metals

Article
Chalcopyrite Leaching with Hydrogen Peroxide and Iodine
Species in Acidic Chloride Media at Room Temperature:
Technical and Economic Evaluation
Germán A. Moraga, Nathalie E. Jamett , Pía C. Hernández , Teófilo A. Graber and María E. Taboada *

Departamento de Ingeniería Química y Procesos de Minerales, Universidad de Antofagasta, Av. Angamos 601,
Antofagasta 1240000, Chile; german.moraga.villaroel@ua.cl (G.A.M.); nathalie.jamett@uantof.cl (N.E.J.);
pia.hernandez@uantof.cl (P.C.H.); teofilo.graber@uantof.cl (T.A.G.)
* Correspondence: mariaelisa.taboada@uantof.cl; Tel.: +56-55-637345






Citation: Moraga, G.A.; Jamett, N.E.;
Hernández, P.C.; Graber, T.A.;
Taboada, M.E. Chalcopyrite Leaching
with Hydrogen Peroxide and Iodine
Species in Acidic Chloride Media at
Room Temperature: Technical and
Economic Evaluation. Metals 2021, 11,
1567. https://doi.org/10.3390/
met11101567
Abstract: In Chile, the hydrometallurgical plants are operating below their capacity due to a depletion
of copper oxide ores. To obtain suitable pregnant leach solutions (PLSs) for hydrometallurgical plants,
leaching solutions combining iodine-based oxidants and hydrogen peroxide in a chloride–acid
medium, at room temperature and pressure were studied. Factorial experiments were conducted to
evaluate the effects of the different leaching solution reagents (KI, NaIO3 , NaCl, H2 O2 , and H2 SO4 ).
The results showed that the most influential variable is the H2 O2 concentration; increasing the
PLS concentration from 3 g/L to 15 g/L increased the copper extraction percentage by ~25%. In
decreasing order of importance, the factorial experimental results showed that the H2 O2 , H2 SO4 ,
NaCl, NaIO3 , and KI concentrations affect the copper extraction percentage. The highest copper
extraction percentage (i.e., 60.6%) was obtained using a leaching solution containing the highest
reagent concentrations. At these conditions, the copper concentration in the PLS was 16.9 g/L. An
economic evaluation of the laboratory-scale leaching experiments showed an increase in the unit
cost (USD/t Cu) for experiments involving leaching solutions without H2 O2 because of poor copper
concentration in the PLS. As the concentrations of the reagents NaIO3 and KI, increase, the unit
cost increases, because the reagents are relatively expensive and have a limited effect on the copper
extraction percentage.
Keywords: chalcopyrite; leaching; chloride; iodine; peroxide; oxidant; copper

Academic Editor: Jean François Blais

Received: 3 August 2021 1. Introduction

Accepted: 24 September 2021
Copper in the earth’s crust occurs as native copper or copper-bearing minerals such
Published: 30 September 2021
as copper sulfides (e.g., chalcopyrite, chalcocite, covellite, bornite, and enargite) and
copper oxides (e.g., cuprite, tenorite, chrysocolla, atacamite, and brochantite). Of these,
Publisher’s Note: MDPI stays neutral
chalcopyrite is the most abundant, accounting for 70% of all copper-bearing minerals in
with regard to jurisdictional claims in
the earth’s crust [1]; however, most current reserves contain approximately 0.5% copper
published maps and institutional affil-
and are steadily depleting [2].
iations.
Copper oxide and copper sulfide ores are typically processed in hydrometallurgical
and concentrator plants, respectively. However, because of the nature of mineral deposits
and the deepening pits, copper sulfide ore extraction is increasing, whereas copper oxide ore
extraction is decreasing [3,4]. According to Cochilco, Comisión Chilena del Cobre [5], the
Copyright: © 2021 by the authors.
hydrometallurgical production of copper in Chile will decrease by 52% by 2030 compared
Licensee MDPI, Basel, Switzerland.
to the production in 2018. Owing to the scarcity of leaching resources and no new projects
This article is an open access article
in this area, it is estimated that approximately 15 Chilean hydrometallurgical plants will be
distributed under the terms and
closed before 2030 [6].
conditions of the Creative Commons
According to some studies [7–9], concentrator–refinery plants are characterized by
Attribution (CC BY) license (https://
higher operational costs and processes that require more complex equipment than those
creativecommons.org/licenses/by/
4.0/).
in hydrometallurgical plants. Hydrometallurgical processes are less energy-intensive,

Metals 2021, 11, 1567. https://doi.org/10.3390/met11101567 https://www.mdpi.com/journal/metals

Metals 2021, 11, 1567 2 of 17

more suitable for low-grade ore, and have a lower environmental impact due to the lack
of SO2 generation. For these reasons, the heap leaching of copper sulfide ore has been
extensively explored. The choice of an optimal lixiviant depends primarily on the mineral-
ogy of the ore [10]; however, in general, the leaching of sulfide minerals is conducted in
an oxidizing environment using chemical reagents such as sulfates, chlorides, ammonia,
nitrates, and ozone, in combination with high temperatures and pressures. In some cases,
the sulfide ore is pretreated [4,9,11–15]. Some sulfate-media-based technologies, in the pilot
or commercial stages of implementation, are total pressure oxidation (POX; high pressure
and temperature), direct EW and SX (MT-DEW-SX), and BioSigma bioleaching (involving
leaching bacteria). In chloride media, technologies include the Cuprochlor process, the
CESL copper process (under high pressure and temperature), and hydrocopper technol-
ogy (employing agitated reactors) [6]. In order to process primary sulfide ores, all these
technologies use increased temperature, or pressure in some cases, to optimize the cop-
per extraction and overall residence time. The Chilean Copper Corporation (CODELCO)
estimated that, for the next ten years, low-grade chalcopyrite would represent over 80%
of copper resources [15]. The slow kinetics of chalcopyrite leaching is considered a conse-
quence of forming a passivation layer that inhibits the dissolution of copper, causing poor
copper extractions [15,16].
Conditions such as high temperature and pressure are difficult to implement and
operate at a large scale in the existing facilities of traditional copper mine industries. For this
reason, this study aims to develop an alternative leaching process to treat copper sulfide
concentrate that yields suitable pregnant leach solutions (PLSs) for SX–EW processes,
minimizing changes in the current installations.
The basis of the leaching solution is a combination of salts, such as potassium iodide
(KI), sodium iodate (NaIO3 ) (both produced in the north of Chile), and hydrogen peroxide
(H2 O2 ) in a chloride–acid medium at room temperature.

2. Mechanisms
Hydrogen peroxide is a well-known powerful oxidant. Reaction (1) shows its decom-
position reaction into water and oxygen:

2H2 O2 → 2H2 O + O2 E◦ = 0.492 V (1)

Hydrogen peroxide reacts with iodide. In the literature, three mechanisms that de-
scribe the transformation of iodine species reacting with hydrogen peroxide in acidic media
have been reported. The nonradical mechanisms were postulated by Liebhafsky [17,18] and
Schmitz [19], and the radical mechanism was proposed by Noyes [20]. The decomposition
of hydrogen peroxide using iodide may seem simple; however, the reaction occurs through
a series of intermediates such as I2 , I3 − , and short-lived intermediates such as HIO, OH·,
and OOH· [21]. The overall peroxide decomposition reaction equations involving iodide
and iodate are expressed in Reactions (2) and (3), respectively:

H2 O2 + 2I− + 2H+ → I2 + 2H2 O E◦ = 1.141 V (2)

5H2 O2 + 2IO3− + 2H+ → I2 + 5O2 + 6H2 O E◦ = 2.083 V (3)

The complete transformation of iodide to iodine is possible at sufficiently high con-
centrations of acid [22]; however, the concentration of iodide ions will always be governed
by the equilibrium of Reaction (4):

I2 + I− ↔ I3− E◦ = 0.082 V (4)

In the absence of hydrogen peroxide, iodide also reacts in acidic media, oxidizing to
produce iodine and water. See Reaction (5) [23]:

IO3− + 5I− + 6H+ → 3I2 + 3H2 O E◦ = 0.477 V (5)

Metals 2021, 11, 1567 3 of 17

Considering the fast kinetics of the reaction of Reaction (4), Reaction (5) can also be
described using Reaction (6):

IO3− + 8I− + 6H+ → 3I3− + 3H2 O E◦ = 0.559 V (6)

On the other hand, the use of iodide in the leaching of gold-bearing materials has
been extensively studied. Old technologies such as roasting and smelting pose severe
environmental risks; consequently, lixiviants such as thiourea, thiosulfate, and halide
(chloride, bromide, and iodide) systems have been researched.
Iodide-based gold leaching is a nontoxic cyanide-free process and involves the for-
mation of stable gold–iodide complexes. It is understood that, under general conditions,
iodine dissolves in the presence of iodide to form triiodide ions, which oxidize elemental
gold to produce gold(I)–iodide complexes [24–26].
Over the last decade, several studies have focused on copper sulfide ore leaching,
specifically, on refractory copper ores such as chalcopyrite. Studies of oxidizing agents
used to enhance chalcopyrite leaching and prevent the formation of a passivation layer
show that the redox potential is a very important variable in establishing a potential range
in which chalcopyrite is not passivated [27]. The use of iodine as an oxidant in the leaching
of copper sulfide ores was studied by Granata et al. [28]. The proposed mechanism is
a two-step cyclic process in which ferric ions oxidize iodide to iodine (see Reaction (7)),
which, in turn, oxidizes chalcopyrite according to Reaction (8):

2I− + 2Fe+3 = I2 + 2Fe+2 E◦ = 0.074 V (7)

CuFeS2 + 2H2 SO4 + 2I2 = CuSO4 + FeSO4 + 4HI + 2S0 E◦ = 0.164 V (8)
Following this two-step process, the iodide is reoxidized to initiate a new cycle of
reactions. The effects of ferric ion concentration, temperature, and iodide concentration on
chalcopyrite leaching were investigated. It was found that after eight hours of leaching at
room temperature in 0.5 g/L of iodide, the copper extraction increased from <10% to ~40%
for the ore with a size fraction of 45 µm. When the temperature was increased to 50 ◦ C,
copper extraction reached 60%. Winarko et al. [29] studied the effect of different parameters
on the kinetics of copper extraction in the presence of iodine. The experimental results
showed that redox potential was the principal factor determining the leaching performance
via controlling the iodine speciation.
Furthermore, Manabe [30] patented a leaching process conducted at room temperature
and atmospheric pressure, in which the acidic leaching solution contained ferric ions,
iodide, and chloride. The number of ferric ions in the leaching solution must exceed the
amount of iodide by a factor of 23–120. Similarly, the amount of chloride in the leaching
solution must exceed the number of ferric ions by a factor of 0.1–2.3. Maximum extraction
of ~70% was achieved in a leaching solution containing 100 mg/L of iodine, 12 g/L of Fe+3 ,
and 20 g/L of Cl− , with a pH equal to 1.5 after 20 days of leaching the copper concentrate.
Later, Sato and Manabe [31] patented a two-step leaching process for mixed sulfide
copper ores at room temperature. In this process, the first stage, copper oxides and
secondary sulfides copper ores are leached based on an oxidative leaching reaction using
Fe+3 . Then, in a second step, primary copper sulfide ores are leached by a solution
containing additional iodine at low concentrations. The concentration of iodide ions to be
added is 50 to 300 mg/L and preferably 50 to 100 mg/L.
Kawashiro and Miura [32] described a similar process in which the leaching solution
contained 100 mg/L iodine and 5 g/L iron with a pH of 1.8. The process included a
recovery step to minimize iodine loss.
In this study, ferric ions were not added to the leaching solution; however, the oxidation
of iodide was achieved by adding hydrogen peroxide, according to Reactions (2) and (3).
The mechanism proposed for chalcopyrite leaching is promoted by the action of several
oxidants, such as triiodide, resulting from iodide/iodate oxidation, oxygen generation
from peroxide decomposition, and ferric ion liberation through chalcopyrite dissolution.
Metals 2021, 11, 1567 4 of 17

Effects of PLS conditions (i.e., temperature and potential) and concentration in the
following stages, such as solvent extraction and electrowinning, have been studied [33–38].
In solvent extraction, operational problems such as degradation of the extractants, diluents,
crud formation, and phase trapping could be produced. In the electrowinning stage, the
generation of contaminating gases, a decrease in the current density, and corrosion are the
main problems in processing chloride solutions. Concerning copper solvent extraction,
there is no consensus, and diverse conclusions can be found. Lu and Dreisinger [39]
studied the copper extraction for four LIX extractants (LIX84-I, LIX612N-LV, XI-04003, and
LIX984N); it was concluded that the copper extraction was sensitive to pH below 0.5 and
was not affected by impurities except for Fe (III). Later, Lu and Dreisinger [40] proposed a
novel process for copper recovery by chloride leaching and cupric solvent extraction, and a
conventional sulfate electrowinning circuit. Yañez et al. [41] studied the chemical behavior
of oximes (ketoxime LIX84I and modified aldoxime LIX684N-LV) both with and without
chloride in the PLS. The authors found improvements in the behavior of the oximes at
low pH in a chloride media, having positive effects on copper loaded in organic and in
the extraction kinetics. The ketoxime extractant presented a better performance than the
modified aldoxime.
Conversely, Ruiz et al. [42] reported a negative effect of chloride on the copper ex-
traction equilibria using ketoxime (LIX 84-IC) or salicylaldoxime (LIX 860 N-IC). An
improvement in extraction was found when the temperature was increased from 25 to
35 ◦ C. Later, Ruiz et al. [43] studied the effects of chloride on extraction, using ketoxime
(LIX 84-IC) and nonylaldoxime (LIX 860N-IC) extractants to elucidate the reasons for
these negative effects on the extraction. The presence of chloride had a large effect on
the extraction equilibria with the ketoxime and a small negative effect when the nony-
laldoxime was used. This deleterious effect is attributed to an increase in the hydrogen
ion activity, which decreases the equilibrium pH. Similar results were obtained using a
mixed ketoxime–nonylaldoxime (LIX 984N) and an ester-modified nonylaldoxime (Acorga
M5910) extractant [44]. Shakibania et al. [45] studied the chloride effect on the copper
extraction also with a mixed ketoxime–nonylaldoxime (LIX 984 N) extractant. The chlo-
ride addition showed a positive impact on extraction at low pH and improvement in
the kinetic. Still, it negatively affected the extraction isotherms due to a decrease in the
extraction-driven forces.
One major concern on the processing solutions with high chloride concentrations
(more than 30 ppm) is the corrosion by the pitting of stainless-steel cathodes. Additionally,
a decrease in the number of free cupric nuclei, the decrease of the adhesive strength of
the copper deposit, and the increase in the current density are the main issues in the
electrowinning stage. For these reasons, washing stages were proposed to control these
undesired effects [45]. For example, Zhu et al. [46] proposed two successive scrubbing
stages in a synergistic solvent extraction process for chloride solutions to avoid electrolyte
contamination in the electrowinning stage. In Fletcher et al. [47], the effectivity of the
loaded organic washing without the loss of copper was analyzed. The results indicated
that the copper presented a chloride complex that was bonded as a copper cation into the
extractant reagent after the wash.
On the other hand, the requirement of iodide salts in the process is relatively low, and
the effects of iodide ions at these concentrations in the solvent extraction or electrowinning
stages have not been reported. There are some concerns related to possible iodine losses to
the ambient affecting the operational costs of the process. Granata et al. [28] mentioned the
requirement of recovery stages after the leaching stage due to the KI cost. Kuwano et al. [48]
proposed a new process that includes the recovery of the iodide reagents. After the leaching
stage of copper sulfide ores, the copper from the pregnant solution is recovered in a solvent
extraction stage. The remaining raffinate is sent to an oxidizing process, and the produced
iodine is recovered in an adsorption process with activated carbon.
Metals 2021, 11, 1567 5 of 17

In conclusion, there is no consensus on the effect of chloride in copper solvent extrac-

tion, and further studies should be done. Washing stages must be included in any design
of the hydrometallurgical process considering copper chloride solutions.

3. Materials and Methods

3.1. Concentrate Characterization
Copper concentrate was used in the experiments. The samples were characterized
by scanning electron microscopy (QEMSCAN, Model Zeiss EVO 50, Zeiss, Oberkochen,
Germany) and X-ray diffraction (XRD) (XRD-7000 Shimadzu, Shimadzu Corporation,
Kyoto, Japan). The total copper concentration was determined by atomic absorption
spectrometry (AAS) (AA-6880 Shimadzu), and soluble copper was also quantified by AAS
after leaching the sample in sulfuric acid at 5%.
The mineral characterization results are shown in Table 1. The total copper con-
centration was 29% (w/w), and the soluble copper concentration was 0.78% (w/w). The
concentrate particle size corresponds to 69.4% -325# Tyler, measured with an FBRM probe
(Mettler Toledo).
Table 1. Mineral characterization of the copper concentrate.

Mineral Amount (w/w%)

Digenite 3.30
Covellite 0.80
Chalcopyrite 63.70
Enargite 1.20
Tennantite 0.02
Bornite 6.40
Pyrite 16.40
Molybdenite 0.30
Hematite 0.10
Limonite 0.04
Gangue 7.30
Sphalerite 0.20
Pyrargyrite 0.10
Magnetite 0.10

3.2. Procedure of the Leaching Experiments

3.2.1. Effects of Hydrogen Peroxide on the Extraction of Copper during
Concentrate Leaching
Leaching experiments were conducted in 1000 mL flasks. Copper concentrate (100 g) was
added to the leaching solution, and the flasks were sealed with a film to avoid evaporation.
A mechanical stirrer, IKA RW 20, was used to stir the suspension at 500–600 rpm.
Samples (in duplicate) were collected every 15 min for the first hour. Subsequently, samples
were collected after 6, 24, 48, and 96 h of leaching. All the experiments were carried out at
room temperature (18–20 ◦ C).
Four leaching solutions were used in the experiments. The concentrations of the
reagents used are listed in Table 2.
Table 2. Leaching solution composition.

Leaching Solution
Reagent A B C D
(M) (g/L) (M) (g/L) (M) (g/L) (M) (g/L)
NaCl 0.00 0.00 1.54 90.00 0.00 0.00 1.54 90.00
NaIO3 0.00 0.00 0.03 6.20 0.00 0.00 0.03 6.20
KI 0.00 0.00 0.04 6.50 0.00 0.00 0.04 6.50
H2 O2 0.00 0.00 0.00 0.00 0.09 3.00 0.44 15.00
H2 SO4 0.05 5.30 0.27 26.30 0.05 5.30 0.27 26.30
Metals 2021, 11, 1567 6 of 17

Leaching experiments were performed using leaching solutions A and B (i.e., without
hydrogen peroxide). Leaching solutions C and D additionally contained 3 g/L and 15 g/L
hydrogen peroxide, respectively. In all experiments, the copper concentrations in the PLS
were determined as a function of time.

3.2.2. Effect of Iodide, Hydrogen Peroxide, and Chloride on the Extraction of Copper
during Concentrate Leaching
Leaching experiments were designed based on the 2k factorial design. The variables
analyzed and their levels are shown in Table 3. The variables included in the design matrix
were pH (H2 SO4 concentration) and the concentrations of iodine (KI and NaIO3 ), hydrogen
peroxide (H2 O2 ), and chloride (NaCl). The iodide concentrations were determined accord-
ing to the relation between the iodide and copper content in the concentrate. According to
the literature [30,49], the relation KI/Cuconcentrate (i.e., using mol concentration) can vary
from 0.053 to 0.028. In this study, the ratio was 0.03. The leaching ratio of all experiments
was 10 m3 /t, according to previous leaching tests [27,50]. This leaching rate was lower
than the one used in patents [30], leading to higher iodine species concentration in the
leaching solutions.
Table 3. Factors included in the experimental design and their levels.

Low Level High Level

Factor
(M) (g/L) (M) (g/L)
NaCl 0.00 0.00 1.54 90.00
NaIO3 0.00 0.00 0.01 2.00
KI 0.00 0.00 0.01 2.30
H2 O2 0.09 3.00 0.44 15.00
H2 SO4 0.05 5.30 0.27 26.30

Minitab (v.18) statistical software was used in the experimental design and the analysis
of the results. In total, 32 leaching experiments were performed in duplicate. The copper
concentration in the PLS was determined after 45 min of stirring, (i.e., the time needed to
reach the steady state in the experiments described in Section 3.2.1). All the experiments
were carried out at room temperature (18–20 ◦ C) and atmospheric pressure.

4. Results
4.1. Effect of Hydrogen Peroxide Concentration on Copper Extraction during Concentrate Leaching
The results of the leaching experiments in the presence and absence of hydrogen
peroxide are shown in Table 4 and Figure 1.
Table 4. Experimental results for leaching performed in the presence and absence of hydrogen peroxide.

Cu Extraction (%)
Leaching Time (h) Leaching Leaching Leaching Leaching
Solution A Solution B Solution C Solution D
0.25 1 1.9 3.8 12.5
0.5 1.6 3 11.1 41.6
0.75 1.7 3.7 16.2 55.1
1 2.2 4.5 15.3 54.8
6 4.2 9 17.4 57.1
24 6.2 12 16 58.7
48 7.1 15.3 15.5 58.5
96 9.3 19.4 17.3 60.2
 0.5 1.6 3 11.1 41.6
0.75 1.7 3.7 16.2 55.1
1 2.2 4.5 15.3 54.8
6 4.2 9 17.4 57.1
Metals 2021, 11, 1567
24 6.2 12 16 58.7 7 of 17
48 7.1 15.3 15.5 58.5
96 9.3 19.4 17.3 60.2

Figure1.
Figure 1. Effect
Effect of
of hydrogen
hydrogenperoxide
peroxideon
oncopper
copperextraction.
extraction.

In the absence of hydrogen peroxide, low extraction percentages, less than 10% after
In the absence of hydrogen peroxide, low extraction percentages, less than 10% af-
six hours of leaching, were achieved. Adding the reagents NaCl, KI, and NaIO3 and
ter six hours of leaching, were achieved. Adding the reagents NaCl, KI, and NaIO3 and a
a higher acid concentration slightly increased copper extraction from 4.2% to 9% after
higher acid concentration slightly increased copper extraction from 4.2% to 9% after six
six hours of leaching. In experiments using leaching solutions without peroxide, the steady
hours of leaching. In experiments using leaching solutions without peroxide, the steady
state was not reached after 96 h of leaching.
state was not reached after 96 h of leaching.
Adding 3 g/L of hydrogen peroxide to the leaching solution increased the copper
Adding 3 g/L of hydrogen peroxide to the leaching solution increased the copper
extraction from 4.2% to 17.4% (solutions A and C, respectively). In a solution containing
extraction from 4.2% to 17.4% (solutions A and C, respectively). In a solution containing
iodine and chlorine species and a high acid concentration, the effect of peroxide was
iodine and chlorine species and a high acid concentration, the effect of peroxide was sig-
significant, increasing the extraction from 9% (solution B) to 57.1% (solution D) after
nificant, increasing the extraction from 9% (solution B) to 57.1% (solution D) after six
six hours of leaching.
hours of leaching.
4.2. Effects of Iodide, Hydrogen Peroxide, and Chloride on the Extraction of Copper during
4.2. Effects of
Concentrate Iodide, Hydrogen Peroxide, and Chloride on the Extraction of Copper during
Leaching
Concentrate Leaching
The results from the factorial experiments are shown in Table 5. These results were
statistically evaluated.
The results from the factorial experiments are shown in Table 5. These results were
statistically evaluated.
4.2.1. Analysis of the Pareto Chart of Effects
The Pareto chart allows detecting the most influential factor and interaction effect
in the leaching process based on the copper extraction results. It displays the absolute
value of the standardized effects of different factor combinations in decreasing order. The
standardized effects are t-statistics that test the null hypothesis that the effect is zero [51].
The chart also plots a reference line to indicate which effect is statistically significant. In
order of importance, the most influential factors in the leaching experiments were the
concentrations of hydrogen peroxide, sulfuric acid, sodium chloride, sodium iodate, and
potassium iodide. Figures 2 and 3 show that the hydrogen peroxide concentration is the
most influential variable in the leaching process and, on average, increases the overall
extraction by approximately 25%. The same order of importance was obtained when the
evaluated response was the PLS copper concentration (g/L).

4.2.2. Analysis of the Main Effects

In Figure 3, the plots for the main effect exhibit the mean extraction and the mean
copper concentration in the PLS, determined for each concentration (level) of the analyzed
factors. A line connects each mean value. Horizontal lines represent the low effect of
factors on the response (i.e., extraction or copper concentration). On the other hand, the
Metals 2021, 11, 1567 8 of 17

lines that are not horizontal represent an effect on the response. The slopes of the lines
represent the magnitude of the effect.
Table 5. Results for experiments based on the 2k factorial design.

NaCl NaIO3 KI H2 O2 H2 SO4 Cu Extraction Cu

Test
(g/L) (g/L) (g/L) (g/L) (g/L) (%) (g/L)
1 0 0 0 3 5.3 16.6 4.8
2 90 0 0 15 26.3 55.1 16.0
3 90 0 2.3 3 5.3 22.4 6.5
4 90 2 0 3 5.3 23.0 6.7
5 90 2 0 15 26.3 59.1 17.1
6 90 2 2.3 3 26.3 37.2 10.8
7 0 2 2.3 15 5.3 46.3 13.4
8 90 0 2.3 3 26.3 34.0 9.9
9 0 0 2.3 3 26.3 29.6 8.6
10 90 2 0 15 5.3 49.0 14.2
11 90 0 0 3 5.3 19.8 5.8
12 0 2 0 15 26.3 55.2 16.0
13 90 0 2.3 15 5.3 49.4 14.3
14 0 2 2.3 3 26.3 33.8 9.8
15 0 2 2.3 15 26.3 59.1 17.1
16 0 2 2.3 3 5.3 23.1 6.7
17 0 0 2.3 3 5.3 19.6 5.7
18 0 2 0 15 5.3 46.6 13.5
19 90 0 0 15 5.3 45.4 13.2
20 0 2 0 3 5.3 20.1 5.8
21 0 2 0 3 26.3 31.0 9.0
22 0 0 0 3 26.3 28.6 8.3
23 0 0 0 15 26.3 52.4 15.2
24 0 0 0 15 5.3 41.3 12.0
25 90 2 2.3 15 5.3 52.0 15.1
26 90 2 2.3 15 26.3 60.6 17.6
27 90 0 2.3 15 26.3 58.4 16.9
28 0 0 2.3 15 26.3 54.0 15.6
29 90 2 0 3 26.3 35.4 10.3
30 90 2 2.3 3 5.3 25.8 7.5
Metals 2021, 11, x FOR PEER REVIEW 31 90 0 0 3 26.3 32.5 9 of 9.4
18
32 0 0 2.3 15 5.3 43.3 12.6

Figure 2.
Figure 2. Pareto
Paretochart
chartofofeffects.
effects.
Metals 2021, 11, 1567 9 of 17
Figure 2. Pareto chart of effects.

(a)

(b)
Figure
Figure 3.
3. Main
Maineffect
effect plots.
plots. (a)
(a)Main
Maineffects
effects on
on %
% Extraction
Extraction as
as response.
response. (b)
(b) Main
Main effects
effects on
on Cu
Cu concentration
concentration in
in PLS.
PLS.
Figure 3a shows that the hydrogen peroxide concentration has the most significant
4.2.2. Analysis of the Main Effects
effect on the leaching process, increasing the average extraction by ~25% when the con-
In Figure
centration 3, the plots
is increased fromfor the main
3 g/L effectInexhibit
to 15 g/L. theincreasing
contrast, mean extraction
the acidand the mean
concentration
copper
from 5.26 g/L to 26.32 g/L increases the copper extraction by only 10%. The the
concentration in the PLS, determined for each concentration (level) of ana-
effect of
lyzed factors. A line connects each mean value. Horizontal lines represent the
NaCl, KI, and NaIO3 concentration on copper extraction is negligible, with less than 5% low effect
of factors on the
improvement response
between the (i.e.,
minimumextraction or copper of
and maximum concentration). On the other hand,
the reagent concentration.
The copper concentrations in the PLS strongly depend on the hydrogen peroxide
content of the leaching solution (Figure 3b). The Cu concentration increases from 8 g/L to
15 g/L when the hydrogen peroxide concentration in the leaching solutions is increased
from 3 g/L to 15 g/L. Increasing the acid concentration from 5.3 g/L to 26.3 g/L increases
the copper concentration from 10 g/L to 13 g/L. The remaining reagents do not significantly
affect the copper concentrations in the PLS.
The maximum extraction (i.e., 60.6%) and maximum copper concentration in a PLS
(17.6 g/L) are achieved using the leaching solution containing the highest reagent concentrations.

4.2.3. Analysis of the Interaction Plot

The interaction plot shows the dependence between two factors on a response. In this
case, the response is copper extraction.
Parallel lines indicate no interaction between the factors, while the degree of inter-
action increases as the difference between the slope lines increases. Figure 4 shows no
interaction between the factors analyzed; therefore, there is no dependence between the
factors affecting copper extraction.

Metals 2021, 11, 1567
4.2.3. Analysis of the Interaction Plot
The interaction plot shows the dependence between two factors on a response. In
this case, the response is copper extraction.
Parallel lines indicate no interaction between the factors, while the degree of inter-
action increases as the difference between the slope lines increases. Figure 4 shows 10 of no
17
interaction between the factors analyzed; therefore, there is no dependence between the
factors affecting copper extraction.

Figure 4.
Figure 4. Interaction
Interaction plot.
plot.

4.2.4.
4.2.4. Analysis of the Bubble
Bubble Chart
Chart
Metals 2021, 11, x FOR PEER REVIEW
Figure
Figure 55 shows
shows the
theoverall
overalleffect
effectof
ofthe
theadded
addedreagent
reagentconcentrations
concentrations(H
(H2O
2O2 ,2,H22SO
H11SO 4,
of 418
KI, NaIO
KI, NaIO33, and NaCl) on copper extraction during the leaching experiments. The size
on copper extraction during the leaching experiments. The size of of
the
the bubble
bubble represents
represents the
the copper
copper extraction
extractionpercentage.
percentage.

Figure 5.5. Representation

Figure Representation of
of the
the effects
effects of
of reagents
reagents as
as aa function
function of
ofhydrogen
hydrogenperoxide
peroxideand
andacid
acid
concentrations during copper extraction.
concentrations during copper extraction.
The
Thedark-gray
dark-graybubbles represent
bubbles the extraction
represent achieved
the extraction in leaching
achieved solutionssolutions
in leaching without
reagents KI, NaIO3 , and NaCl, as a function of the acid and hydrogen peroxide concentra-
without reagents KI, NaIO3, and NaCl, as a function of the acid and hydrogen peroxide
tions. The lowest extraction is obtained at the lower concentrations of acid (5.3 g/L) and
concentrations. The lowest extraction is obtained at the lower concentrations of acid (5.3
hydrogen peroxide (3 g/L). Increasing the acid concentration in the leaching solution to
g/L) and hydrogen peroxide (3 g/L). Increasing the acid concentration in the leaching
26.3 g/L increases the extraction from 17% to 29%, while increasing the hydrogen peroxide
solution to 26.3 g/L increases the extraction from 17% to 29%, while increasing the hy-
concentration to 15 g/L increases the extraction from 17% to 41%. Finally, increasing both
drogen peroxide concentration to 15 g/L increases the extraction from 17% to 41%. Fi-
the acid and peroxide concentrations increases the extraction to 52%.
nally, increasing both the acid and peroxide concentrations increases the extraction to
52%.
The addition of KI, NaIO3, and NaCl to the leaching solutions (represented by
light-gray bubbles) in concentrations of 2.3 g/L, 2 g/L, and 90 g/L, respectively, increases
the copper extraction by ~50% at low concentrations of acid and hydrogen peroxide. As
the concentration of acid and hydrogen peroxide increases, the copper extraction in-
Metals 2021, 11, 1567 11 of 17

The addition of KI, NaIO3 , and NaCl to the leaching solutions (represented by light-
gray bubbles) in concentrations of 2.3 g/L, 2 g/L, and 90 g/L, respectively, increases
the copper extraction by ~50% at low concentrations of acid and hydrogen peroxide.
As the concentration of acid and hydrogen peroxide increases, the copper extraction
increases to ~25%. In the case of the leaching solution containing maximum acid and
peroxide concentrations, the extraction increases to 17%. Summarizing, the leaching
solution containing 90 g/L NaCl, 2 g/L NaIO3 , 2.3 g/L KI, 26.3 g/L H2 SO4 , and 15 g/L
H2 O2 maximizes copper extraction (61%) after 45 min of leaching.

5. Economic Evaluation
This section presents a simplistic cost evaluation to support the discussion [52,53]. The
operational costs of the leaching experiments depend on factors such as the concentration
and price of the reagents used, as well the electricity and water consumption. Only the
reagent consumption is considered in this evaluation because other economic factors do not
vary between experiments. Table 6 shows the prices of the reagents used in the evaluation,
according to the Chilean market.
Table 6. Reagent prices used in the economic evaluation.

Reagent Price (USD/t)

H2 SO4 98% w/w 250
H2 O2 50% w/w 1000
NaIO3 30,000
KI 10,000
NaCl 50

The unit cost per ton of the extracted copper is determined using Equation (9), where
Ck is the concentration of reagent k, Vsol is the volume of the leaching solution, Pk is the
reagent price, and CCu is the copper concentration in the PLS.

∑ Ck ·Vsol ·Pk
Unit Cost = (9)
CCu ·Vsol

Table 7 lists each experiment and its associated unit cost based on the corresponding
reagent consumption. Unit costs vary from 0.89 USD/t Cu to 13.06 USD/t Cu.
Table 7. Unit costs of leaching experiments.

NaCl NaIO3 KI H2 O2 H2 SO4 Unit Cost

Subsets
(g/L) (g/L) (g/L) (g/L) (g/L) (US$/t Cu)
90 2 2.3 3 26.3 9.0
0 2 2.3 3 26.3 9.4
0 2 2.3 3 5.3 13.1
90 2 2.3 3 5.3 12.3
0 2 0 3 5.3 11.0
HC-LE
90 2 0 3 5.3 10.3
0 2 0 3 26.3 7.7
90 2 0 3 26.3 7.2
0 0 2.3 3 5.3 4.8
90 0 2.3 3 5.3 4.9
0 2 2.3 15 26.3 6.1
90 2 2.3 15 26.3 6.2
90 2 2.3 15 5.3 6.9
0 2 2.3 15 5.3 7.4
HC-HE
90 2 0 15 26.3 5.0
0 2 0 15 26.3 5.1
90 2 0 15 5.3 5.7
0 2 0 15 5.3 5.7
Metals 2021, 11, x FOR PEER REVIEW 13 of 18

peroxide concentrations, explaining the low copper extraction percentages. The addition
Metals 2021, 11, 1567 12 of 17
of NaCl, KI, and NaIO3 significantly increases the unit costs.
On the other hand, subset LC-HE represents experiments with a low cost and high
extraction. The average unit cost in this subset is 2.2 USD/t Cu, and the average extrac-
tion is
Table 50%. These experiments include high concentrations of hydrogen peroxide. In
7. Cont.
cases with the lowest unit cost, the concentrations of KI and NaIO3 are zero. The maxi-
mum extractionNaCl
Subsets percentageNaIOachieved
3 KI subset His2 O58.4%,
in this 2 H2 SOa4 unit Unit
with cost Cost
of 2.9
(g/L) (g/L) (g/L) (g/L) (g/L) (US$/t Cu)
USD/t.
The experiments 90 in subset0 HC-HE are2.3 characterized 3 by high extraction
26.3 3.8
percentages
and high unit costs, 0 with an average
0 2.3
approximately three3 times higher26.3 than the unit
3.8 cost
90 0 0 3 26.3 1.5
for LC-LE
experiments in subset LC-HE. The experiments in subset LC-LE are characterized by
0 0 0 3 26.3 1.2
low unit costs and0low extraction 0 percentages 0 because of3 the absence5.3of hydrogen 0.9perox-
ide in the leaching90solutions. 0 0 3 5.3 1.5
Increasing the 0
concentrations
0
of KI and
2.3
NaIO 3 can increase the copper extraction
15 5.3 3.1
percentages, as demonstrated
0 0in Section 4.2.2;
2.3 however, 15 the unit 26.3
cost increases2.8conse-
quently. Figure 790shows the evolution0 of 2.3
the copper extraction
15 percentage
5.3 as 3.1
the rea-
gents are added. Experiment C1 uses a leaching solution containing 90 g/L NaCl, 15 g/L
90 0 2.3 15 26.3 2.9
LC-HE
H2O2, and 26.3 g/L0H2SO4. The 0leaching solution 0 15
in experiment 5.3
C2 contained 1.4
additionally
2.3 g/L of KI, and experiment C3 contained additionally 2.3 g/L of KI and 2 g/L of1.4NaIO3.
0 0 0 15 26.3
90 0 0 15 5.3 1.6
The added KI in 90 experiment C2 0
increases 0the extraction 15
percentage26.3
from 55% 1.6 to 58%,
while the unit cost increases to 77% compared to experiment C1. The added KI and
NaIO 3 in experiment C3 increase the extraction from 55% to 61%. Nevertheless, the unit
Four subsets can be identified and are graphically represented in Figure 6. The
cost is increased
experiments associated by a factor
withofsubset
approximately
HC-LE arefourthe compared to experiment
most economically C1.
unfavorable, with
On the other hand, as demonstrated in Section 4.2.1, hydrogen
high unit costs and low extraction percentages. The average unit cost is 9 USD/t peroxide is the
Cu,main
and
factor
the determining
average theisexperimental
extraction 27.1%. All the results; high concentrations
experiments in this sectionpromote
involve lowextraction.
hydrogen For
this reason, the effect of hydrogen peroxide on the final unit cost is also
peroxide concentrations, explaining the low copper extraction percentages. The addition of evaluated. Four
experiments
NaCl, KI, andwere
NaIOconducted and compared.
3 significantly increases the unit costs.

Figure6.
Figure 6. Representation
Representationof
ofdifferent
differenteconomic
economicevaluation
evaluationsubsets.
subsets.
On the other hand, subset LC-HE represents experiments with a low cost and high
extraction. The average unit cost in this subset is 2.2 USD/t Cu, and the average extraction
is 50%. These experiments include high concentrations of hydrogen peroxide. In cases with
the lowest unit cost, the concentrations of KI and NaIO3 are zero. The maximum extraction
percentage achieved in this subset is 58.4%, with a unit cost of 2.9 USD/t.
The experiments in subset HC-HE are characterized by high extraction percentages
and high unit costs, with an average approximately three times higher than the unit cost
for experiments in subset LC-HE. The experiments in subset LC-LE are characterized by
low unit costs and low extraction percentages because of the absence of hydrogen peroxide
in the leaching solutions.
Metals 2021, 11, 1567 13 of 17

Increasing the concentrations of KI and NaIO3 can increase the copper extraction
percentages, as demonstrated in Section 4.2.2; however, the unit cost increases consequently.
Figure 7 shows the evolution of the copper extraction percentage as the reagents are added.
Experiment C1 uses a leaching solution containing 90 g/L NaCl, 15 g/L H2 O2 , and 26.3 g/L
H2 SO4 . The leaching solution in experiment C2 contained additionally 2.3 g/L of KI, and
experiment C3 contained additionally 2.3 g/L of KI and 2 g/L of NaIO3 . The added KI in
experiment C2 increases the extraction percentage from 55% to 58%, while the unit cost
increases to 77% compared to experiment C1. The added KI and NaIO3 in experiment C3
Metals 2021, 11, x FOR PEER REVIEW
increase the extraction from 55% to 61%. Nevertheless, the unit cost is increased by a 14 of 18
factor
of approximately four compared to experiment C1.

Figure 7.
Figure 7. Comparison
Comparisonof
ofthe
theextraction
extractionpercentage
percentageand
andunit
unitcost
cost
asas a function
a function of of
thethe reagents
reagents add-
added.
ed.
On the other hand, as demonstrated in Section 4.2.1, hydrogen peroxide is the main
factorExperiments
determiningC4 theand
experimental results; high
C5 used leaching concentrations
solutions promote
with an acid extraction.ofFor
concentration 5.3
this reason,
g/L and the effectorofiodine
no chlorine hydrogen peroxide
species. on the final
The leaching unitused
solution cost is
inalso evaluated.
experiment Four
C5 addi-
experiments were conducted
tionally contained 15 g/L of and compared.
hydrogen peroxide; the experimental conditions for both
Experiments C4 and C5 used
experiments were the same. When hydrogen leaching solutions withisanpresent,
peroxide acid concentration
the copper of 5.3 g/L
extraction
and no chlorine or iodine species. The leaching solution used in experiment
increases from 1.7% to 41.3% (see Figure 8a). As seen in the literature review, an acidic C5 additionally
contained
environment 15 g/L of hydrogen
is insufficient toperoxide;
dissolve the experimental
chalcopyrite; conditions
therefore, for bothisexperiments
an oxidant used to ac-
were
celerate the dissolution of copper species. Even though the unit cost is lowincreases
the same. When hydrogen peroxide is present, the copper extraction from
in both cases,
1.7% to 41.3%
the unit cost in(see Figure 8a).
experiment C5 isAs45%
seen in the
lower literature
than review, an acidic
that in experiment environment
C4, owing to the in-
is insufficient to dissolve
creased copper extraction. chalcopyrite; therefore, an oxidant is used to accelerate the
dissolution of copper species. Even though the unit cost is low in
Figure 8b shows the results of experiments C6 and C7. Experiment C7 shows the both cases, the unit
cost
best in experiment
results C5 isthe
concerning 45%extraction
lower than that in experiment
percentage and copper C4, owing to theinincreased
concentration the PLS;
copper extraction.
the leaching solution contained 90 g/L NaCl, 2 g/L NaIO3, 2.3 g/L KI, 26.3 g/L H2SO4, and
15 g/LFigure
H2O28b shows the C6
. Experiment results
usedofa experiments C6 and
leaching solution C7.the
with Experiment
same reagent C7 shows the
concentra-
best results concerning
tions but without H2O2. the extraction percentage and copper concentration in the PLS; the
leaching solution contained 90 g/L NaCl, 2 g/L NaIO3 , 2.3 g/L KI, 26.3 g/L H2 SO4 , and
Experiment C6 achieves a low extraction percentage (i.e., 3.7%) and copper concen-
15 g/L H2 O2 . Experiment C6 used a leaching solution with the same reagent concentrations
tration in the PLS. For this reason, the unit cost increases significantly to 84 USD/t Cu. In
but without H2 O2 .
experiment C7, the significant copper extraction percentage (i.e., 60.6%) and associated
Experiment C6 achieves a low extraction percentage (i.e., 3.7%) and copper concen-
copper concentration in the PLS reduce the unit cost to 6.2 USD/t.
tration in the PLS. For this reason, the unit cost increases significantly to 84 USD/t Cu. In
experiment C7, the significant copper extraction percentage (i.e., 60.6%) and associated
copper concentration in the PLS reduce the unit cost to 6.2 USD/t.
Metals 2021, 11, 1567 14 of 17
Metals 2021, 11, x FOR PEER REVIEW 15 of 18

Figure8.8.Analysis
Figure Analysisofof copper
copper extraction
extraction andand
unitunit
costcost of experiments.
of experiments. (a) Leaching
(a) Leaching solution
solution con-
contained
tained only sulfuric acid. (b) Leaching solution contained the highest concentration of
only sulfuric acid. (b) Leaching solution contained the highest concentration of reagents. reagents.

6.6.Conclusions
Conclusions
Thisstudy
This studypresented
presented an alternative
an alternative leaching
leaching process,
process, in which in the
whichbasethe base
of the of the
leaching
leachingwas
solution solution was a combination
a combination of sulfuric ofacid
sulfuric
and acid and salts,
oxidant oxidant suchsalts, such as potassium
as potassium iodide
iodide
(KI) and(KI)
sodiumandiodate
sodium iodate
(NaIO 3 ), in(NaIO 3), in
chloride mediachloride
usingmedia
hydrogen usingperoxide
hydrogen (H2peroxide
O2 ) as a
(H2O2) as
catalyst at aroom
catalyst at room temperature.
temperature.
Inorder
In orderofofrelevance,
relevance, according
according to the
to the resultsresults
fromfrom the experimental
the experimental design,design, the
the most
most significant
significant reagentsreagents thatthe
that affect affect the leaching
leaching results are results
H2 Oare
2 > H22O SO2 >
4H SO4 >>NaCl
> 2NaCl NaIO>3NaIO
> KI.3
> KI.
The Theeffect
main mainplots
effect plots demonstrated
demonstrated the relevance
the relevance of the concentration
of the concentration of hydrogen of peroxide;
hydrogen
increasing this from 3this
peroxide; increasing g/Lfrom
to 153g/L g/L increased the copperthe
to 15 g/L increased extraction by ~25% on
copper extraction byaverage.
~25% on
The addition
average. Theofaddition
reagents ofNaCl, KI, and
reagents NaIOKI,
NaCl, 3 , combined
and NaIO with
3 , a higher
combined acid
with concentration,
a higher acid
increased the extraction
concentration, increasedbythe less than 10%by
extraction onless
average.
than 10% on average.
Metals 2021, 11, 1567 15 of 17

Also, the experiments showed that the slow leaching kinetics can be improved with
the addition of hydrogen peroxide, reducing the required residence time, and increasing
the copper extraction percentage.
The economic evaluation identified four economic subsets. The subset with the highest
extraction and lower costs was characterized by experiments involving the highest concen-
trations of hydrogen peroxide and low concentrations of iodine species, contributing to less
downstream contamination. Moreover, the economic analysis showed that an increase in
the concentration of these species increases copper extraction but at a significantly higher
cost. Conversely, an increase in the hydrogen peroxide concentration reduces the unit cost
because of the increase in the copper extraction percentage.
Finally, it is worth mentioning that currently, in the second stage of this study, the
measure of pH and potential are included in the experimental procedure to provide a
deeper understanding of the leaching process.

Author Contributions: P.C.H. contributed to the experimental design and analysis of the results;
N.E.J. contributed to the results review and writing; M.E.T. contributed to the review and editing;
G.A.M. contributed to the experimentation and results analysis; T.A.G. contributed to the results
analysis and review. All authors have read and agreed to the published version of the manuscript.
Funding: The authors are grateful for the financial support provided by the Project ING2030 CORFO
Code 16ENI2-71940.
Institutional Review Board Statement: Not applicable.
Informed Consent Statement: Not applicable.
Data Availability Statement: Not applicable.
Acknowledgments: The authors would like to thank Osvaldo Herreros (QEPD) and the Doctorado
en Ingeniería de Procesos de Minerales de la Universidad de Antofagasta.
Conflicts of Interest: The authors declare no conflict of interest.

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