extractants
is: LIX984N > LIX612N-LV, XI04003 > LIX84-I.
The copper extraction in organic solution was virtually not affected
by impurities except for Fe(III). The iron extraction in the organic solution increased with decreasing copper extraction. The Cu/Fe ratio in the
organic solution increased with increasing copper extraction as iron
extraction decreased. The selectivity of copper over iron is related not

17

only to the extractant own properties, but also to the pH and copper
extraction in organic solution. The extractions of silver and lead were
1 mg/L or lower. The other impurities (Zn, Ni, Cd, Cr, Hg, As and Sb)
were virtually not loaded into the organic solution.
The recommended operating conditions are as follows: (1) pH
should be controlled around 0.5 to maintain a high copper extraction
and a low iron extraction, and prevent the precipitation of ferric hydroxide at a higher pH; and (2) copper extraction should be close to
its full loading capacity to suppress iron extraction and maintain a
high Cu/Fe ratio in organic solution.

Acknowledgments
The authors would like to thank Falconbridge Limited (now
XSTRATA) for funding this project and allowing for publication, and
also thank BASF (Cognis) for supplying the solvents.

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