Hydrometallurgy 171 (2017) 165–171
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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet
The effect of carbon black on the oxidative leaching of enargite by
manganese(IV) dioxide in sulfuric acid media
Hiroshi Nakazawa⁎, Shin Koshiya, Hideki Kobayashi, Takashi Matsuhashi
Graduate School of Engineering, Iwate University, Morioka 020-8551, Japan
1. Introduction
Leaching processes have been considered as viable alternatives to
produce a clean copper concentrate or collective recovery of copper
from chalcopyrite and enargite. Several leaching processes for enargite
have been investigated such as acid leaching (Dutrizac and MacDonald,
1972; Escobar et al., 1997; Padilla et al., 2005) alkaline sulfide leaching
(Filippou et al., 2007; Curreli et al., 2009; Tongamp et al., 2009),
pressure leaching (Padilla et al., 2008; Ruiz et al., 2011; Conner and
Anderson, 2013) and bioleaching (Ehrlich, 1964; Escobar et al., 2000;
Muñoz et al., 2006).
Enargite is a refractory mineral in aqueous media, especially in
sulfuric acid (Dutrizac and MacDonald, 1972; Escobar et al., 1997). The
leaching rate of enargite in sulfuric acid media at atmospheric pressure
is very slow using either oxygen or ferric ions as oxidants. Peacey et al.
(2004) have compared the solubility of copper sulfides in acidic ferric
sulfate media. At 35–50 °C, the following order holds true for the
solubility of copper sulfides:
chalcocite > bornite > covellite > chalcopyrite > enargite.
Galvanic interactions among electrical conducting minerals are
well-known phenomena. When two of these minerals are in contact
with each other in acid electrolyte, a galvanic couple is formed in which
the mineral of lower rest potential corrodes at an enhanced rate as the
anode of the couple, and the one with higher rest potential acts as the
cathode. This interaction accelerates or retards the dissolution of
minerals in acid media (Dutrizac et al., 1971; Dutrizac and
MacDonald, 1973; Linge, 1977; Peters, 1977).
Rivera-Vasquez and Dixon (2015) developed a new leaching method
to accelerate the kinetics of enargite leaching by the addition of pyrite
as catalyst in acidic ferric sulfate media at 80 °C. Since pyrite is nobler
than enargite, pyrite and enargite form galvanic couple in contact with
each other. In this process, electrons move to pyrite from enargite, and
pyrite works as cathodic site where ferric ions are reduced to ferrous
ions in the leaching media, resulting in acceleration of the enargite
leaching kinetics.
Ghamad (2008) found that activate carbon enhances the enargite
leaching kinetics in ferric sulfate solution at 85 °C, suggesting that
activated carbon act as cathodic site like pyrite as described above.
⁎
Corresponding author.
E-mail address: nakazawa@iwate-u.ac.jp (H. Nakazawa).
http://dx.doi.org/10.1016/j.hydromet.2017.05.002
Received 21 April 2016; Received in revised form 17 February 2017; Accepted 8 May 2017
Available online 11 May 2017
0304-386X/ © 2017 Elsevier B.V. All rights reserved.
MARK
Dixon and Rivera-Vasquez (2010) also reported that activated carbon
improves the leaching rate of chalcopyrite in the presence of an oxygen-
containing gas in acidic sulfate solutions containing Fe(II) and Fe(III) at
80 °C.
Manganese (IV) oxide (MnO2) is a semiconductor having a rest
potential that is much higher than that of sulfide minerals such as pyrite
(Kumari and Natarajan, 2002), sphalerite (Rath and Paramguru, 1994),
and chalcopyrite (Gantayat et al., 2000; Nakazawa and Hareyama,
2016). Table 1 shows the rest potentials of MnO2 and sulfide minerals.
In a case where MnO2 is in contact with one such mineral, a galvanic
corrosion couple can form wherein the former acts as the cathode and
the latter as the anode. This leads to a strong galvanic interaction
between the minerals. Rath and Paramguru (1994) investigated the
galvanic interaction between sphalerite and MnO2 in sulfuric acid
solution and found a substantial increase in the leaching of both
minerals.
Nakazawa and Hareyama (2016) investigated the galvanic leaching
of chalcopyrite in sulfuric acid media using chemical reagent MnO2 or
the black paste collected from spent zinc-carbon batteries. The black
paste contained MnO2 and carbon powder. The black paste enhanced
the kinetics of chalcopyrite leaching more dramatically than MnO2;
with 83% of the Cu in chalcopyrite extracted in 40 h. They suggested
that the carbon powder within the black paste could play an important
role in the galvanic leaching of chalcopyrite in the presence of MnO2.
MnO2 is used as the cathode of various electrochemical cells, but
MnO2 is not sufficiently conductive. Carbon materials are used to
improve the conductivity of the cathode in zinc-carbon batteries and
alkaline batteries because they are chemically inert and electrically
conductive. Among the carbon materials carbon black is particularly
common for this purpose (Chung, 2007).
In this study, we conducted the enargite leaching experiments using
MnO2 and carbon black and investigated the effect of several factors
such as ratios of carbon and MnO2 to enargite, temperature, and pH on
the enargite leaching in sulfuric acid media.
2. Experimental
Enargite ore used in this study was provided by a mine in the
H. Nakazawa et al.
Table 1
Rest potentials of MnO2 and sulfide minerals.
Rest potential
Pyrolusite +910 mV vs SCE
Pyrite +490 mV vs SCE
MnO2 +871 mV vs SCE
Sphalerite +60 mV vs SCE
MnO2 +1171 mV vs SHE
Chalcopyrite +524 mV vs SHE
Relative Intensity (scale unit =500cps)
10 20 30
Fig. 1. XRD pattern of enargite.
Taiwan. The ore was clashed and sieved to obtain − 102 μm size
fraction. A XRD pattern of the enargite was determined with a
diffractometer (Regaku Corp., Rint2100) at 40 kV and 20 mA. The
result is shown in Fig. 1. Only enargite peaks were observed. The
chemical compositions of the sample were 42.8% Cu, 13.2% As, and
0.2% Fe.
MnO2 powder (extra pure grade reagent, median diameter 52 μm)
was provided by Kanto chemical Co. Ltd. The chemical composition of
MnO2 was measured by digesting 0.5 g samples with aqua regia (20 mL
of 1:3 HNO3/HCl) by gentle boiling on a hot plate for 4 h. The solutions
were filtered and the filtrates were analyzed with an atomic absorption
spectrophotometer (Hitachi Z-5000). The weight percentage of Mn was
54.9%.
Carbon black, which is produced by the continuous thermal
decomposition of acetylene gas, was provides by Denki Kagaku
Kogyou Co. Ltd. Table 2 presents the basic characteristics of the carbon
black. It is a very fine powder and extremely electrically conductive.
Leaching experiments were carried out in 300 mL erlenmeyer flasks
with 200 mL sulfuric acid solution. After samples were added into the
flasks, flasks were sealed with silicon caps and placed on a magnetic
stirrer at 200 rpm at room temperature. At desired intervals, the pH and
the redox potential of the leaching solution were measured. The redox
potential was measured using a Pt electrode with an Ag - AgCl (3.3 M
KCl) reference electrode and it was converted and reported with respect
to the standard hydrogen electrode (SHE). Next, an aliquot of the
solution was withdrawn and centrifuged at 10,000 rpm for 10 min. The
supernatant was analyzed for Cu, Mn, total As (arsenate (As(V))
+ arsenite(As(III))), and As(III). Concentrations of Cu and Mn were
measured with the atomic absorption spectrophotometer.
Table 2
Basic characteristics of carbon black.
Black median diameter
Specific surface area
Electric resistivity
Hydrometallurgy 171 (2017) 165–171
Total As concentration was measured with the atomic absorption
spectrophotometer equipped with a continuous hydride generator
(Hitachi HFS-3). As(III) concentration was determined by the method
medium Reference
developed by Yokoyama et al. (1993). It consists of a flow system using
1 M H2SO4 Kumari and Natarajan, ion-exclusion chromatography, the continuous hydride generator, and
2002 the atomic absorption spectrophotometer. As(III) and As(V) were
0.1 M H2SO4 Rath and Paramguru, 1994
separated using an anion-exchange resin, SP-Sephadex C-25(Pharmacia
pH 0.8, Nakazawa and Hareyama, Fine Chemicals Co.). 0.1 M NH3 -NH4Cl (pH 8.3) was used as an eluent.
H2SO4 2016 Solution removed from the flasks by sampling was replaced by
adding equal volume of the medium. At the end of the leaching
experiment the leachate was filtered, and the residue was recovered
and dried at 60 °C prior to conducting the XRD measurements.
A Cupric sulfate solution and As(V) solution used in this study were
1 Enargite
prepared by dissolving reagent-grade CuSO4·9H2O (Kanto Chemical Co.
Inc.) and 3As2O5·5H2O (Merck Ltd.) in distilled water, respectively.
Rest potential was measured using electrodes of MnO2 and enargite
prepared by mounting granular MnO2 (extra pure grade, Kanto
chemical Co. Ltd.)and enargite in 6.25 mm ID Lucite tubing as
described by Adam et al. (1984). Electrical contact was made using
silver paste to a platinum wire. Before each measurement, the electrode
surfaces were cleaned by polishing with 400 and 600 grit abrasive
papers followed by polishing on a metallurgical polishing wheel with
0.5 μm diamond powder as the abrasive.
40 50 60 70 3. Results and discussion
2θ
3.1. Rest potential of MnO2 and enargite
The steady-state rest potentials of MnO2 and enargite in one hour in
sulfuric acid solution at pH 1.0 were 1.140 V and 4.95 V (SHE),
respectively. The rest potential of MnO2 is close to that of pyrolusite
(0.910 V vs SCE) in 1 M H2SO4 reported by Kumari and Natarajan
(2002). Asbjornsson et al. (2004) reported the rest potential (open
circuit potential) of enargite as 0.4 V vs SHE in 0.1 M HCl solution.
These materials are expected to form galvanic couple in contact with
each other. MnO2 can act as the cathode, while enargite serves as the
anode, suggesting that enargite is oxidized to dissolve.
3.2. Effect of MnO2 on enargite leaching
Fig. 2 shows the effect of the MnO2 on the enargite leaching. It also
includes the results of the experiments performed to investigate the
effect of enargite on the MnO2 leaching. The leaching rate of enargite
increased in the presence of MnO2. Under these conditions the
extraction yield of Cu was 48% in 239 h, whereas it was 3% in the
absence of MnO2. The total Fe concentration was 2.8 mg/L in 239 h
with the MnO2.
The leaching rate of As also increased by the addition of MnO2.
Total As concentration in the presence of MnO2 was 158 mg/L, which
amounted to 40% of As in the enargite, and the analyses of As(III) in the
leachate showed that As almost occurred as As(V). MnO2 did not
dissolve independently, but its dissolution was accelerated in the
presence of enargite. The extraction yield of Mn was 23% with the
addition of 0.5 g of enargite in 239 h. The XRD pattern of the leaching
residue shown in Fig. 3(a) indicates the peaks of elemental sulfur. In the
presence of MnO2, the redox potential remained at nearly 900 mV
during the experiments, whereas it was approximately at 700 mV in the
absence of MnO2.
Since MnO2 is nobler than enargite, they form galvanic circuit in
contact with each other. In the galvanic contact, enargite acts as the
anode to be oxidized, while MnO2 acts as the cathode to be reduced.
36 nm
Enargite and MnO2 can be leached according to reaction (1).
65 m2/g 2Cu3AsS4 + 11MnO2 + 34H+ → 6Cu2+ + 2H3AsO4 + 11Mn2+ + 14H2 O
0.20 Ω cm + 8S0 (1)
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H. Nakazawa et al. Hydrometallurgy 171 (2017) 165–171

70 70

60 (a) MnO2
60 (b) Enargite
0g 2g
0g 0.5 g
50 50

Cu extracted, %

Mn extracted, %
40 Enargite 0.5 g 40
Initial pH 1.0 MnO2 2 g
30 30
Initial pH 1.0
20 20

10 10

0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time, h Time, h

(c) (d)
150 1000
As concentation, mg/L

0g 2g

Eh, mV vs SHE
100 Enargite 0.5 g
Initial pH 1.0
500
MnO
50 Enargite 0.5 g 0g 2g
Initial pH 1.0

0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time, h Time, h
Fig. 2. Effect of MnO2 on enargite leaching(a) Cu extraction (b) Mn extraction (c) As concentration (d) Eh.
Relative Intensity (scale unit =500cps)

Therefore, in the presence of MnO2 at pH 1.0, enargite can be

1 1 Enargite
3
(a)
33
3 be oxidized to sulfate by MnO2, resulting in a higher Mn/Cu molar ratio
33
(b)
10 20
Fig. 3. XRD patterns of residues from leaching experiments(a) with 2 g MnO2, (b) with
2 g MnO2 and 0.5 g carbon.
For the leaching experiments with the addition of MnO2, the molar
ratio of dissolved Mn ions to Cu ions observed in the leaching
experiment was 3.0 which was relatively high compared to the
stoichiometric value of 1.8 predicted by reaction (1). This difference
between the observed and stoichiometric values is attributable to some
excess MnO2 dissolution by other reactions such as oxidation of sulfidic
sulfur in enargite to sulfate.
Dutrizac and MacDonald (1972) investigated the acidified ferric
sulfate leaching of discs of synthetic enargite at 80 °C. They showed that
ferric ions oxidized enargite and that about 70% of sulfidic sulfur in
enargite was oxidized to element sulfur and just 30% of sulfidic sulfur
to sulfate.
Padilla et al. (2008) constructed the Eh-pH diagram for the CuAsS4-
H2 system at 25 °C considering the activities of the soluble species of
Cu, As, and S equal to 0.1. The resulting Eh-pH diagram for this system
indicated that at Eh > 0.58 V and pH < 2, the predominant species
will be Cu2 +, H3AsO4, and HSO4−.
leached to form sulfate according to reaction (2).
2 MnO2
3 Sulfur 2Cu3AsS4 + 35MnO2 + 44H2O → 6Cu2+ + 2H3AsO4 + 8HSO4− + 35Mn2+
1 (2)
+ 74OH−
1
1
1 For reaction (2), the predicted molar ratio of dissolved Mn ions to
1 1
2
2 1 Cu ions in the leaching experiments is 5.8. In the leaching experiments
2
in the presence of MnO2, some part of sulfidic sulfur in enargite would
than the predicted value by reaction (1).
The Cu/As molar ratio observed in the leaching experiment in the
30 40 50 60 70 presence of MnO2 was 3.6 at the end of the experiment, which is higher
than the stoichiometric value of 3.0. It is well known that MnO2 adsorbs
2θ
arsenic (Driehaus et al., 1994; Chiu and Hering, 2000; Manning et al.,
2002).
In order to investigate the adsorption of As(V) and Cu on the MnO2
surface, an experiments was carried out using sulfuric solution contain-
ing As(V) (44 mg/L) and Cu (78 mg/L) at pH 1.0. The results are shown
in Fig. 4. The As concentration decreased from 44 mg/L to 10 mg/L in
4 h, and it reached 5.8 mg/L at the end of the experiment, indicating
that arsenate adsorbed on the surface of MnO2. The Cu concentration
did not change after 48 h of the experiment. In the leaching experi-
ments, As(V) dissolved from enargite could adsorb on the surface of
undissolved MnO2, but Cu ions did not. Therefore, the Cu/As molar
ratio in the leaching experiment was higher than the value predicted by
the reactions (1) and (2).
3.3. Effect of carbon black on enargite leaching in the presence of MnO2
Fig. 5 shows the results of leaching experiments conducted with
different amount of added carbon black (0, 0.3, and 0.5 g) at a MnO2/
enargite ratio of 4. The figure also includes the result of the experiment
performed by adding 0.5 g of carbon black in the absence of MnO2.
Copper did not dissolve from enargite in the presence of the carbon

167
H. Nakazawa et al. Hydrometallurgy 171 (2017) 165–171

100 respectively.
For the additions of 0.3 g and 0.5 g of carbon black, the molar ratios
90 of Mn to Cu ions were 3.0 and 3.1 which were similar to that without
As, Cu concentration,mg/L

80
70
60
50
40
30
20
10
0 3.4. Effect of contact between enargite and MnO2 on enargite leaching in the
0 10
Fig. 4. Adsorption of As(V) and Cu(II) by MnO2.
black only. However, the rate and the extent of Cu extraction increased
with increasing carbon black dosage in the presence of MnO2. The
extraction yields of Cu were 37%, 61%, and 74% after 172 h of leaching
in ascending order of carbon black dosage. The dissolution rate of Mn
from MnO2 also increased with increasing the amount of added carbon
black. The leaching rate of As also increased by the addition of carbon
black. Total As concentration in the presence of 0.5 g carbon black was
260 mg/L, which accounted for 74% of As in the enargite.
Fig. 3(b) shows the XRD pattern of the leaching residue from the
experiment with addition of 0.5 g of carbon black. The peaks of enargite
were diminished relatively compared with these of MnO2 and the peaks
of elemental sulfur were observed. The broad peaks of about 23° and
25° at 2θ correspond to the peaks of MnO2 and carbon black,
the addition of carbon black. This suggests that carbon black accelerate
the galvanic interaction between enargite and MnO2.
The Cu/As molar ratio observed in the leaching experiment in the
Cu As presence of 0.5 g of carbon back was 3.3 at the end of the experiment,
whereas it was 3.6 in the absence of carbon black. In order to
investigate the adsorption of As(V) and Cu on the carbon black, an
MnO2 2 g adsorption experiment was performed using the same medium as that
Initial Cu 78 mg/L in the experiment conducted using MnO2 (seeing Fig. 3). The carbon
Initial As(V) 44 mg/L black did not adsorbed arsenic and copper (results not shown). One
Initial pH 1.0 reason for the lower Cu/As molar ratio could be attributive to higher
dissolution yield of MnO2 in the presence of carbon black.
20 30 40 50 60 presence of carbon black
Time, min
Two leaching experiments were carried out using − 75 + 53 μm
size fractions of enargite and MnO2 that were obtained by sieving the
both samples. One experiment was performed in the regular way. In the
other experiment, 1 g of the MnO2 was packed into a small bag
(30 mm × 30 mm) made from bolting cloth (opening 20 μm, AS One
Co. Ltd.), and the leaching test was conducted by suspending the bag in
the leaching solution containing enargite and carbon black. The open-
ing of the bolting cloth was sufficiently small; enargite and MnO2 were
not able to make direct contact with each other. The results are shown
in Fig. 6. The Cu dissolution was not enhanced without contact,
suggesting that the contact between enargite and MnO2 is vital for
the acceleration of enargite leaching in the presence of carbon black.
MnO2 serves as the cathode of various electrochemical cells, but it is
not significantly electrically conductive. Due to the chemical inert and
electrically conductive nature of carbons, especially carbon black is
used as the conductive additive in zinc-carbon batteries and alkaline
batteries (Chung, 2007). The carbon black is a very fine powder and

100 100
90 Carbon black 90 (b)
0g 0.3 g 0.5 g Carbon black
80 80
0g 0.3 g
0.5 g without MnO2
Cu extracted, %

70 70
Mn extracted, %

0.5 g
60 Enargite 0.5 g 60
MnO2 2 g Enargite 0.5 g
50 Initial pH 1.0 50
MnO2 2 g
40 40 Initial pH 1.0
30 30
20 20
10 10
0 0
0 50 100 150 200 0 50 100 150 200
Time, h Time, h
300

250
Carbon black
1000
(d)
0g 0.5 g
As concentation, mg/L

Eh, mV vs SHE

200 Enargite 0.5 g

MnO2 2 g
150 Initial pH 1.0 Carbon black
500 0g 0.3g
100
0.5g

50

0 0
0 20 40 60 80 100 120 140 160 180 200 0 20 40 60 80 100 120 140 160 180
Time, h Time, h
Fig. 5. Effect of carbon black dosage on enargite leaching in the presence of MnO2 (a) Cu extraction, (b) Mn extraction, (c) As concentration (d) Eh.

168
H. Nakazawa et al. Hydrometallurgy 171 (2017) 165–171

100 enargite. The leaching recovery of Cu was 88% at initial pH 0.6,

whereas it was 40% at initial pH 1.4 in 120 h. For initial pH 1.4, pH
90 increased to 1.8 in 43 h because of the consumption of H+ and the
80 With contact production of OH– in the galvanic reactions between enargite and MnO2
according to reactions (4) and (5).
Cu extracted, %

70 Without contact

60 3.5.3. Effect of stirring speed

50 The experiments were carried out by varying stirring speed of a
magnetic stirrer from 100 rpm to 400 rpm at room temperature. The
40 Enargite 0.5 g results are presented in Fig. 9. The extraction rates of Cu and Mn
MnO2 1 g increased with increasing stirring speed. Increasing agitation rate could
30 Carbon black 0.5 g improve collision rate among enargite, carbon black, and MnO2,
20 Initial pH 1.0 resulting in acceleration of galvanic leaching of enargite.
10
3.5.4. Effect of temperature
0 Dutrizac and MacDonald (1972) investigated the dissolution ki-
0 20 40 60 80 100 120 140 160 180 200 netics of pellets of resin impregnated synthetic enargite in acidic ferric
Time, h sulfate media in the temperature range of 60–95 °C, and reported that
extraction rate of Cu from enargite increased with increase in tempera-
Fig. 6. Effect of contact between enargite and MnO2 on enargite leaching in the presence ture.
of carbon black. To study the effect of temperature on the enargite leaching, leaching
experiments were conducted by maintaining the Erlenmeyer flasks in a
electrically conductive. One reason for the acceleration of extraction hot water bath equipped with a magnetic stirrer at 70 °C and 50 °C. The
rate of Cu from enargite could be that electron transfer from enargite to experimental conditions were as follows; the initial pH 0.6, stirring
MnO2 is facilitated via carbon black. Increase in electron flow could speed 200 rpm. The results are shown in Fig. 10. It also contains the
enhance the galvanic interaction between the both materials and result of the test performed at the room temperature. Elevating
improve the extraction rate of Cu from enargite. temperature resulted in enhancement of enargite leaching kinetics.
The extraction yield of Cu was 94% at 70 °C in 54 h, whereas it was
3.5. Effect of different factors in the presence of both MnO2 and carbon 60% at room temperature in 78 h in the presence of both MnO2 and
black carbon black.

3.5.1. Effect of MnO2 dosage
In order to investigate the effect of MnO2 dosage on enargite
leaching, leaching experiments were conducted by varying amount of
MnO2 added from 0 g to 2 g at a carbon black/enargite ratio of 1:1 at
room temperature. The results are shown in Fig. 7. The extraction rate
of Cu from enargite increased with increasing MnO2 dosage. For MnO2
dosage of 2 g, > 80% of Cu in the enargite was extracted in 238 h,
whereas the extraction yield of Cu was 53% with the addition of 0.5 g
MnO2. For the addition of 0.5 g of MnO2, MnO2 almost completely
dissolved in the leaching experiment, therefore, MnO2 was insufficient
to induce complete galvanic leaching of enargite.
3.5.2. Effect of initial pH
In order to evaluate the effect of initial pH on the kinetics of
enargite leaching, leaching experiments were carried out by varying
initial pH from 0.6 to 1.4 at room temperature. The results in Fig. 8
indicate that decreasing initial pH accelerated the kinetics of enargite
leaching and increased the rate and extent of the Cu extraction from
3.6. Reuse of carbon black from the residue for enargite leaching
The feasibility of reusing carbon black for treating subsequent
charges of enargite and MnO2 was examined. The first experiment
was performed using 0.5 g of enargite in the presence of MnO2 and
carbon black at 50 °C. Upon the completion of the first test (Run 1), the
solid was allowed to settle for 10 min and the leachate was extracted
from the flask. Another 200 mL of sulfuric acid medium at pH 1.0 was
added to the flask and the flask was maintained in the hot water bath at
50 °C. After the setting temperature of the medium in the flask was
reestablished, 0.5 g of new enargite and 1 g of MnO2 were added and
the test (Run 2) was restarted. The results are shown in Fig. 11. The
leaching rate in Run 2 was almost the same as that in Run 1. The carbon
black in the residue enhanced the kinetics of enargite leaching with
addition of MnO2, indicating that the carbon black in leaching residue
can be reused for the galvanic leaching of enargite using MnO2. Because
the carbon black used in this study flocculated well and settled quickly
under the experimental conditions, the residue which contain the

100 100
90 (a) Enargite 0.5 g 90 (b) Enargite 0.5 g
Carbon black 0.5 g Carbon black 0.5 g
Mn extracted, %

80 Initial pH 1.0
80 Initial pH 1.0
Cu extracted, %

70 70
60 60
50 50
40 40
30 30
20 MnO2 20 MnO2
0.5 g 1g 2g
10 10 0.5 g 1g 2g
0 0
0 50 100 150 200 250 0 50 100 150 200 250
Time, h Time, h

Fig. 7. Effect of amount of MnO2 on enargite leaching in the presence of carbon black (a) Cu extraction (b) Mn extraction.

169
H. Nakazawa et al. Hydrometallurgy 171 (2017) 165–171

100 2
90
80

Cu extracted, %
70
60 Enargite 0.5 g
MnO2 1 g

pH
50 1 Carbon black 0.5 g
40
30
Initial pH
20 pH 0.6 pH 0.8 pH 0.6 pH 0.8 pH 1.2
10 pH 1.2 pH 1.4 pH 1.4
0 0
0 20 40 60 80 100 120 140 0 20 40 60 80 100 120 140
Time, h Time, h
Fig. 8. Effect of initial pH on enargite leaching (a) Cu extraction (b) pH.

100 100
90 Strirring speed 90
80 100 rpm 80
Run 1
Cu extracted, %

Cu extracted, %
70 200 rpm 70 Enargite 0.5 g
MnO2 1 g
60 400 rpm 60 Carbon black 0.5 g
50 50 50 oC
Initial pH 1.0
40 40 Run 2
30 30 leaching residue
Enargite 0.5 g
Enargite 0.5 g
20 MnO2 1 g
Carbon black 0.5 g
20 MnO2 1 g
10 50 oC
Initial pH 1.0 10 Initial pH 1.0
0 0
0 50 100 150 200 250 0 20 40 60 80 100 120 140
Time, h
Time, h
Fig. 9. Effect of stirring speed on enargite leaching.
Fig. 11. Reuse of carbon black in the residue for the galvanic leaching of chalcopyrite
using MnO2.
100
90 Enargite 0.5 g chemical reagent MnO2 in the sulfuric media. In the presence of MnO2,
MnO2 1g the leaching rate of enargite improved, and 48% of copper in enargite
80 Carbon black 0.5 g dissolved in 239 h, whereas the extraction yield was 3% in the absence
Cu extracted, %

70 Initial pH 0.6 of MnO2. The addition of carbon black accelerated the kinetics of
enargite leaching significantly in the presence of MnO2, and the
60 extraction yield of copper was 74% after 172 h with the addition of
50 0.5 g of carbon black. Because carbon black is extremely fine powder
and electrically conductive, carbon black could facilitate electron
40 transfer from enargite to MnO2, resulting in enhancement of the
30 Room Temperature galvanic leaching of enargite. Decreased pH and elevated temperature
increased the extraction rate of copper from enargite in the presence of
20 50 °C MnO2 and carbon black. 94% of copper in the enargite was leached in
10 70 °C 54 h at 70 °C and pH 0.6 in the presence of MnO2 and carbon black.

0 References
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