Hydrometallurgy 187 (2019) 54–62

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

Investigation on chalcopyrite leaching with methanesulfonic acid (MSA) and T

hydrogen peroxide
Junmo Ahn, Jiajia Wu, Jaeheon Lee
⁎

The Department of Mining and Geological Engineering, University of Arizona, United States

ARTICLE INFO ABSTRACT

Keywords: Methanesulfonic acid (MSA) is an organic acid and was used to leach copper from chalcopyrite. MSA is a strong
Chalcopyrite acid with higher solubility of various metals. A suite of leaching tests of chalcopyrite at 75 °C with various
Alternative lixiviants lixiviants exhibited that MSA showed the highest copper extraction of 47% at 96 h with 30 g/L MSA and 5 g/L
MSA ferric. The copper extraction increased to over 90% with hydrogen peroxide as an oxidant at 75 °C. The acti-
Methanesulfonic acid
vation energy of the reaction with MSA and hydrogen peroxide was calculated to be 39.9 kJ/mol, indicating that
Hydrogen peroxide
the reaction is chemical reaction controlled.

1. Introduction
Chalcopyrite (CuFeS2) is the most abundant copper resource and
represents about 70% of copper deposit in the world (Córdoba et al.,
2008a). The common practice for leaching chalcopyrite is to use sul-
furic acid with ferric ion as an oxidant (Antonijević and Bogdanović,
2004; Klauber, 2008). However, it is very difficult to extract copper
from chalcopyrite to greater extraction percentages due to its refractory
nature. (Rodrıguez et al., 2003; Córdoba et al., 2008a). There are a few
factors affecting the difficulties of chalcopyrite leaching and the most
common cause is the formation of passive film on chalcopyrite surface
due to the byproducts such as elemental sulfur, metal sulfides, or jar-
osites (Hackl et al., 1995; Klauber, 2008). There are several processing
options to leach copper from chalcopyrite in higher efficiency including
bioleaching, pressure oxidation, and pyrite addition (McDonald and
Muir, 2007; Córdoba et al., 2008c; Khoshkhoo et al., 2017). The authors
aimed to find alternative chemicals suitable for copper leaching from
chalcopyrite without complex pretreatment or addition of other mi-
nerals. MSA was used as a chemical lixiviant to investigate the effi-
ciency of copper extraction from chalcopyrite.
MSA (methanesulfonic acid, CH3SO3H) is an organic acid widely
applied in several industries as an organic solvent for esterification and
alkylation catalysts, polymer solvents and electroplating (Gernon,
1999). MSA was originally developed as an anti-scaling agent with high
solubility of metal ions. (Bell, 1998; Gernon, 1999; Sangeeta and
MacDonald, 1999; Heidenfelder et al., 2009; Fassbender et al., 2016).
MSA forms highly stable metal complexes because of its characteristic
of stability. Due to its stability, it was reported that prevention of
oxidation of Sn (II) to Sn (IV) was observed, which stabilizes the state of
Sn in MSA solution matrix (Gernon, 1999). Therefore, stability in MSA
solution matrix of metals such as Fe (II) can prevent hydrolysis, which
can diminish passivation of chalcopyrite due to ferric originated by-
products.
MSA is also a strong acid as it can be completely ionized into proton
and methanesulfonate anion (CH3SO3−). Because of its high acidity,
MSA can be also used as a lixiviant to extract metals from ores and
concentrates. Compared to the conventional lixiviant, sulfuric acid, it
has higher affinity with metal ions such as Cu and Fe (Robinson et al.,
1983; Gernon, 1999). Additionally, its low toxicity and less corrosive-
ness can be advantageous properties to be applied in leaching sites and
hydrometallurgical plants (Finšgar and Milošev, 2010).
A few studies for leaching metals using MSA have been reported.
Galena (PbS) concentrate leaching test was conducted with MSA
and > 95% of lead was extracted using 0.5 M MSA with 0.25 M ferric in
0.4% pulp density at 65 °C (Wu et al., 2014). Pure malachite
(Cu2CO3(OH)2) sample was tested and the copper extraction was over
90% using 0.36 M MSA in 1.0% pulp density at 65 °C (Feng et al.,
2015). Chalcopyrite leaching by MSA was reported by Hidalgo's re-
search team in the presence of ferric chloride as an oxidant. Chalco-
pyrite leaching was performed in 10% pulp density at 90 °C with 0.5 M
MSA and 3 M ferric chloride as a baseline condition and the copper
extraction was 100% with 101 kJ/mol of activation energy (Hidalgo
et al., 2018).
The reaction of chalcopyrite leaching by conventional acid (sulfuric
acid) can be written by Eq. (1) as below:

⁎
Corresponding author.
E-mail address: jaeheon@email.arizona.edu (J. Lee).

https://doi.org/10.1016/j.hydromet.2019.05.001
Received 30 November 2018; Received in revised form 21 April 2019; Accepted 5 May 2019
Available online 07 May 2019
0304-386X/ © 2019 Elsevier B.V. All rights reserved.
J. Ahn, et al. Hydrometallurgy 187 (2019) 54–62

CuFeS2 + 2H2 SO4 + O2 Cu2 + + Fe 2 + + 2SO4 2 + 2H2 O + 2S (1) Table 2

Normally, copper and iron can be released from chalcopyrite, and
ferrous sulfate and elemental sulfur can be formed in the presence of
oxygen as an oxidant. The reaction can be regarded as spontaneous by
thermodynamic analysis ( Go298 = 298.56 kJ/mol) at 298 K (Goldberg
and Parker, 1985; Hiroyoshi et al., 2002). Similarly, the generation of
one mole of protons for each mole of MSA and the pairing of this acid as
a lixiviant to chalcopyrite are both thermodynamically spontaneous
and can be written as Eq. (2) ( Go298 = 80.22 kJ/mol) and Eq. (3)
( Go298 = 624.64 kJ/mol) , respectively (Guthrie et al., 1998; Pliego Jr
and Riveros, 2002).
CH3 SO3 H CH3 SO3 + H+ (2)
CuFeS2 + 4CH3 SO3 H + O2 Cu2 + + Fe 2 + + 4CH3 S3 + 2H2 O + 2S
(3)
When MSA is used as a lixiviant for chalcopyrite leaching, most
byproducts are the same as for a conventional leaching by sulfuric acid,
except generation of methanesulfonate ion, which has high affinity with
metal ions. All of reactions showed negative standard Gibbs free energy
value, meaning spontaneous reaction based on thermodynamic calcu-
lation at 298 K.
Conventionally, ferric ion is used as an oxidant for copper sulfide
leaching. In this study, hydrogen peroxide was used to investigate its
effect on copper leaching. The benefit of hydrogen peroxide is the
higher redox potential (1.77 V vs. SHE) compared to ferric (0.77 V vs.
SHE) (Hamann et al., 2007; Mahajan et al., 2007) and has advantages
environmentally as it produces water as a byproduct. Copper extraction
of 55% was achieved from chalcopyrite using 1.0 M H2SO4, 0.26 M
H2O2 and 8 mL ethylene glycol at 0.125% pulp density. At lower tem-
perature (40 °C), copper extraction of 50% was reported using 5.0 M
H2SO4 with 2.0 M H2O2 at 0.11% pulp density (Antonijević et al.,
2004). The leaching kinetics of MSA with hydrogen peroxide may
achieve a higher copper dissolution, thus the foci of this study are 1) to
compare copper extraction from chalcopyrite between sulfuric acid and
MSA, 2) investigate the role of hydrogen peroxide in chalcopyrite
leaching, and 3) optimize chalcopyrite leaching condition.
XRD analysis of chalcopyrite concentrate sample in this study.
Material Composition (%)
Chalcopyrite (CuFeS2) 89.5
Pyrite (FeS2) 5.0
Molybdenite (MoS2) 0.2
Quartz 0.7
K-Feldspar 3.1
Plagioclase 1.5%
in 100 mL solution at 75 °C. A watch glass cover was placed on top of
the beaker to prevent the evaporative loss of the solution during the
leach test. Leach tests using sulfuric acid with ferric as an oxidant were
performed as baseline tests. MSA was used as an alternative lixiviant to
compare the results with those of sulfuric acid. The leach test was run
initially for 24 h and increased up to 144 h. The lixiviants' concentra-
tions were changed from 5 to 50 g/L for sulfuric acid with ferric ion as
an oxidant which varied from 0 to 15 g/L. The MSA concentration was
set from 10 to 50 g/L with 0 to 10 g/L ferric. After 24 h leaching tests,
several conditions from these lixiviants were selected and 96-h tests
were performed to further investigate the effects on overall leaching
performance. Multi-stage leaching tests were also performed by using
fresh lixiviant and oxidant in every 48 h and ran up to 144 h to find out
the ultimate copper extraction from the sample.
The leaching efficacy of hydrogen peroxide to chalcopyrite was also
studied. Sulfuric acid and MSA were used with H2O2 as an oxidant to
compare copper extraction. MSA was tested using 10 to 30 g/L to find
the effect of its concentration on chalcopyrite leaching with H2O2.
Periodic addition of hydrogen peroxide during the leach test was also
studied. Hydrogen peroxide of 0.3, 0.6, 0.9, 1.5, 3.0 and 4.5% (v/v) was
added in every 24 h during the 96-hour leaching tests to optimize the
oxidant concentration for copper extraction. The overall copper ex-
traction was studied in different temperatures ranging from 25 °C to
75 °C and the activation energy of the reaction was calculated using
Arrhenius equation. Table 3 summarizes all the conditions of leaching
tests.

2. Materials and methods

2.3. Analytical method (AAS and titration)
2.1. Sample preparation
Kinetics samples were taken at 2, 6, 24, 48, 72 and 96 h. When
samples were collected, both Eh and pH were monitored, and DI water
Chalcopyrite concentrate with particle size of P80 40 μm was re-
was added to keep the overall solution volume constant during the test.
ceived from an activate copper mine in southern Arizona and used for
Solution samples were filtered by 0.45 μm syringe filters, and the
the leaching tests. Table 1 shows the multi-elements ICP-OES (In-
copper and iron concentrations were analyzed by Atomic Absorption
ductively Coupled Plasma Optical Emission Spectrometry) analysis re-
Spectrophotometer (AAS, Perkin-Elmer, USA). Ferrous and total iron
sults of the chalcopyrite concentrate. It contains 28.8% Cu, 26.4% Fe,
concentrations were also measured by ceric sulfate coulometric titra-
and 30.8% S. It also contains small amount of molybdenum (0.19%)
tion methods using ferroin as indicator. Samples were acidified by 1 N
and silver (90.5 ppm). The overall chalcopyrite content is 89.5% in the
sulfuric acid for ferrous titration. The solution was titrated with 0.01 M
concentrate with 5.0% pyrite and 0.2% molybdenite as shown in
ceric sulfate with a few drops of ferroin indicator for ferrous iron
Table 2.
concentration. For total iron, 10% hydrochloric acid was mixed with
the sampled solution followed by boiling with analytical grade lead
2.2. Leaching test
metal to reduce all ferric iron to ferrous iron. Then, the solution was
titrated with ceric sulfate with a few drops of ferroin indicator.
All leaching tests were carried out in a beaker with 1 g solid sample

Table 1
Elemental composition of chalcopyrite concentrate sample in this study.
Element Ag Al As Cd Co Cr Cu Fe Mn Mo Na Ni
Unit ppm % ppm ppm ppm ppm % % ppm % % ppm
Concentration 90.5 0.62 195 < 0.5 4.0 13.7 28.8 26.4 21 0.19 0.14 11
Element P Pb S Sb Se Sn U V W Zn Zr
Unit ppm ppm % ppm ppm ppm ppm ppm ppm % ppm
Concentration 30 582 30.8 119 92 6.9 4.0 6 3.5 0.18 2.3

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J. Ahn, et al. Hydrometallurgy 187 (2019) 54–62

Table 3
Summary of the condition of leaching tests (pulp density 1%).
Test Lixiviant Lixiviant concentration Oxidant Oxidant concentration Leaching time Temperature

3+
24 h Leaching test H2SO4 5–50 g/L Fe 0–10 g/L 24 h 75 °C
MSA 10–50 g/L Fe3+ 0–10 g/L 24 h 75 °C
96 h Leaching test H2SO4 5, 10, 15 g/L Fe3+ 1–10 g/L 96 h 75 °C
MSA 10, 20, 30 g/L Fe3+ 1–10 g/L 96 h 75 °C
Multi Stage Leaching test MSA 30 g/L Fe3+ 5 g/L 48 h × 3 = 144 h 75 °C
Acid & H2O2 Leaching Test H2SO4 5 g/L H2O2 1.5–4.5% 96 h 75 °C
MSA 30 g/L H2O2 1.5–4.5% 96 h 75 °C
MSA & H2O2 Leaching Test MSA 10–30 g/L H2O2 0.3–4.5% 96 h 75 °C
Temperature effect test H2SO4 5 g/L H2O2 0.9% 96 h 25–75 °C
MSA 30 g/L H2O2 0.9% 96 h 25–75 °C

Fig. 1. Copper extraction from 1% pulp density of chalcopyrite by various concentration of (a) sulfuric acid with ferric and (b) MSA with ferric for 24 hours leaching
at 75 °C.

3. Results and discussion concentrations of ferric were selected for further tests. In addition to
MSA leaching study, 5, 10 and 15 g/L of sulfuric acid with the same
3.1. Baseline leaching with sulfuric acid for 24 h conditions of ferric were tested.

Fig. 1(a) shows the copper extraction using various concentrations
of sulfuric acid and ferric ion. Overall copper extraction ranged be-
tween 15 and 20% in most of conditions. Copper extraction of about
19% was observed using 5, 10, 25 g/L sulfuric acid with 5 g/L ferric as
an oxidant resulting in no significant effect on overall copper extrac-
tion. The sulfuric acid concentration was further increased to 50 g/L
with increased ferric ion concentration to 10 g/L. The copper extraction
ranged from 16% to 21% indicating that copper extraction from chal-
copyrite using sulfuric acid was not effective.
Copper extraction was only 7% with 10 g/L sulfuric acid without
ferric but it increased to 18% with 10 g/L ferric. It indicates the im-
portant role of an oxidant in chalcopyrite leaching. However, increase
of ferric addition didn't show improved copper extraction under this
condition.
3.2. MSA leaching for 24 h
Fig. 1(b) illustrates the result of 24 h chalcopyrite leaching tests
with MSA and ferric. In general, copper extraction increased by in-
creasing MSA concentration up to 30 g/L MSA. Copper extraction in-
creased from 22% to 28% when MSA concentration increased from 10
to 30 g/L with 5 g/L ferric. Further increase of MSA to 40 g/L and 50 g/
L with 5 g/L ferric showed decreased copper extraction of 19% and
21%, respectively.
The copper extraction with 10 g/L MSA only (without ferric)
showed only 4% indicating the ferric is essential for the leaching. When
25 g/L MSA was used, the effect of ferric was negligible.
In comparison to leaching by sulfuric acid, MSA showed better
copper extraction for most conditions. The highest copper extraction of
28% was observed at 30 g/L MSA with 5 g/L ferric. To investigate the
leaching kinetics of chalcopyrite, 10, 20 and 30 g/L MSA with various
3.3. Chalcopyrite leaching by sulfuric acid with ferric ion for 96 h
Fig. 2(a) illustrates the leaching kinetics of copper using 5, 10 and
15 g/L sulfuric acid with 5 g/L ferric at 75 °C showing gradual increase
of extraction within 96 h. The highest copper extraction of 39% was
observed at 5 g/L sulfuric acid. The copper extraction of 33% was ob-
served from both 10 and 15 g/L sulfuric acid.
The ferric concentration was changed from 1 g/L to 10 g/L with 5 g/
L sulfuric acid to investigate the effect of the oxidant concentration. As
shown in Fig. 2(b), the copper extraction was low with 1 g/L (21%) and
extraction plateaued at 37% with 3, 5, 10 g/L ferric.
3.4. Chalcopyrite leaching by MSA with ferric ion for 96 h
For leaching by MSA and ferric, there are discrete increases of
copper extraction with each increase to the concentration of MSA as
shown in Fig. 3(a), unlike what is shown for sulfuric acid leaching. The
highest copper extraction of 46% was observed with 30 g/L MSA
while < 38% copper extractions were observed using sulfuric acid.
Different ferric concentrations were applied using 30 g/L MSA to
investigate the effect of the oxidant concentration on the leaching ki-
netics as illustrated in Fig. 3(b). Copper extraction was increased as
ferric concentration increased from 1 g/L to 5 g/L, but it decreased with
10 g/L ferric. This phenomenon was observed with sulfuric acid
leaching tests as shown in Fig. 2(b). It could be explained due to the
precipitation of surplus ferric passivating the chalcopyrite surface in the
form of iron oxide or jarosites (Córdoba et al., 2008b) in acidic and
thermal condition. It was reported that lower than 30% copper ex-
traction was observed with solution potential > 500 mV vs. Ag/AgCl
while higher than 80% copper extraction was achieved using lower
solution potential < 400 mV vs. Ag/AgCl. In addition, iron oxide and

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J. Ahn, et al.
Fig. 2. Copper extraction from 1% pulp density of chalcopyrite by (a) 5, 10 and 15 g/L of H2SO4 with 5 g/L ferric, (b) 1, 3, 5 and 10 g/L ferric with 5 g/L H2SO4 for
96 hours leaching at 75 °C.
jarosites were detected at higher Eh conditions which hinder copper
dissolution from chalcopyrite. In this test, most conditions showed a
solution redox potential higher than 500 mV vs. Ag/AgCl and the pas-
sivation of chalcopyrite could very likely be happening due to the
presence of ferric ion in excess of 5 g/L. Therefore, 30 g/L MSA with
5 g/L ferric was found to be the optimum condition for chalcopyrite
leaching at high temperature. This condition was used for further
leaching tests to increase chalcopyrite extraction.
3.5. Multi-stage leaching tests by MSA & ferric ion
Multi stage leaching tests were conducted to enhance the overall
copper extraction from chalcopyrite using MSA and ferric as an oxidant.
The leaching solution, 30 g/L MSA and 5 g/L ferric, was refreshed every
48 h for a total of 144 h. This method of refreshing the solution was
adapted in response to a plateau in copper extraction beginning at 48 h,
demonstrated by an analysis of kinetics in Fig. 3(a).
Fig. 4(a) illustrates the result of multi stages leaching by 30 g/L MSA
and 5 g/L ferric. Copper extraction increased up to 55% with three
consecutive stages of extraction for 48 h per stage and overall 144 h
leaching time. The copper extraction from each stage was 30%, 18%,
and 7% indicating the leaching reaction was hindered even with fresh
lixiviant and oxidant. Fig. 4(b) illustrates the ferric concentration de-
crease with time resulting from the ferric consumption by the chemical
reaction which corresponds well with the decreased copper extraction
in each stage. At the first stage, the ferric concentration decreased from
5000 ppm to < 500 ppm. The ferric concentration decrease was smaller
in the second stage and it dropped to 2000 ppm. At the third stage, the
Fig. 3. Copper extraction from 1% pulp density of chalcopyrite by (a) 10, 20 and 30 g/L of MSA with 5 g/L ferric, (b) 1, 3, 5 and 10 g/L ferric with 30 g/L MSA for
96 hours leaching at 75 °C.
57
Hydrometallurgy 187 (2019) 54–62
decrease was even smaller with 4000 ppm ferric left at the end of this
last stage. It shows that fresh solution with ferric ion enhanced the
leaching performance, but the limitation was obvious. The role of ferric
iron as an oxidant is key to this process, as such further work was
performed by testing alternative oxidants, hydrogen peroxide, to fur-
ther increase the copper extraction from chalcopyrite concentrate.
3.6. Hydrogen peroxide as an oxidant
Using hydrogen peroxide as an oxidant, two acids were used to
investigate the copper leaching kinetics from chalcopyrite and the re-
sults are shown in Fig. 5. The concentrations of sulfuric acid and MSA
was 5 g/L and 30 g/L, respectively. The concentrations of hydrogen
peroxide were 1.5, 3.0, and 4.5%. Sulfuric acid leaches copper from
chalcopyrite up to 40% with 3.0 and 4.5% hydrogen peroxide and 1.5%
hydrogen peroxide condition showed 32% of copper extraction as
shown in Fig. 5(a). The 40% copper extraction was close to that with
5 g/L ferric as an oxidant (39%), indicating the effect of different oxi-
dant was not significant.
MSA with hydrogen peroxide shows a significant increase of copper
extraction in 96 h. The copper extractions were 59, 61 and 63% by 1.5,
3.0 and 4.5% of hydrogen peroxide (v/v), respectively. Higher copper
extractions were observed compared to other lixiviant-oxidant combi-
nations. Compared to ferric leaching (47% copper extraction), higher
copper extractions around 60% were achieved for all conditions. One of
the reasons is that the higher molarity of hydrogen peroxide (1.5%
H2O2–0.64 mol/L) is likely why it was better than ferric (0.09 mol/L).
The hydrogen peroxide activity persists at higher molarity than was
J. Ahn, et al. Hydrometallurgy 187 (2019) 54–62

Fig. 4. (a) Copper extraction and (b) ferric concentration of multi stage leaching test by feeding fresh leaching solution at every 48 h until 144 hours leaching at 1%
pulp density of chalcopyrite with 30 g/L MSA and 5 g/L ferric at 75 °C.

achieved using ferric iron. The concentration of hydrogen peroxide was

measured with time during the leaching tests at 75 °C and shows higher
consumption rate within 2 h. It is believed that the hydrogen peroxide
was consumed by the reaction and was destroyed in higher temperature
conditions. To maintain the optimum oxidant in the system, hydrogen
peroxide was periodically added to the leaching solution to enhance the
overall extraction.
The result of periodical addition of hydrogen peroxide for every
24 h is demonstrated in Fig. 6. The amount of hydrogen peroxide added
at each step was zero, 0.6%, and 1.5% in the presence of 30 g/L MSA.
One of the interesting findings was that the significant copper extrac-
tion in 48 h was observed without additional hydrogen peroxide. It can
be explained by the oxidation of ferrous iron released from chalcopyrite
leaching into ferric iron, which can behave as an additional oxidant for
copper leaching. Higher addition (1.5%) of hydrogen peroxide achieved
higher copper extraction (75%) than lower addition (0.6%) showing
69% of copper extraction. Without addition of hydrogen peroxide, the
copper extraction in 96 h was 59% which is close to that of 0.6% hy- Fig. 6. Effect periodical addition of hydrogen peroxide for no further addition,
drogen peroxide addition. However, the kinetics are faster with addi- 0.6% and 1.5% of periodical addition at every 24 h with initial addition of 1.5%
tion of hydrogen peroxide showing the maximum extraction was hydrogen peroxide on copper extraction from 1% pulp density of chalcopyrite
reached in 48 h. Similar result was observed with 1.5% hydrogen per- with 30 g/L MSA for 96 hours leaching at 75 °C.
oxide addition showing over 80% copper extraction in 48 h.
Leached residues were collected for scanning electron microscope samples but the whole grain was still visible as seen in Fig. 7(b). When
(SEM) and X-Ray Diffraction (XRD) analyses. Fig. 7 shows the SEM 0.6% and 1.5% hydrogen peroxide were added, unleached chalcopyrite
images of the head (a) and three leached residues (b-d) from the tests grains were no longer visible and the surface morphologies were totally
reported in Fig. 6. The chalcopyrite head sample shows many irregular- changed. The surface was characterized by Energy Dispersive X-ray
shaped small particles on a larger grain. As the hydrogen peroxide Spectroscopy (EDS) and higher concentration of sulfur was observed in
addition increased resulting in higher copper extractions, the surface of these residue samples. The sulfur content in the residue sample of
the chalcopyrite grain significantly changed as shown in Fig. 7(b), (c), Fig. 7(c), corresponding leached residue in Fig. 6 with 0.6% hydrogen
and (d). When no additional hydrogen peroxide was provided (Fig. 6, peroxide added, increased to 96.0% with 2.1% copper. The sulfur
no further addition), the surface became smoother than the head content increased to 97.1% in the sample of Fig. 7(d), corresponding

Fig. 5. Copper extraction from 1% pulp density of chalcopyrite by (a) 5 g/L H2SO4 and (b) 30 g/L MSA with 1.5, 3.0 and 4.5% H2O2 for 96 hours leaching at 75 °C.

58
J. Ahn, et al.
Fig. 7. SEM microphotographs of chalcopyrite grains from (a) head and (b)–(d) leached residues under different conditions.
leached residue in Fig. 6 with 1.5% hydrogen peroxide added, and the
copper content further decreased to 1.4%.
The XRD analysis also supported the observations from SEM/EDS
analysis. Fig. 8 shows the XRD results of three residue samples. The
intensity of copper peaks decreased from (a) to (c) while gradual in-
crease of sulfur peak's intensity was observed. The copper content of the
residue samples was 15, 10, and 6% for sample (a), (b), and (c), re-
spectively. The sulfur content of samples (a), (b), and (c) was 85%,
90%, and 94%. The SEM/EDS and XRD analyses showed that chalco-
pyrite leached well under the conditions used and the dominant by-
product was elemental sulfur.
3.7. Chalcopyrite leaching by MSA with hydrogen peroxide
Fig. 9 illustrates the effect of MSA concentration on chalcopyrite
leaching in the presence of different concentrations of H2O2. MSA
concentrations used were 10, 20, and 30 g/L with 1.5, 3.0 and 4.5% of
H2O2 and periodical addition of 0.6, 1.2 and 1.8% respectively at every
24 h. All conditions showed copper extraction of 70% in 96 h. However,
the MSA concentration increase from 10 g/L to 30 g/L shows increased
kinetics especially between 24 h and 48 h. It can be seen in Fig. 9(a),
(b), and (c) illustrating increased slope of the line between 24 and 48 h.
With 10 g/L MSA, the copper extraction gradually increased until 96 h
while the copper extraction levels out at 72 h with 20 g/L MSA and at
48 h with 30 g/L MSA.
The overall copper extraction was not increased in 30 g/L MSA
compared with 10 g/L MSA, so the hydrogen peroxide concentrations
were further increased to investigate the effect on this. The initial
concentration of hydrogen peroxide was from 0.3 to 4.5% with the
same amount of periodical addition in every 24 h with 30 g/L MSA.
Fig. 10(a) and (b) show the copper and iron extractions from the
leaching tests, respectively. The highest copper extraction of 99% was
observed with 0.9% hydrogen peroxide and it decreased with further
59
Hydrometallurgy 187 (2019) 54–62
increase of hydrogen peroxide concentration. When the concentrations
of 1.5, 3.0, and 4.5% were used, the kinetics were faster than the other
conditions up to 48 h without further increase of the copper extraction
after that. The iron extraction showed similar results as shown in
Fig. 10(b) with higher extraction with 0.6% and 0.9% hydrogen per-
oxide.
The periodical addition of hydrogen peroxide increases copper ex-
traction from chalcopyrite by the direct oxidation of the mineral and
oxidation of leached ferrous to ferric iron. Lower copper extraction with
an addition of H2O2 lower than 0.9% was due to the insufficient oxidant
for chalcopyrite leaching. The reason of lower copper extraction with
higher than 0.9% addition of hydrogen peroxide is not clear. However,
there are two reasons to explain this phenomenon. One of the possi-
bilities is the passivation mechanism by ferric. Ferric can be hydrolyzed
in highly oxidizing conditions, for example in acidic thermal condi-
tions, which produces iron hydroxide, oxyhydroxides and jarosites
(Stott et al., 2000). Formation of passivation layer by hydrolysis such as
jarosites and goethite was reported from bioleaching study, which was
conducted at highly oxidized condition (Eh > 600 mV vs. Ag/AgCl)
and at high temperature (68 °C). Copper extraction of 20% was ob-
tained at higher solution potential while higher than 90% copper ex-
traction was achieved at 400 mV vs. Ag/AgCl condition at the same
temperature (Córdoba et al., 2008c). In this study, the Eh of the solution
was measured higher than 700 mV vs. Ag/AgCl with > 0.9% hydrogen
peroxide resulting in a suitable condition for ferric hydrolysis, which
could potentially lead to the chalcopyrite passivation.
The other reason for this phenomenon can be passivation on the
surface due to excessive usage of H2O2. Several researchers have pre-
sented passivation by large amount of H2O2 on metals surfaces.
Kolotyrkin's group studied the role of hydrogen peroxide in passivation
of Fe—Cr alloy in sulfuric acid solution system. The current density
significantly decreased with increase H2O2 concentration up to 0.4 M. It
is also highly likely that high dosage of oxygen containing oxidant can
J. Ahn, et al. Hydrometallurgy 187 (2019) 54–62

Fig. 8. XRD peaks of leached residues from different periodical addition of hydrogen peroxide. (a) no further addition, (b) 0.6%, and (c) 1.5%.

adsorb on the surface and work as a reaction barrier (Kolotyrkin et al.,
1976). The passivation of metal surface by high addition of hydrogen
peroxide due to the formation of oxide layer was also reported. A
dramatic decrease of current density was also observed by addition of
H2O2 from 1.5% to 10% (Seal et al., 2003). In this research, high
amount of H2O2 > 0.9% did not increase copper extraction from chal-
copyrite. This can be also explained by passivation under high con-
centration of H2O2, which might form a passive layer on the surface to
hinder mass transport. To avoid passivation, < 1.5% hydrogen per-
oxide addition should be utilized. Therefore, the optimal condition for
copper leaching from chalcopyrite using MSA and hydrogen peroxide is
found to be 30 g/L MSA and periodic addition of 0.9% hydrogen per-
oxide.
3.8. Effect of temperature
Multiple leaching tests with the optimal condition were carried out
to investigate the reaction mechanism of MSA and H2O2 at different
temperatures. The reaction mechanism and the rate-controlled reaction
can be determined by the calculated activation energy. The reaction is
generally considered as a mass transfer controlled when the activation
energy was < 20 kJ/mol. The activation energy can be calculated using

Fig. 9. Effect of MSA concentration from (a) 10 g/L (b) 20 g/L and (c) 30 g/L on copper extraction with 1.5, 3.0 and 4.5% (v/v) of hydrogen peroxide at initial and
periodical addition of 0.6, 1.2 and 1.8% respectively at every 24 h at 1% pulp density for 96 hours leaching at 75 °C.

60
J. Ahn, et al. Hydrometallurgy 187 (2019) 54–62

Fig. 10. Effect of hydrogen peroxide concentration from 0.3 to 0.6, 0.9, 1.5, 3.0 and 4.5% (v/v) with periodical addition of the same amount at every 24 h on (a)
copper and (b) iron extraction by 30 g/L MSA at 1% pulp density for 96 hours leaching at 75 °C.

the Arrhenius equation as seen in Eq. (4) using experimental data ob- increased at 60 and 75 °C as shown in Fig. 11(a). Copper extraction by
tained from different temperatures. sulfuric acid with hydrogen peroxide showed a gradual increase but the
remained relatively lower compared to that of MSA as seen in
Ea 1
ln k = + ln A Fig. 11(b). Fig. 11(c) and (d) are Arrhenius plots for MSA and sulfuric
R T (4)
acid, respectively. The calculated activation energy of MSA with hy-
where, k is rate constant, drogen peroxide was 39.9 kJ/mol indicating the overall reaction is
controlled by the surface chemical reaction. The 19.1 kJ/mol of acti-
Ea is experimental activation energy (J/mol), vation energy calculated from the sulfuric acid and hydrogen peroxide
R is gas constant (8.314 J/K∙mol), system might infer the reaction is controlled by the mass transport re-
T is absolute temperature (K), and action. However, the lower activation energy must be due to the pas-
A is the constant. sivation on the surface resulting in lower overall reaction kinetics. It is a
noteworthy phenomenon that the rate determining step in sulfuric acid
Rate constants of each temperature can be obtained, and activation system is also a surface chemical reaction not the mass transfer reac-
energy can be calculated from the slope (−Ea/R) of the plot (Laidler, tion.
1984). Activation energy of chalcopyrite leaching from literatures showed
Fig. 11 shows copper extraction with MSA and sulfuric acid with in the range from 40 to 130 kJ/mol. When 0.2 M ferric chloride was
hydrogen peroxide as an oxidant. The copper extraction gradually in- used as an oxidant in the presence of 0.3 M HCl, activation energy was
creased with increasing temperature up to 55 °C and significantly

Fig. 11. Effect of temperature from 25 to 75 °C on copper leaching by (a) 30 g/L MSA (b) 5 g/L sulfuric acid with periodical addition of 0.9% hydrogen peroxide at
24 h for 96 hours leaching and Arrhenius plot for the calculation of activation energy of leaching test by (c) 30 g/L MSA and (d) 5 g/L sulfuric acid.

61
J. Ahn, et al.
63 kJ/mol at the temperature range of 40 to 100 °C (Dutrizac, 1981).
Normal sulfuric acid and ferric sulfate leaching achieved activation
energy 77, 83 and 88 kJ/mol respectively by 0.01, 0.1 and 1.0 M ferric
sulfate in the presence of 0.2 M sulfuric acid at the temperature from 50
to 81 °C (Hirato et al., 1987). At the lower region of Eh (400 mV vs. Ag/
AgCl), 130 kJ/mol of activation energy was reported when sulfuric acid
(set pH: 1.8) and 5 g/L ferric/ferrous sulfate were tested, at the tem-
perature range from 35 to 68 °C (Córdoba et al., 2008b). Chalcopyrite
leaching tests with 2.0 M sulfuric acid and 2.0 M hydrogen peroxide
showed 60 kJ/mol at the temperature between 25 and 50 °C
(Antonijević et al., 2004). Compared to activation energy obtained from
listed literatures, lower activation energy was calculated in this study
(39.9 kJ/mol). It is because MSA is a very strong acid and the chemical
reaction was enhanced compared to the sulfuric acid or ferric chloride
system.
4. Conclusion
As an alternative lixivant, MSA (Methanesulfonic acid) showed
higher copper extraction from chalcopyrite compared to sulfuric acid in
the presence of ferric as an oxidant. Using hydrogen peroxide as an
oxidant, the copper extraction was improved up to 60% in 96 h.
Additional copper extraction increase up to 99% was observed by the
periodic addition of hydrogen peroxide of 0.9% every 24 h with 30 g/L
MSA. The EDS and XRD analyses showed the elemental sulfur was the
main byproduct of the chalcopyrite leaching. The new lixiviant-oxidant
combination of methanesulfonic acid with hydrogen peroxide showed a
promising result of copper extraction from chalcopyrite concentrate.
The activation energy of the copper extraction from chalcopyrite under
this condition was calculated to be 39.9 kJ/mol, indicating the rate
determining step is the surface chemical reaction.
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