Minerals Engineering 156 (2020) 106498

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Minerals Engineering
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The effect of chloride ions on copper solvent extraction from sulfate-chloride T

medium using LIX 984N
Sina Shakibania, Alireza Mahmoudi, Mohammad Mokmeli , Fereshteh Rashchi
⁎

School of Metallurgy and Materials Engineering, College of Engineering, University of Tehran, Tehran, Iran

ARTICLE INFO ABSTRACT

Keywords: The supply of fresh water is becoming an increasingly important issue in hydrometallurgical treatment of mi-
Solvent extraction neral ores. The problem may significantly reduce if the extraction process can incorporate the usage of saltwater
Copper extraction throughout the whole hydrometallurgical operation. Seawater as the main source of saltwater is a potential
LIX 984N alternative to freshwater. In this research, the effect of the chloride ions, in a range of 0 to 40 g/L, on the solvent
Thermodynamic simulation
extraction of copper with LIX 984N was studied. LIX 984N has been commercially used in copper solvent ex-
Seawater
traction around the world. Increasing the concentration of Cl− was shown to increase the H+ activity and
formation of CuCl+ and CuCl2 species. The solution acidity did not have a negative effect on the extent of copper
extraction and extraction rate, in the presence and absence of chloride ion, in contrast to recent studies. The
chloride addition was even showed to have a positive impact on copper extraction at pHs below 2 and at shorter
mixing times. Through thermodynamic studies, it was shown that increasing chloride concentration results in
both higher H+ activity and an increase in the activity of copper chloride complexes, of which the latter factor
counteracts the former and overall improves the extent of copper extraction. Increasing the chloride con-
centration was found to negatively affect the copper extraction isotherms. The impact became more significant at
lower concentrations of the extractant. It is therefore suggested that cupric chloride complex ion inhibits copper
extraction by lowering the extraction driving forces. Also, it was shown that increasing aqueous chloride con-
centration promotes involvement of more extractant molecules per Cu2+ species in the extraction reaction in
contrast to the reaction without chloride ions. The negative effect of chloride ions on copper solvent extraction
then is due to the change in the reaction stoichiometry and decrease in the extraction driving force rather than
the types of aqueous Cu2+ speciation. The effect of wash stages on the removal of the chloride ion from loaded
organic solution was then investigated and the optimum conditions for the wash stage were found at wash
solution to loaded organic ratio of 1 to 7 and sulfuric acid concentration of 10 g/L.

1. Introduction Bobadilla-Fazzini et al., 2017; Hashemzadeh et al., 2019; Ruiz et al.,

Due to water scarcity, the use of seawater in mineral processing and
hydrometallurgical processes is increasing (Hernández et al., 2015).
Seawater in average contains about 20 g/L of chloride ions in a form of
different chloride salts such as NaCl, MgCl2, CaCl2, and KCl
(Hashemzadeh et al., 2019). Hydrometallurgical extraction of copper
usually consists of three main processes, leaching, solvent extraction
(SX), and electrowinning (EW) (Davenport et al., 2002). Presence of
chloride ion in the leaching solution can significantly increase the
dissolution rate of copper sulfides, especially the chalcopyrite mineral.
The effects of chloride ion on the leaching of copper sulfides have been
extensively investigated, and its positive impact on the dissolution rate
has been reported in several publications (Al-Harahsheh et al., 2008;
2011; Senanayake, 2009). However, high content of chloride ion in the
pregnant leach solution (PLS) can impose significant challenges to the
next stages of copper extraction process: SX, and EW operations.
Solvent extraction process is used for purification and concentration
of copper bearing solution. Selective separation of copper from other
impurities is done by an organic extractant according to the following
reaction (Alguacil et al., 1999):
2HR org + Cu2aq+ = CuR2org + 2H+aq (1)
In which, HRorg represents the organic solvent molecules. In pre-
sence of chloride ion in PLS, the transformation of Cu2+ to chloro-
complexes of copper happens. This also increases the activity coefficient
of the proton ions (Senanayake, 2007). These changes in the system can

⁎
Corresponding author at: College of Engineering, University of Tehran, School of Metallurgy and Materials Engineering, Tehran 11155-4563, Iran.
E-mail address: mokmeli@ut.ac.ir (M. Mokmeli).

https://doi.org/10.1016/j.mineng.2020.106498
Received 2 February 2020; Received in revised form 1 June 2020; Accepted 2 June 2020
0892-6875/ © 2020 Elsevier Ltd. All rights reserved.
S. Shakibania, et al.
negatively affect the extraction of copper. Since by increasing H+ ac-
tivity coefficient, the system tendency toward stripping will increase.
Hydroxyoxime extractants (e.g., LIX groups) have been commer-
cially used for copper solvent extraction since the latter half of the
1970s (Jergensen, 1999); however, the effect of the chloride ions on
solvent extraction of copper has not yet been thoroughly investigated.
Ruiz et al. (2019) investigated the effect of the chloride ions on ex-
traction equilibrium of copper with LIX 84-IC and LIX 860N-IC. They
showed that as the concentration of the chloride in the solution in-
creased, the equilibria isotherms with both extractants shifted to the
right (Ruiz et al., 2019). Ruiz et al. (2020) studied the effect of the
chloride ions, on three levels of 0, 60, and 110 g/L, on the copper ex-
traction using LIX 984N and Acorga M5910. In this work, the effect of
the chloride ion on the extraction and stripping isotherms of copper
were investigated (Ruiz et al., 2020). The reasoning for the negative
impact of the chloride ion was not however sufficiently provided. It was
shown that the presence of the chloride ions in the solution negatively
affected the extraction equilibriums of copper. For both extractants,
equilibrium isotherms shifted to the right, and the same results were
observed as the extraction with LIX 84-IC and LIX 860N-IC.
Zhou et al. (1988) studied the extraction of copper from the chloride
media with LIX 65N. It was shown that in the presence of chloride,
Cu2+ converts to the CuCl+. This transformation in the species of
copper resulted in an increase in the extraction rate of copper (Zhou
et al., 1988). When chloride concentration was around 1.5–2 M, the
extraction rate was maximum. The following reactions were proposed
as the probable main extraction reactions of copper from a chloride
media:
HR org + CuCl+aq = CuRCl ad + H+aq (2)
H+aq
CuRCl ad + HR org = CuR2org + + Claq (3)
Based on these reactions, chloride does not enter the organic phase
through a chemical reaction with copper. Chloride is one of the im-
purities that physically entrains to the loaded organic (Cole et al.,
2016). A certain amount of chloride in the electrolyte is desirable since
it enhances the conductivity of the solution (Littlejohn and Dreisinger,
2007; Yanson and Rost, 2013). However, excessive transfer of chloride
ions from the loaded organic to the electrolyte can cause some severe
issues. If the concentration of the chloride in the electrolyte passes over
30 ppm, pitting of stainless-steel cathodes can happen (Davenport et al.,
2002). Other issues related to the increasing chloride concentration
over the electrowinning process are the decrease in the number of free
cupric nuclei (Panda, 2013; Sun and O’Keefe, 1992), the increase in the
size of the nuclei(Luyima et al., 2016; Sun and O’Keefe, 1992), the
decrease of the adhesive strength of the copper deposit (Murray et al.,
2016), and requires an increase in the current density (Lin et al., 1991).
Inclusion of a wash stage between extraction and stripping stage is
an effective way to control chloride concentration in the electrolyte
(Burkhardt, 2003; Regel-Rosocka and Alguacil, 2013). The main aim of
utilizing washing stages is to remove or reduce the concentration of the
impurities that are physically entrained to the loaded organic. A typical
wash liquor is a diluted solution of sulfuric acid. A mixture of lean
electrolyte and dilution water can also be used for the washing of the
loaded organic (Davenport et al., 2002).
As stated earlier, the average concentration of the chloride in the
seawater is around 20 g/L. However, due to the evaporation and re-
circulation of water over the heap leaching operation, the concentration
of the chloride ion in a PLS can double (Watling et al., 2014). The
present work studies the effect of chloride ion concentration in the
synthetic copper PLS with a similar chemical composition to that of a
solvent extraction plant. For the experiments, LIX 984N was selected as
the extractant. The range of the chloride concentration in a synthetic
PLS set to be from 0 to 40 g/L. The experiments were conducted to
investigate the chloride impact on the extraction of copper, the ex-
traction mechanisms of Cu2+ and CuCl+ and the thermodynamic
2
Minerals Engineering 156 (2020) 106498
behavior of copper in chloride solution. A set of experiments were also
designed to evaluate the efficiency of the wash stages in controlling the
transfer of chloride ion to the rich electrolyte.
2. Thermodynamic study
In this section, the thermodynamic behavior of copper with chloride
is presented. The effect of chloride ion in PLS on the solvent extraction
of copper was described in two main subsections: First, the effects of the
different parameters, such as chloride concentration, temperature, and
the initial copper concentration on the fraction of copper chloro-com-
plexes have been investigated. Then, the effects of the chloride ions on
dominant species of copper at different pH, potential, and chloride
concentration have been discussed describing the assumptions, used
data, and explanation of results. It is hoped that identifying the copper-
chloride species will provide a better understanding of the studied
system and interpretation of the results. Incorporation of chloride ions
through seawater in leaching of copper ores significantly affect the
aqueous species of the dissolved copper. Apart from changes in copper
species, the existence of chloride ions affects the activity of aqueous
species, which can potentially lower the efficiency of copper extraction
during the SX process. Therefore, this paper’s primary objective is to
investigate the thermodynamic behavior of the Cu-H2O-Cl system.
The general reaction of the complexation of cupric ions with
chloride is:
Cu2 + + iCl = CuCl 2i i
i = 1, 2, 3, 4 (4)
The thermodynamic modeling of cupric complexation with chloride
ion may be based on a few assumptions: 1. The temperature of the
system was assumed constant and equal to 25 °C. 2. The system was run
under atmospheric pressure. 3. The activity of the species is assumed to
be equal to the concentration of the species (activity coefficients are
considered to be 1). 4. All the reactions are assumed to be in the
equilibrium state.
The thermodynamic data to calculate the equilibrium constants was
obtained from the Puigdomenec (2000) study (Puigdomenech and
Taxén, 2000). The complexation reactions of copper with chloride and
their equilibrium constants are:
Cu2 + + Cl = CuCl+ logK1 = + 0.64 (5)
Cu2 + + 2Cl = CuCl2 logK2 = + 0.24 (6)
Cu2 + + 3Cl = CuCl3 logK3 = 1.28 (7)
Cu2 + + 4Cl = CuCl logK 4 = 3.98 (8)
The concentration of the chloride complexes of cupric can be
written as a function of cupric concentration, chloride concentration,
and the equilibrium constant. Considering the total concentration of the
cupric and chloride, the equilibrium constant of copper complexation
reactions and the concentration of chloride-cupric complexes, the total
concentration of the cupric and chloride are calculated as follows:
g/LCl
[Cl ]T = = [Cl ] + 10 0.64 [Cu2 +][Cl ] + 2 × 100.24 [Cu2 +][Cl ]2
35.45
+ 3 × 10 1.28 [Cu2 +][Cl ]3 + 4 × 10 3.98 [Cu2 +][Cl ]4 (9)
g/LCu2 +
[Cu2+]T = = [Cu2+] + 100.64 [Cu2+][Cl ] + 100.24 [Cu2 +][Cl ]2
63.55
+ 10 1.28 [Cu2 +][Cl ]3 + 10 3.98 [Cu2 +][Cl ]4 (10)
By replacing the actual value of the total concentration of cupric in
the present work (3.3 g/L = 0.052 M) in Eq. (10), varying the total
concentration of chloride (from 0 to 40 g/L), and solving the two
equations with two variables ([Cu2+] and [Cl−]), species distribution
diagram of copper chloride complexes is plotted (Fig. 1).
As it evident in Fig. 1, by increasing the concentration of the
chloride ions in the system, the concentration of the chloro-complexes
S. Shakibania, et al.
Fig. 1. Effect of chloride concentration on Cu2+ species distribution diagram:
T = 25 °C and [Cu2+] = 0.052 M.
of the cupric ions increases. Yet when the concentration of the chloride
ions increases from 0 to 40 g/L, the concentrations of the generated
CuCl3− and CuCl42− are negligible. However, in the same range of
chloride concentration, a considerable amount of Cu2+ transforms into
CuCl+ and CuCl2. A common chelating reagent extracts copper in a
process called chelation, which in some cases, involves cation exchange
(Eq. (1)). In the previous works (Ruiz et al., 2018, 2017), the generation
of CuCl2 was stated to be detrimental to the solvent extraction of copper
that undergoes a cationic mechanism.
In order to fully investigate the cupric ion complexation with
chloride ions, the effects of the temperature and initial cupric con-
centration were also studied. Figs. 2 and 3 show the effects of the
temperature and chloride ion concentration on the fraction of CuCl+
and CuCl2 in the Cu-H2O-Cl system. The Criss-Cobble method was used
to calculate higher temperature thermodynamic data (by HSC software
database, Outokumpu research). With the increase of temperature,
while the fraction of CuCl+ increases, the fraction of CuCl2 decreases.
At 75 °C, the fraction of the generated CuCl2 in the presence of 40 g/L of
chloride ions is around 0.15, which is almost 0.1 lesser than its fraction
at 25 °C. However, PLS with higher temperatures can affect the organic
health. The chemical and physical properties of organic solution can be
altered by increasing the temperature of PLS. The elevated temperature
will increase the loss of organic solution due to evaporation and also
will cause an increase in hydrolytic degradation (Littlejohn and
Dreisinger, 2007). Therefore, increasing the temperature over a specific
limit for decreasing the fraction of CuCl2 is not practical. Moreover, in
the SX plants, the temperature of the spent electrolyte returning for
Fig. 2. Effects of the chloride concentration and temperature on fraction of
CuCl+ for [Cu] = 0.052 M.
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Minerals Engineering 156 (2020) 106498
Fig. 3. Effects of the chloride concentration and temperature on fraction of
CuCl2 for [Cu] = 0.052 M.
stripping of the loaded organic is usually kept below 40 °C to avoid
degradation of the organic phase (Davenport et al., 2002).
Figs. 4 and 5 show the effect of the initial cupric concentration on
the fraction of CuCl+ and CuCl2, respectively. Despite a slight decrease
in the fraction of cupric chloride complexes, increasing cupric con-
centration have an insignificant effect on the copper complexation with
chloride.
For simplicity, in all the previous calculations, the activity coeffi-
cients were assumed constant and equal to 1. However, as Zhou et al.
(1988) reported, activity proportions of Cu2+ and CuCl+ to H+ plays
an important role in determining the extraction mechanism of copper
(Zhou et al., 1988). Pitzer’s model (Pytkowicz, 1979) was used to cal-
culate activity coefficients (with HSC software). As a result, the activ-
ities of the three major copper chloride species and H+ as a function of
chloride concentration were determined. The obtained results are
shown in Fig. 6.
As it is apparent, aCu2+ is a decreasing function of chloride con-
centration. When chloride concentration exceeds over 20 g/L, aCuCl2
surpasses the aCu2+. In the chloride concentrations above 5 g/L, aCuCl+
has the highest activity relative to the other Cu2+ species. Another
aspect of Fig. 6 that should be evaluated is the comparison between the
activity of the copper chloride species and H+. Considering the ex-
traction reactions (Eqs. (1) and (2)), extraction of metal ion species
results in an H+ release from the extractant to the raffinate solution. By
increasing the chloride ion concentration, the aH+ increases. At higher
H+ activities, the backward reaction is more favorable and therefore
lesser extraction is expected.
Six main factors affect the dominant thermodynamic species in the
Fig. 4. Effects of the chloride concentration and initial cupric concentration on
fraction of CuCl+ at T = 25 °C.
S. Shakibania, et al. Minerals Engineering 156 (2020) 106498

Fig. 5. Effects of the chloride concentration and initial cupric concentration on

fraction of CuCl2 at T = 25 °C.

Fig. 8. log [Cl]-pH diagram for Cu2+–H2O-Cl system at 25 °C, and

[Cu] = 0.052 M, P = 1 atm, and Eh = 0.6 V.

Fig. 6. Effect of the chloride concentration on activity of the cupric chloride

complexes and H+ at 25 °C, pH = 2, P = 1 atm, and [Cu] = 0.052.

studied system (impurities are excluded): potential, pH, [Cl−], tem-

perature, pressure, and initial [Cu]. Three of these parameters: tem-
perature, pressure, and initial [Cu] are assumed constant, and the ef-
fects of potential, pH and [Cl−] are shown in Figs. 7–10. Fig. 9. Eh-pH diagram for Cu-H2O system at 25 °C, P = 1 atm, and
The effect of the chloride concentration and Eh on the pre- [Cu] = 0.052 M.
dominance area of the copper species, in a system consists of Cu-H2O-Cl
is shown in Fig. 7. The thermodynamic data to plot this diagram is

Fig. 10. Eh-pH diagram for Cu-H2O-Cl system at 25 °C, P = 1 atm, and
[Cu] = 0.052 M, [Cl] = 1.128 M.
Fig. 7. Eh-log [Cl−] diagram for Cu-H2O-Cl system at 25 °C, [Cu] = 0.052,
pH = 2 and P = 1 atm.

4
S. Shakibania, et al. Minerals Engineering 156 (2020) 106498

Table 1 Table 3
Redox potential of major reactions in the studied system. Chemical composition of the synthetic PLS.
Reaction Eo (V) vs SHE Eh (V)* Elements Cu2 + Fe2 + Fe3 + Cl

Cl2(a) + 2e = 2Cl 1.40 1.25 Concentration (g/L) 3.3 1.2 1 0–40

O2(a) + 4H+ + 4e = 2H2 O 1.27 1.06
Fe3 + + e = Fe2 + 0.77 0.78
Cu2 + + e = Cu+ 0.16 0.38 sulfate salts, based on Table 3, in deionized water. The selected con-
centrations of copper and iron were based on the PLS analysis of
* Nernst equation was used to calculate the Eh. The activity of species was Sarcheshmeh. The concentration of the chloride in the solution was
assumed to equal to their concentration. The concentration of dissolved oxygen adjusted by the addition of sodium chloride.
in the atmospheric condition was assumed 10 ppm. The activities of Cu+ and
Cl2(a) were considered to be 10−6.
3.2. Experimental procedure
taken from Puigdomenec (2000) study. Depending on the solution
Experiments were designed in two parts. First, the effect of chloride
oxidation–reduction potential, in the approximate chloride concentra-
ions on the extraction of copper was investigated; then, the feasibility of
tion of 10 g/L, CuCl+ becomes the dominant species of an acidic so-
controlling chloride ions concentration in loaded organic through
lution (pH = 2) containing Cu (3.3 g/L) and Cl−. If the concentration of
washing stages was studied.
the chloride passes over 80 g/L, CuCl2 turns into the dominant specie in
the solution. The presence of other elements in the solution such as Fe
3.2.1. Extraction efficiency versus pH
can affect the equilibrium lines in the diagrams since they can also react
The effect of the chloride ions on the extraction of copper was
with chloride and consume some of the chloride ions in the system;
studied by mixing 20 ml of the aqueous solution containing chloride
therefore, different chloride species becomes dominant at higher
ions at three levels of 0, 20, and 40 g/L with 20 ml of the 12% v/v
chloride concentrations. In this study, the solution Eh and pH of the PLS
organic solution at room temperature (T = 30 °C), for 10 min (although
were identified above 0.55 V and below 2.75, respectively. Over this
equilibrium is attained faster, for confidence, 10 min mixing was
range, cupric species were found dominant. Some reaction which can
chosen as the contact time). Six different initial pHs of 1, 1.25, 1.5, 2,
increase the Eh of the distilled water (0.25 V), in the experimental
2.5 and 2.75, were chosen for plotting extraction-pH diagram. In each
condition of this research, are listed in Table 1 (By HSC software da-
test, pH was adjusted by adding either sulfuric acid (300 g/L) or sodium
tabase). Based on this table, the Eh of the solution was more affected by
hydroxide (200 g/L) dropwise. The pH of the aqueous solution was
redox reaction Fe3+/Fe2+ and the decrease of pH. Due to the low
monitored by pH meter PB-11 (Sartorius, Germany) with a reference
dissolved oxygen concentration, and high potential of Cl2/Cl− couple,
electrode of Ag/AgCl (3 M KCl). After ten minutes of agitation on the
these species do not affect the solution potential.
magnetic stirrer (Alfa D500, Iran), the aqueous and organic phase were
Fig. 8 shows the simultaneous effects of pH and log [Cl−] on the
separated in a separatory funnel, the aqueous solution was sampled,
dominant species of the cupric-chloride system. The theoretical Eh to
and the concentration of the copper was analyzed by atomic absorption
plot this diagram was considered 0.6 V so that only cupric species
spectroscopy, AAS (Agilent 200 series, United States). The concentra-
would be stable. Chloride complexes of cupric ions are dominant at
tion of the copper in the organic phase was determined through mass
higher concentrations of chloride and lower pH. In order to compare
balance. Parameters of solvent extraction, distribution coefficient and
the effect of the chloride addition to the system, the Eh-pH diagram of
extraction percentage of copper were calculated through the following:
copper at two different chloride concentrations of 0 and 40 g/L are
shown in Figs. 9 and 10. As it is evident, the existence of the chloride [M]org
D=
ions resulted in the presence of two chloride complexes of copper in pH [M]aq (11)
below 6.
[M]org
E% =
3. Experimental [M]o,aq (12)
where [M]org and [M]aq are the concentration of the element M in the
3.1. Materials organic and aqueous solutions after extraction, and [M]0,aq is the initial
concentration of element M in the PLS.
The PLS was synthesized using copper (II) sulfate (> 99% pure) iron
(II) sulfate (> 99.5% pure), iron (III) sulfate (> 80% pure, main im-
3.2.2. Extraction equilibrium isotherm
purity was molecular water) and sodium chloride (> 99% pure) re-
Equilibrium isotherms were plotted contacting a volume of 12% v/v
agents from Merck, Germany. The organic extractant used in this re-
organic solution with 20 ml of the aqueous solution for 10 min. The
search was an industrial-grade, LIX 984N, provided by Sarcheshmeh
initial pH of the aqueous solution set at 2 in all extraction tests with
Copper Complex, Iran. The properties of the organic are illustrated in
sulfuric acid (300 g/L). By varying the organic to aqueous ratio, from 1/
Table 2. For diluent, a mixture of different organic compounds, applied
8 to 8, extraction isotherm line was plotted. The effect of the chloride
industrially at Sarcheshmeh Copper Complex, was used. Sodium hy-
ions on the copper extraction equilibriums was investigated on three
droxide (> 99% pure) and sulfuric acid (> 95% pure) from Merck
levels of 0, 20, and 40 g/L in the PLS. After extraction, the aqueous
Germany were used for pH adjustment.
solution was sampled, and the concentration of the copper in the
The synthetic PLS was prepared by dissolving copper and iron
aqueous solution was analyzed by AAS.

Table 2
3.2.3. Effect of the contact time and the extractant concentration
Chemical and physical properties of LIX 984N.
The effect of the contact time was investigated for 20 ml of 12% v/v
Characteristics LIX 984N organic extractant mixed with 20 ml of the aqueous solution containing
Molecular Weight (g/Mole) ≈270
chloride at three levels of 0, 20, and 40 g/L. The initial pH of the
Density (g/cm3 ) 0.9136
aqueous solution was equal to 2 in all experiments. The contact time
Viscosity (csT at T = 25 °C) 38.2
Flash Point (oC) 97 was varied from 10 s to 10 min. After mixing, the aqueous and organic
solutions were separated, and the aqueous solution was sampled. The

5
S. Shakibania, et al.
concentration of the Cu in the aqueous solution was determined by
AAS. The same procedure was repeated; however, in the new tests, the
contact time was constant (10 min), and the concentration of the or-
ganic extractant was varied from 4 to 20% v/v.
3.2.4. Wash stage
To assess the efficiency of the wash stages in the removal of the
chloride ion from the loaded organic, a set of experiments were con-
ducted. The acidity of the wash solution and the ratio of wash solution
to the loaded organic were the two main studied parameters. First, in
the constant ratio of 1:7 of wash solution to loaded organic, the effect of
the H2SO4 concentration in the wash solution was investigated. The
H2SO4 concentration varied from 0 to 25 g/L. Then, the effect of the
washing solution to loaded organic ratio (from 1:7 to 1:50), in the
constant concentration of 10 g/L H2SO4, was studied. In all experi-
ments, 10 ml of the wash solution was mixed with the specified amount
of the loaded organic (based on washing solution to loaded organic
ratio) for 10 min. The loaded organic was prepared by contacting the
fresh organic solution with the PLS containing 40 g/L of chloride for
10 min at a pH of 2. In the end, the concentration of copper in the wash
solution was determined by AAS and the chloride concentration in the
wash solution was measured by titration (Metrohm, Titro plus 848,
United States)
4. Results and discussion
4.1. Copper extraction from the chloride-sulfate solution
4.1.1. Effects of pH
The effects of the pH and chloride concentration on the extraction of
copper were investigated. The obtained results are shown in Fig. 11 for
pH value and chloride concentration ranging from 1 to 2.75 and 0 to
40 g/L, respectively.
This figure indicates that in the pH below 2, the extraction of copper
in the presence of chloride ion is higher. This could be related to the
activity of the species. In the chloride concentration of 20 and 40 g/L,
CuCl+, and the absence of chloride ions, Cu2+ are the dominant spe-
cies. According to Fig. 6, increasing the chloride concentration results
in increasing CuCl+ activity; meanwhile, the activity of the H+ also
increases. However, the activity ratio of the CuCl+ to H+ in chloride
concentrations of 20 and 40 g/L is higher compared to the activity ratio
of Cu2+ to H+ in the absence of chloride ion. This trend is repeated at
lower pHs. Accordingly, it can be concluded that because of the higher
tendency of the system toward extraction, in the presence of chloride in
pH below 2, the copper extractions were higher as compared to the
absence of chloride. In pH values above 2, copper extraction has
reached to almost its maximum value. As an expression of system
Fig. 11. Effects of pH and organic extractant on copper extraction:
extractant = LIX 984 (12% v/v), contact time = 10 min, O/A = 1.
6
Minerals Engineering 156 (2020) 106498
Table 4
Activity ratio of copper cations to H+ in different chloride concentrations.
[Cl] (g/L) aCu2+/aH+ aCuCl+/aH+
0 2.208 –
20 0.757 2.782
40 0.424 2.822
tendency toward extraction, the activity ratio of copper cations to H+,
in different chloride concentration was determined and is presented in
Table 4. The values are calculated from Fig. 6. The activity ratio of
CuCl+ to H+ in 20 and 40 g/L of chloride is higher in compared to
activity ratio of Cu2+ to H+ in the absence of chloride, which verifies
higher copper in the presence of chloride. The activity ratio of Cu2+ to
H+ decreases by increasing chloride concentration; however, the con-
centration of cupric also decreases. Above pH 2, the tendency of the
system towards copper extraction is high enough. Accordingly, at this
pH range, an insignificant difference in the extraction of copper at
different chloride concentrations was observed.
4.1.2. Effect of the contact time
The effect of the contact time and chloride concentration on the
extraction of 3.3 g/L copper ions using an organic solution of 12% v/v
at the pH of 2 is shown in Fig. 12.The results show that at equilibrium
state, which is obtained at enough mixing time, increasing chloride
concentration from 0 to 40 does not significantly affect the extraction
rate of copper. However, copper extraction, in the presence of chloride
in solution, was slightly faster at shorter mixing times, which is in
agreement with the results obtained by Zhou (1988) and Ruiz (2019)
(Ruiz et al., 2019; Zhou et al., 1988). Regardless of the chloride ion
concentration, the sufficient contact time is around 5 min.
Higher copper extraction at shorter mixing times, and in the pre-
sence of chloride ion, may be attributed to the species activities. At
shorter mixing times, such as 10 and 30 s, the system has not reached
the equilibrium state. As shown in previous sections, the presence of
chloride ion shifts the reaction towards extraction by increasing the
activity of the copper chloride complexes. Accordingly, due to the en-
hanced activity of the species, higher copper extraction in the presence
of chloride ion at shorter mixing times is expected. By increasing the
contact time, the system becomes closer to the equilibrium state, and
the differences in copper extraction, in the presence and absence of
chloride ion, become less pronounced. As was shown in Section 4.1.1,
differences in copper extraction at different chloride concentrations at
pH 2 and equilibrium state was negligible.
In the solvent extraction plants, the aqueous and organic phases are
usually contacted in mixers for at least 3 min. In this study, the copper
extraction efficiency at different chloride concentrations was nearly
Fig. 12. Effects of chloride concentration and contact time on copper extrac-
tion: pH = 2, extractant = LIX 984 (12% v/v), O/A = 1.
S. Shakibania, et al.
Fig. 13. Effects of chloride cocentration and organic extractant on copper ex-
traction: pH = 2, contact time = 10 min, O/A = 1.
constant after 5 min of mixing. Similarly, at around 3 min, the copper
extractions in the presence of chloride at concentrations of 0 and 20 g/L
are almost identical. As a result, any increase in copper extraction due
to the addition of chloride ion at the mixing times below 3 min, is in
fact redundant.
4.1.3. Effect of extractant concentration
The effect of the extractant and chloride ion concentration on the
extraction of copper is shown in Fig. 13. As explained in the previous
sections, increasing chloride concentration results in the conversion of a
significant fraction of cupric to cupric chloride complexes. The chloride
complexation of cupric could potentially somewhat inhibits copper
extraction. As the extractant concentration drops, the driving force to
extract copper decreases. Accordingly, the effect of moderately weak
chloride complexion of cupric, with a simultaneous decrease of the
extraction driving force, has resulted in lower copper extraction in the
presence of chloride ion. As expected, increasing the extractant con-
centration results in higher extraction yield of copper. Further increase
of the extractant concentration over 12% v/v did not significantly affect
the copper extraction. Over this range of extraction concentration, the
effect of chloride concentration in inhibiting the extraction is counter-
balanced by the high extractant concentration.
4.1.4. Extraction stoichiometry
High chloride concentration has little effect on copper extraction at
pH 2 and above, contact times greater than 5 min and extractant con-
centrations above 12% as indicated by the results in Sections 4.1.1,
4.1.2 and 4.1.3. In all of those stated conditions, copper extraction in
the presence of chloride was the same as copper extraction in the ab-
sence of chloride; even in some cases, addition of chloride positively
affected the copper extraction. In this study; however, negative effect of
chloride became apparent at extractant concentrations of < 12%.
Therefore, unlike previous researches (Ruiz et al., 2020, 2019, 2017), it
was concluded that the negative effect of the chloride ions on the
copper extraction is not totally due to the changes in aqueous species
that are generated because of addition of chloride ion. According to
speciation diagrams described in Section 2, in Cl-of 40 g/L, about 25%
of the aqueous copper is in the nonionic form of CuCl2, and also, ad-
dition of chloride results in an increase in the activity coefficient of H+
which was stated to reduce the extraction efficiency. However, no
tangible difference in copper extraction in the presence of chloride was
observed in the above-stated conditions, which showed that cupric is
even readily extracted from Cu+2-chloride complexes into the organic
solution. In contrast, the addition of chloride had a positive impact on
copper extraction at pHs below 2 dues to the relative changes in the H+
and copper species activities. The presence of chloride ions, however,
was shown to have an adverse effect on copper extraction at lower
extractant concentrations. which indicated that there must be another
7
Minerals Engineering 156 (2020) 106498
reason for the negative effect of chloride ions apart from changes in
aqueous species and activities. In previous researches (Ruiz et al., 2020,
2019, 2017), the negative effect of chloride ions on copper extraction
was shown by presenting the equilibrium isotherms graphs but the
reasoning did not seemed justified according to the observations in this
research. Equilibrium isotherms are plotted by differing the ratio of
organic to aqueous solution. Based on this explanation and the obtained
results in previous section, it can be concluded that the negative effect
of chloride ions on copper extraction becomes evident as the changes
are made in the amount of extractant. Therefore, despite the insights
from the previous section on the effect of chloride ion on the extraction
driving forces, copper extraction stoichiometry, in the presence and
absence of chloride ions, were determined.
The presence of the chloride ions in the PLS can change the aqueous
species of copper. The change in copper speciation alters the me-
chanism of copper extraction, respectively. As the chloride concentra-
tion increases, more Cu2+ reacts with Cl−, and more chloro-complexes
of copper are formed. As was discussed in Section 2, as a result of the
addition of chloride ion up to 40 g/L, a significant fraction of cupric
transforms to CuCl+ and CuCl2. Based on Fig. 1, in the approximate
concentration of 18 g/L of chloride, the concentration of the CuCl+
reaches to its maximum value, in which around 60% of the initial Cu2+
has been converted to CuCl+ and this value remains almost constant by
increasing the chloride concentration to 40 g/L. Over the same chloride
concentration, the maximum fraction of CuCl2 is around 0.25, which
based on the results in previous sections, is another extractable species
of copper. Since there are different extractable species of copper in the
concentration of 0–40 g/L of chloride, two mechanisms can be pro-
posed for copper extraction in the absence and the presence of chloride.
The overall extraction mechanism of a cation can be expressed as:
(m + n)
P+n aq + (H2 R2)org = (PRn (HR) m )org + nH+aq
2 (13)
In which is the cation, H2R2 is the organic extractant, n is the
P+aqn
valence of cation and m is the number of the organic molecules in-
volved additionally in the reaction. For determining the mechanism,
H2R2 is considered as the copper extractant since the extractant exists
mainly as the dimer, two molecules of the extractant are involved in the
extracted complex of copper. Fig. 14 shows the schematic of this me-
chanism.
The equilibrium constant of the reaction can be written as:
[H+aq]n × [(PRn (HR) m)org ]
K=
[(H2 R2 )org)]( )
m+n
2 × [P+aqn ]eq (14)
By assuming that the concentration of [(PRn (HR) m)]org equals to
[Porg ]eq , the distribution coefficient is obtained as follows:
[Porg ]eq [(PRn (HR)m )org ]
D= =
[P+aqn ]eq [P+aqn ]eq (15)
By substituting Eq. (15) in Eq. (14), Eq. (14) can be rewritten as:
K × [(H2 R2)org ]( )
m+n
[H+aq]n × D 2
K= D=
[(H2 R2)org)](
m+n
2 ) [H+aq]n
(16)
By taking logarithm from both sides of Eq. (16):
m+n
logD = logK + × log[(H2 R2)org] + n × pH
2 (17)
According to Eq. (17), and at a constant concentration of the ex-
tractant at various pHs, n can be calculated by plotting the log D versus
pH. Similarly, by plotting log D versus extractant concentration, m is
determined by varying the concentration of the extractant at fixed pH.
Based on predominance diagram plotted in Section 2 at chloride ion
concentration of 40 g/L, [Cu2+] = 0.052 M, pH < 5, and Eh above
0.5 V, the dominant species is CuCl+ in a Cu-H2O-Cl system. However,
S. Shakibania, et al. Minerals Engineering 156 (2020) 106498

Fig. 14. Copper extraction by ion exchange chelation (Wilson et al., 2014).

based on the species distribution diagrams, at these conditions, around

15% and 25% of the copper species are Cu2+ and CuCl2, respectively.
Therefore, a sole reaction for the extraction of CuCl+ cannot be de-
termined. In the studied system, pH was below 2.5 and Eh was above
0.55 V. Consequently, data in the concentration range of 0 g/L of
chloride were used to identify the extraction mechanism of Cu2+ and
data in 40 g/L of chloride were used to determine the copper extraction
mechanism from a PLS containing chloride.
Stoichiometric constants for copper extraction reaction, in the pre-
sence and absence of chloride ion, are determined and presented in
plots of Figs. 15–19. An important point to consider in these plots are
the curvature characteristic of the graphs. The reason for this could be
related to the presence of different extractable species of copper, var-
ious organic complexes of copper, and also the effect of varying ex-
tractant concentration. However, to obtain a rough first approximation,
they are all considered as straight lines. Accordingly, the approxima-
tions could be with some errors in determining the stoichiometric
constants.
As shown in Fig. 15 for Cu2+, the plot of log D as a function of pH, at
Fig. 16. Logarithmic relation between Cu+2 distribution ratio and extractant
constant organic extractant concentration, gives a linear line with a concentration.
slope of about 2, which is in agreement with complete ion exchange
extraction of Cu2+. Therefore the “n” coefficient in Eq. (17) for Cu2+ is
2. The plot of log D versus extractant concentration at pH 2 is shown in

Fig. 17. Logarithmic relation between CuCl+, Cu2+ distribution ratio and pH.

Fig. 15. Logarithmic relation between Cu+2 distribution ratio and pH.

8
S. Shakibania, et al. Minerals Engineering 156 (2020) 106498

Fig. 18. Logarithmic relation between CuCl+, Cu2+ distribution ratio and ex-
tractant concentration. Fig. 20. McCabe-Thiele diagram in the absence of chloride ions: aqueous to
organic ratio = 1, pH = 2, extractant = LIX 984N (12 %v/v), contact
time = 10 min.

suggested that the extraction of CuCl2 happens by chelation and then,

similar to Eq. (3), chloride ions are released to the aqueous solution and
copper is extracted as a cupric ion.

4.1.5. Equilibrium isotherm

Fig. 19. Effect of chloride ions on extraction isotherm of copper: pH = 2,
extractant = LIX 984N (12 %v/v), contact time = 10 min.
Fig. 16. The slope of the obtained line is equivalent to m + n , accordingly
2
“m” can be determined, which is equal to 1. As a result, the mechanism
2+
for the extraction of Cu , at the initial copper concentration of 3.3 g/L
at 25 °C with an organic solution of 12% v/v LIX 984N may be pre-
sented as:
3
Cu+2 aq + (H2 R2)org = (CuR2 (HR))org + 2H+aq
2 (18)
Extraction isotherm of copper with LIX 984N in three levels of
chloride ions concentration is plotted in Fig. 19. As shown, the presence
of the chloride ions in the aqueous solution negatively affected the
extraction of copper. Increasing chloride concentration shifted the
equilibrium extraction line to the right that implies an increase in the
extraction stages and the copper concentration in the raffinate solution.
In order to understand the effect of the chloride ions on the solvent
extraction circuit, in Figs. 20 and 21, the McCabe-Thiele diagrams were
plotted for the above-mentioned conditions. The results obtained from
these diagrams are summarized in Table 5. To plot these diagrams, the
operating line (the ratio of organic phase to aqueous or flowrates of
organic to aqueous phase) was assumed 1. It is noteworthy that in the
SX plants, this ratio is often between 0.8 and 1.2; therefore, the average
value of 1 was used here.

Similarly, the same procedure was taken to determine the extraction

stoichiometry of copper from a chloride media. The slope of the log D
vs. pH (Fig. 17) is about 2, which suggests that the copper extraction is
conducted by the release of two protons, which is in agreement with
extraction of the copper as cupric. At a pH of 2, the slope of the log D vs.
extractant concentration line (Fig. 18) is about 2, which indicates m in
the reaction stoichiometry (Eq (17)) to be 2. Therefore, the mechanism
of copper extraction from a PLS containing 40 g/L of chloride can be
shown as:

(1 x y)Cu2+
xCuCl+ + 2(H2 R2)org = (CuR2 (HR) 2 )org + 2H+aq + (x + 2y)Claq
yCuCl 2
(19)
It can be seen that the presence of the chloride resulted in involving
more extractant molecules in the copper extraction, in agreement with Fig. 21. McCabe-Thiele diagram in the presence of chloride ions [Cl−] = 40 g/
Fig. 13. By decreasing the organic concentration, the effect of the L: aqueous to organic ratio = 1, pH = 2, extractant = LIX 984N (12 %v/v),
chloride ions on copper becomes more pronounced. Accordingly, it is contact time = 10 min.

9
S. Shakibania, et al. Minerals Engineering 156 (2020) 106498

Table 5 Table 6
Results obtained from McCabe-Thiele diagrams. Iron extraction at different conditions and chloride concentrations (At room
temperature, time = 10 min, [LIX 984N = 12% v/v).
[Cl-] (g/ No. of Extraction Copper extraction [Cu] in raffinate (g/
L) stages (%) L) [Cl] g/L Extraction [Fe] ppm [Cl] g/L Extraction [Fe] ppm
condition condition
0 2 98.5 0.04
40 2 93.6 0.21 0 pH = 2 17 0 pH = 2 22
40 3 97.5 0.08 O/A = 1 O/A = 2
40 pH = 2 32 40 pH = 2 41
O/A = 1 O/A = 2
0 pH = 1 9 0 pH = 1 12
O/A = 1 O/A = 2
40 pH = 1 21 40 pH = 1 35
O/A = 1 O/A = 2

presence and absence of the chloride ion was presented. It can be seen
that the iron extraction was higher in the experiments where chloride
was presented in solution. Although the addition of chloride ion has
promoted the iron extraction, the selectivity of copper extraction over
iron seems to be still higher.
Wash solution containing 10 g/L of H2SO4 was chosen for our ex-
periments to lower the loss of copper below 1%, and allow a decent
amount of chloride ions to be removed from the loaded organic.

4.2.2. Effect of loaded organic to wash solution ratio

Another factor that can affect the washing stage is wash solution to
loaded organic ratio (WS/LO).At this point, the effect of the WS/LO on
Fig. 22. The effect of the sulfuric acid concentration on the removal of chloride
removal and loss of copper in constant H2SO4 concentration of 10 g/L is
and copper loss during the washing loaded organic: wash solution to loaded
investigated. The results are shown in Fig. 23. Generally, decreasing
organic ratio = 1/7.
WS/LO results in lower removal of chloride and copper loss. The same
outcome was observed here.
The presence of chloride ions resulted in an increase in the con- As an overall conclusion, based on the obtained results, Fig. 24 is
centration of copper in the raffinate, lower extraction of copper, and drawn to depict the effect of the chloride ions on the solvent extraction
eventually an increase in the number of the extraction stages. circuit of copper. Incorporation of salt water through the copper hy-
drometallurgical route could result in significant changes in the solvent
4.2. Washing stage extraction circuit. The number of required extraction stages may be
increased. A washing stage seems to be required to avoid excessive
4.2.1. Effect of the H2SO4 concentration transfer of chloride and iron to the electrolyte. Overall, using seawater
Fig. 22 shows the effect of H2SO4 in the removal of chloride ions and instead of freshwater can considerably resolve the water shortage
copper loss at the constant ratio of wash solution to loaded organic of 1 problem of the mining industries. The operating and capital costs re-
to 7. In order to remove chloride ions from the loaded organic, a higher levant to the desalination process are reduced by incorporating sea-
concentration of the H2SO4 in the wash solution is desirable. However, water in hydrometallurgical processes. However, some additional costs,
by a increase of H2SO4 concentration in a wash solution, more copper such as higher maintenance costs of equipment, will be probably im-
ions are stripped into wash solution and therefore the loss of copper posed by substitution of freshwater with seawater.
increases.
An important feature of Fig. 22 is that the chloride entrainment to
the wash solution increases significantly by increasing sulfuric acid
concentration, which suggests that chloride could enter to the loaded
organic both physically and chemically. A probable reason for the
chloride extraction seems to be its co-extraction with ferric (Fe3+)
chloride complexes. By the addition of the chloride ion to the PLS, a
significant fraction of Fe3+ is converted to different chloride complexes
of ferric, such as FeCl2+ and FeCl2+(Hashemzadeh and Liu, 2020).
These complexes have been shown to be extracted using hydroxyoxime
extractant (Pekkala et al., 1999). Accordingly, fractions of chloride ion
are entrained to the loaded organic by attaching to the ferric ion. The
common iron complex that is known to get extracted to the loaded
organic is FeR2Cl (Pekkala et al., 1999). Accordingly, through washing
stages, this complex seems to get removed from the loaded organic. The
possible reaction for co-extraction and removal of iron and chloride is
as follow:
Extraction
FeCl3 + 2HR FeR2Cl + 2H+ + 2Cl Fig. 23. The effect of the wash solution to loaded organic ratio on the removal
(20)
Washing
of chloride and copper loss during the washing loaded organic:
In Table 6 the extraction of iron at different conditions and in the [H2SO4] = 10 g/L in wash solution.

10
S. Shakibania, et al.
Fig. 24. Scheme of solvent extraction circuit of copper, a) in the absence of chloride ions, b) in the presence of chloride ions.
5. Conclusions
The influence of the chloride ion on solvent extraction of copper
with LIX 984N was investigated. Thermodynamic results showed that
the presence of chloride ions results in the formation of chloro-com-
plexes of copper. In the chloride concentration of 0 to 40 g/L, the
dominance species are Cu2+, CuCl+, and CuCl2. Moreover, by in-
creasing the chloride concentration, the activity of the H+ increases,
which causes the system having more tendency toward stripping.
However, the experimental results showed that solution acidity and
contact time did not significantly changed the copper extraction in the
presence of chloride ion, even, in pH below 2 and shorter contact,
presence of chloride ions had a positive on copper extraction.
Therefore, it was concluded that changes in the aqueous species and
species activity are not the proper justifications for negative effect of
chloride on copper extraction efficiency. Meanwhile, the negative effect
of chloride ions became more significant as the concentration of the
extractant was reduced. Copper extraction was relatively lower in
presence of chloride ions at lower concentrations of extractant. The
addition of chloride ions also had a negative effect on the extraction
isotherms of copper. Slope analysis was applied to determine the ex-
traction stoichiometry. It was shown that the presence of chloride ions
resulted in involving more organic molecules during the extraction
process. Therefore, the synergistic effects of chloride ion through
complexation of cupric and the extent of dimerization was justified to
be the reason for the negative effect of chloride ion on copper extraction
rather than the changes in the type of aqueous species and activities.
The effect of wash stages on the removal of chloride ion from the
loaded organic and copper loss was investigated. Under the optimum
conditions of wash to loaded organic ratio of 1 to 7, and H2SO4 con-
centration of 10 g/L, the chloride ions were effectively removed from
the loaded organic at copper loss below 1%. Also, it was shown that a
fractions of chloride ion are entrained to the loaded organic chemically
by attaching to the ferric ion.
CRediT authorship contribution statement
Sina Shakibania: Conceptualization, Methodology, Investigation,
Writing - original draft, Formal analysis. Alireza Mahmoudi:
Investigation, Methodology, Data curation, Writing - review & editing.
Mohammad Mokmeli: Conceptualization, Data curation, Writing -
11
Minerals Engineering 156 (2020) 106498
review & editing, Funding acquisition, Supervision. Fereshteh
Rashchi: Data curation, Writing - review & editing, Supervision.
Declaration of Competing Interest
The authors declare that they have no known competing financial
interests or personal relationships that could have appeared to influ-
ence the work reported in this paper.
Acknowledgements
The authors are thankful to National Iranian Copper Industries Co.
for their financial support of this project.
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