Hydrometallurgy 181 (2018) 195–205

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

A study of the electro-assisted reductive leaching of a chalcopyrite T

concentrate in HCl solutions. Part I: Kinetic behavior and nature of the
chalcopyrite reduction
⁎
V.J. Martínez-Gómeza, J.C. Fuentes-Aceitunoa, , R. Pérez-Garibaya, Jae-chun Leeb
a
Centro de Investigación y de Estudios Avanzados del IPN, Unidad Saltillo, Av. Industria Metalúrgica # 1062, Parque Industrial Ramos Arizpe, Ramos Arizpe, Coahuila
25900, Mexico
b
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Republic of Korea

A R T I C LE I N FO A B S T R A C T

Keywords: This first part of research presents an analysis of the electro-assisted reductive leaching (ERL) of refractory
Reductive leaching chalcopyrite (CuFeS2) performed in HCl media using an electrolytic cell operated at room temperature and
Chalcopyrite pressure. This is as an alternative approach to decrease the passivation phenomenon observed in the ERL process
Electroleaching with sulfuric acid, which favored the chalcopyrite reduction kinetics at pulp densities > 10 g/L. Different
Monoatomic hydrogen, Copper
variables were optimized to understand the electro-reduction kinetics of chalcopyrite such as: acid concentra-
tion, current density and pulp density. The reaction mechanism proposed was complemented with the elec-
trochemical techniques, and SEM-EDS and X-ray diffraction analyses. The results revealed that electro-reduction
of chalcopyrite performed in HCl at a pulp density of 100 g/L present a higher reduction rate than that of the
sulfuric acid system. From a mechanistic viewpoint, chalcopyrite can be sequentially reduced to chalcocite and
metallic copper, respectively. The latter is a very reactive species which can be easily oxidized in the presence of
air and remaining hydrochloric acid, to cuprous hydroxychloride or atacamite species (Cu2Cl(OH)3) and cuprite
(Cu2O) when the solid residue is withdrawn from the reactor. These copper species are highly soluble in aqueous
solutions which can permit the recovery of copper. From an energetic viewpoint, the energy consumption of the
HCl electrolytic system is lower than that of the H2SO4 electrolytic system.

1. Introduction Crundwell et al., 2015; Khoshkhoo et al., 2014; Nicol, 2017; Nicol et al.,
2017; Nicol and Basson, 2017). However, its main limitation relates to
About 70% of the world copper resources are present as chalco- the passivation of chalcopyrite due to the formation of elemental sulfur,
pyrite (CuFeS2) (Wang, 2005), which is commonly processed by polysulfide species or iron hydroxysulfate species (Burkin, 1969;
smelting (Najdenov et al., 2012). Recently it has been reported that Córdoba et al., 2008; Ammou-Chokroum et al., 1977; Muñoz et al.,
over 80% of known copper is in porphyry copper and sediment-hosted 1979; Habashi and Toor, 1978; Yoo et al., 2010; Nicol, 2017). In order
copper deposits (Singer, 2017). It is important to develop alternative to decrease such passivation, inorganic acids such as nitric acid, sulfuric
green processes for the recovery of copper from chalcopyrite, due to the acid and hydrochloric acid, have been studied (Al-Harahsheh et al.,
high production costs and pollution in the conventional smelting pro- 2008). It is reported that the chalcopyrite dissolution kinetics is higher
cesses. Therefore, scientists and engineers have considered hydro- in the oxidative systems containing chloride species or hydrochloric
metallurgy as an alternative. In general, the two types of hydro- acid than in those containing sulfate species (Almeida et al., 2016;
metallurgical methods for the recovery of copper from the chalcopyrite Nicol, 2017; Habashi and Toor, 1978; Yoo et al., 2010; Liddicoat and
are based on the oxidative and reductive processes, which have mostly Dreisinger, 2007; Yévenes, 2009).
been studied at laboratory scale. The oxidation of chalcopyrite has been Chemical reductive processes have been considered an alternative
studied by several authors (Burkin, 1969; Ammou-Chokroum et al., to decrease the passivation of chalcopyrite commonly found in oxida-
1977; Muñoz et al., 1979; Prince and Warren, 1986; Nicol and Lázaro, tive processes. In these processes, chalcopyrite is predominantly re-
2003; Córdoba et al., 2008; Yang et al., 2015; Hao-dan et al., 2012; duced to less refractory copper sulfide species such as chalcocite. The

⁎
Corresponding author.
E-mail address: [email protected] (J.C. Fuentes-Aceituno).

https://doi.org/10.1016/j.hydromet.2018.09.012
Received 1 March 2018; Received in revised form 11 September 2018; Accepted 29 September 2018
Available online 01 October 2018
0304-386X/ © 2018 Elsevier B.V. All rights reserved.
V.J. Martínez-Gómez et al. Hydrometallurgy 181 (2018) 195–205

reduction of chalcopyrite has been assessed in the presence of sulfate or addressed in this paper.
chloride media and chemical reducing agents such as: iron, copper, Hydrogen sulfide produced during the reduction of chalcopyrite
lead, aluminum, H2 and SO2 (Hiskey and Wadsworth, 1975; (Eqs. (1), (2), (3), (4) and (6)) can be electro-oxidized at the anode
Avraamides et al., 1980; Sohn and Wadsworth, 1980; Hackl et al., 1987; producing elemental sulfur, which inhibits the hydrogen sulfide emis-
Chae and Wadsworth, 1979; Shirts et al., 1974, Dreisinger and Abed, sions (Fuentes-Aceituno et al., 2008a), while ferrous ions produced
2002; Lapidus and Doyle, 2006). In terms of efficiency, the chloride during the process can be further treated to obtain metallic iron by
chemical-reductive systems present higher chalcopyrite reduction ki- rapid electrodeposition (Kasper, 1937). It is thus possible to obtain
netics than the sulfate reductive systems (Dreisinger and Abed, 2002). valuable products such as Cu, Fe and S, from the chalcopyrite decom-
Chalcopyrite is considered a semi-conductor that can be electro- position. However, recently it has been observed that chalcopyrite
lytically decomposed (Biegler, 1977) producing bornite (Cu5FeS4), electro-assisted reduction kinetics is considerably hindered at the pulp
chalcocite (Cu2S) and metallic copper (Cu0) (Biegler and Constable, densities higher than 10 g/L in sulfuric acid media (Fuentes-Aceituno
1977; Warren et al., 1985; Fuentes-Aceituno et al., 2008a, 2008b). et al., 2008a). This renders the process uneconomical. According to
There are a few references related to the electroreduction of chal- Martínez-Gómez et al. (2016), elemental sulfur is produced on the
copyrite slurries in electrolytic cells (Biegler and Constable, 1977; chalcopyrite particles in such a system promoting the passivation of
Fuentes-Aceituno et al., 2008a; Martínez-Gómez et al., 2016). In many chalcopyrite.
of these investigations sulfuric acid was used as the electrolytic In this research, the electro-assisted reductive leaching of chalco-
medium, while only one reference (Biegler and Constable, 1977) re- pyrite was studied systematically in HCl solutions with different tech-
ported the use of 4 M HCl to perform the continuous electrolytic re- niques, in order to elucidate suitable conditions which can accelerate
duction of a chalcopyrite slurry. However, electroreduction of chalco- and increase the conversion of chalcopyrite reduction at pulp densities
pyrite slurries in HCl with electrolytic cells has not been studied higher than 10 g/L while minimizing the energy consumption. This
systematically, particularly the complete characterization of solid pro- information is valuable to understand the phenomena occurring in the
ducts formed in this system is not presented. chalcopyrite electro-reduction using HCl media, and to develop in fu-
From a mechanistic viewpoint, chalcopyrite can be electrolytically ture an alternate hydrometallurgical reductive process for the recovery
reduced in acid solutions to bornite or chalcocite, according to Eqs. (1) of copper from refractory chalcopyrite.
and (2), respectively (Biegler, 1977; Biegler and Constable, 1977;
Biegler and Swift, 1976): 2. Experimental
5CuFeS2 + 12H+ + 4e− → Cu5 FeS4 + 4Fe2 + + 6H2 S (1)
2.1. Materials
2CuFeS2 + 6H+ + 2e− → Cu2 S + 3H2 S + 2Fe2 + (2)
Electrochemical tests were carried out employing a chalcopyrite
Chalcocite can be further electro-reduced to metallic copper, ac-
electrode. For the preparation of the working electrode, a pure chal-
cording to Eq. (3) (Biegler and Constable, 1977).
copyrite crystal was mounted in a teflon rod in order to obtain a ro-
Cu2 S + 2H+ + 2e− → 2Cu + H2 S (3) tating disk electrode with exposed active area of 19.6 mm2. The ele-
The global reduction of chalcopyrite to copper can be represented mental analysis or EDS (full) of the chalcopyrite crystal was determined
by scanning electron microscopy (SEM, Philips-XL-30-ESEM), which
by Eq. (4):
revealed that chalcopyrite has high purity; its chemical composition is
CuFeS2 + 4H+ + 2e− → Cu + 2H2 S + Fe2 + (4) shown in Table 1.
Electro-assisted reductive leaching of chalcopyrite was studied
Thermodynamic data for chalcopyrite reduction (Eh-pH diagram)
employing a chalcopyrite concentrate obtained from Peñoles, Minera el
revealed that the stability boundaries of these reduced copper phases
Roble, Cuencamé, Durango, which contains: 68.3% chalcopyrite, 15.4%
are all below the reversible hydrogen potential, which means that their
pyrite, 9.1% sphalerite and 1.5% galena. The particle size distribution
actual formation will depend on kinetic factors, in particular the over-
in the concentrate is found to be in the range 11 μm to 16 μm with an
potential of hydrogen evolution (Biegler and Swift, 1976).
average size of 13.3 μm.
Fuentes-Aceituno et al., (2008a), Fuentes-Aceituno, (2010) pro-
posed an alternative reaction mechanism for the electrolytic reduction
of chalcopyrite in sulfuric acid medium, i.e., formation of the inter- 2.2. Electrochemical tests
mediate monoatomic hydrogen species (reducing agent) on the cathode
surface (Eq. (5)). This reducing agent promotes the reduction of chal- The experiments were carried out at room temperature (25 °C)
copyrite to chalcocite according to Eq. (6). employing a conventional three-electrode electrochemical cell, which
comprised of a reference electrode of Ag/AgCl (all potentials presented
2H+ + 2e−→2H· (5)
in this work were changed to the standard hydrogen electrode, SHE), a
2CuFeS2 + 4H+ + 2H· → Cu2 S + 3H2 S + 2Fe2 + (6) graphite rod (Alfa Aesar) as the counter-electrode and a massive crystal
of chalcopyrite as the working electrode. The cell was connected to a
Monoatomic hydrogen can recombine through a chemical or an potentiostat/galvanostat (Versastat 4-400, PAR).
electrochemical event, according to Eqs. (7) and (8), respectively. The surface of the working electrode was polished with a silicon
2H· → H2 (7) carbide paper (800, 1200 and 2400) and was then polished in wet to a
mirror-like finish employing alumina powder (0.5 μm) for 50 min. The
H·+e− + H+ → H2 (8) electrode was rinsed with deionized water and was sonicated with
It is worth mentioning that the number of electrons transferred in
Eq. (6) are the same to that transferred in the direct electro-reduction Table 1
Chemical composition of the chalcopyrite working electrode.
mechanism (Eq. (2)), which suggests that the chalcopyrite reduction
mechanism in this type of electrolytic systems can be explained in terms Element wt% at. %
of: a) electrons transferred directly from cathode to the chalcopyrite
Cu 34.12 24.62
particles, or b) electrons transferred from monoatomic hydrogen to the
Fe 30.91 25.38
chalcopyrite particles. As can be seen the nature of the electron transfer S 34.97 50.00
mechanism is a complex problem, which is not intended to be

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V.J. Martínez-Gómez et al. Hydrometallurgy 181 (2018) 195–205

acetone for 10 min. This methodology was followed before each vol- according to Eq. (4), n = 2.
tammetric experiment.
The electrochemical tests were performed employing an aqueous
solution of 2 M HCl at room temperature. Nitrogen was bubbled in the 3. Results and discussion
aqueous solutions for 30 min to eliminate the dissolved O2 and CO2 and
maintain inert atmosphere in the cell. Open Circuit Potential (OCP) of 3.1. Electrochemical study of chalcopyrite reduction in HCl solutions
the polished chalcopyrite electrode was measured before each vol-
tammetric experiment. The cyclic voltammetry was recorded at 25 mV/ Based on the results reported elsewhere (Martínez-Gómez et al.,
s from the OCP to different cathodic vertex potentials (−100, −400 2016), it can be stated that the reaction mechanism for the electro-
and − 600 mVSHE), finishing the cycle at the OCP. On the other hand, assisted reduction of chalcopyrite in sulfuric acid solutions occurs by
cathodic linear voltammetry was performed at 25 mV/s from the OCP sequential events, through the interaction of chalcopyrite with the
to the same vertex potential. The potential scan rate of 25 mV/s was monoatomic hydrogen produced on the cathode (Eq. (6)) or by the
adequate to reveal the characteristic peaks related to the re-oxidation of direct electronic transfer between the mineral and the cathode (Eq. (2))
products formed during the cathodic polarization of chalcopyrite. At (Fuentes-Aceituno et al., 2008a, 2008c; Fuentes-Aceituno, 2010;
the end of tests, the surface of the electrodes was characterized by EDS Martínez-Gómez et al., 2016; Biegler and Constable, 1977; Biegler and
studies. Swift, 1976). The basic premise is that chalcopyrite is firstly reduced to
chalcocite, which is followed by the reduction of chalcocite to metallic
2.3. Electro-assisted reductive leaching tests copper. Metallic copper is easily oxidized when it is withdrawn from the
reactor producing cupric sulfate or cuprous oxide species (Martínez-
The electro-assisted reductive leaching experiments were carried Gómez et al., 2016). From a mechanistic viewpoint, it would be inter-
out employing the same experimental scheme reported previously esting to study the effect of changing the electrolytic medium from
(Martínez-Gómez et al., 2016), which consisted of a batch electrolytic sulfuric acid to hydrochloric acid on the nature of chalcopyrite reduc-
cell (0.5 L) with the anodic and cathodic compartments separated by an tion as well as the reactivity of the solid products when withdrawn from
anionic membrane (CMI-7001), which avoids the transfer of mineral the reactor. Fig. 1 illustrates the cyclic voltammograms obtained for the
and ferrous ions from the cathodic to the anodic chamber. Carbon chalcopyrite electrode immersed in 2 M HCl. The voltammograms were
plates with a surface area of 70 cm2 were used as the cathode and recorded scanning the potential from OCP into the cathodic direction
anode. In order to perform the reductive leaching experiments in a up to a vertex potential of −100, −400 and − 600 mVSHE; the po-
galvanostatic regime, the cell was connected to a power supply (Tek- tential scan was reversed to the anodic direction up to a vertex potential
tronix, PWS4305). of 1200 mVSHE ending the cycle at OCP.
The procedure employed to carry out the electro-assisted reductive The potential sweep was inverted into the anodic direction in order
leaching experiments was as follows. A 250 mL solution containing 0.5, to elucidate the formation of different copper products that may be
1 or 2 M HCl was placed in the cathodic compartment of the electrolytic obtained during the previous cathodic scan performed at different
cell, and an equal volume (250 mL) of an aqueous solution containing vertex potentials. In addition, linear voltammetries were carried out by
H2SO4 at the same concentration was placed in the anodic compartment scanning the potential from OCP to −100, −400 and − 600 mVSHE,
to decrease the possible production of chlorine gas. 2.5, 12.5 or 25 g of and the modified surfaces of the chalcopyrite electrodes were char-
the chalcopyrite concentrate were placed in the cathodic compartment acterized using the EDS technique. As can be observed in Fig. 1, when
in order to achieve a pulp density of 10, 50 or 100 g/L, respectively. the chalcopyrite electrode is polarized from OCP up to −100 mVSHE,
Both compartments were mechanically agitated at 200 rpm with a te- the chalcopyrite does not exhibit any reduction (see straight line in
flon impeller. A constant current of 0, 0.3, 0.5 or 0.7 A was applied to Fig. 1); this is consistent with the non-appearance of re-oxidation peaks
the electrolytic cell. Chalcopyrite reduction kinetics can be followed by related to chalcocite during the anodic scan. However, it is only pos-
measuring the iron released into the solution. Several samples were sible to observe the characteristic oxidation peak of chalcopyrite (peak
withdrawn from the cathodic compartment at 0, 5, 10, 15, 20, 30, 40, Ox in voltammetry or straight line magnified at 10× in Fig. 1) at ~620
60, 90, 120, 180, 240, 300, 360 min, and the dissolved iron was ana- mVSHE, which is in good agreement with the potential reported by Nicol
lyzed by atomic absorption spectrometry (Spectra AA 220FS). An
electro-assisted reductive leaching of a pure pyrite sample was also
performed at 0.7 A for 360 min, validating that dissolved iron in the
electro- reductive tests only comes from the chalcopyrite species. The
solid residues obtained from the electro-assisted reductive leaching of
chalcopyrite were filtered, and were air dried and characterized by X-
ray diffraction technique. In order to determine the different products
that can be formed with or without rinsing, some solid residues ob-
tained at 0.7 A were rinsed with deionized water to remove the re-
maining hydrochloric acid. These solid residues were left for air drying
and were characterized by X-ray diffraction.
The cumulative current efficiency at any time, t, was calculated for
the electro-assisted reductive leaching experiments as a function of
chalcopyrite conversion using the Eq. (9) (Martínez-Gómez et al.,
2016).
%φ = (QCuFeS2/Qtot )100% = (mCuFeS2 F/It)100% = (mFe2 +Fn/It)100%
(9)
Where QCuFeS2 = cumulative charge used in the reduction of chalco-
pyrite according to Eq. (4), Qtot = total cumulative charge passed
through the cell, mCuFeS2 = moles of chalcopyrite reduced, F = Far- Fig. 1. Cyclic Voltammograms for the chalcopyrite electrode at different
aday's constant, I = applied current, t = time (s), mFe2+ = moles of cathodic vertex potentials. Voltammograms recorded from OCP (100 mVSHE) to
Fe2+ that report to solution and n = number of electrons transferred, different cathodic vertex potentials in 2 M HCl at 25 °C and 25 mV/s.

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Fig. 2. EDS of the chalcopyrite electrode surface subjected to a potential sweep from OCP to (a) −100 mVSHE, (b) −400 mVSHE, and (c) −600 mVSHE in 2 M HCl.

et al. (2017c), for the chalcopyrite oxidation in HCl media, which where: Q = transferred charge density in c/cm2, ν = potential sweep
probably can take place according to Eq. (10): velocity in V/s, j = current density in A/cm2, E = potential in V.
Charge transferred during the cathodic potential scan performed for the
CuFeS2 = CuS + Fe(II) + S + 2e− (10)
cyclic voltammetry up to −400 mVSHE corresponds to 0.196 c or 1 c/
Fig. 2a shows the EDS spectrum for the chalcopyrite surface ob- cm2 while the charge transferred in anodic peak Ox1 (same cyclic
tained during the cathodic scan from OCP to −100 mVSHE; this analysis voltammogram) corresponds to 0.194 c or 0.98 c/cm2. As can be seen,
clearly shows the characteristic peaks of Cu, Fe and S, which suggests charge transferred during the cathodic scan and in anodic peak Ox1 is
the presence of chalcopyrite in the sample. In fact, the semi-quantita- practically the same, which ratifies that peak Ox1 is related to the
tive analysis is very similar to that given in Table 1 for the pure chal- oxidation of chalcocite formed during the cathodic scan. Furthermore,
copyrite. This result is consistent with the cyclic voltammogram shown the first Faraday's Law can be employed to determine the amount of
in Fig. 1, which means that chalcopyrite is not reduced at −100 mVSHE. Cu2S formed during the cathodic scan (Eq. (2)) as well the amount of
When the potential sweep is performed at more cathodic potential Cu2S oxidized at peak Ox1 (Eq. (11). As expected, the result reveals the
than −100 mVSHE, e.g., −400 mVSHE, the presence of a cathodic cur- same amount of Cu2S, i.e., 1.01 × 10−6 mol approximately.
rent is observed (Fig. 1), which is the characteristics of a reductive The EDS analysis for the chalcopyrite electrode polarized from OCP
process of chalcopyrite. Furthermore, when the potential scan is in- to −400 mVSHE (Fig. 2b), illustrates the presence of Cu and S, both
verted into the anodic direction, the formation of an oxidation peak at elements can be related to the presence of chalcocite on the electrode
600 mVSHE is observed (peak Ox1, Fig. 1), which is the characteristics of surface.
the chalcocite oxidation to covellite and cupric ions (Fuentes-Aceituno Finally, the polarization of the chalcopyrite electrode performed
et al., 2008b; Elsherief, 2002), according to Eq. (11). from OCP to −600 mVSHE is also shown in Fig. 1. An increase in the
recorded cathodic current at −600 mVSHE is observed, which can be
Cu2 S = CuS + Cu2 + + 2e− (11) compared to that found at −400 mVSHE. The cathodic behavior is very
similar to that found in sulfuric acid (Martínez-Gómez et al., 2016). The
This result reveals that chalcopyrite can be reduced to chalcocite in
increase in the recorded cathodic current reveals an increase in the
the HCl medium at −400 mVSHE, according to Eq. (2). The production
amount of reduced chalcopyrite. Furthermore, when the potential scan
of chalcocite at this energetic condition was also demonstrated in sul-
is inverted into the anodic direction, two main oxidation peaks are
furic acid system (Martínez-Gómez et al., 2016). An analysis of the
found at −300 mVSHE and 600 mVSHE, (peaks Ox2 and Ox1, Fig. 1)
charge transferred during the cathodic scan as well as in anodic peak
which are characterized by the oxidation of products formed previously
Ox1 can be performed to ratify the formation of chalcocite when
during the cathodic scan. This result reveals the formation of two re-
chalcopyrite is reduced at −400 mVSHE. Charge transferred during the
duction products during the cathodic scan performed from OCP to
cyclic voltammetry shown in Fig. 1 was calculated using the Versas-
−600 mVSHE. Actually, chalcocite is one of the products which can be
tudio software ® included with the potentiostat/galvanostat, this soft-
formed according to Eq. (2). Once chalcocite is formed, it can be re-
ware permits the exact calculation of charge transferred in cyclic vol-
oxidized at the anodic peak of 600 mVSHE (peak Ox1, Fig. 1) according
tammetry experiments avoiding the contributions of the charge or
to Eq. (11), which is the same when the chalcopyrite electrode was
discharge of the double layer. The calculations were ratified integrating
polarized up to −400 mVSHE (peak Ox1, Fig. 1). As regards the anodic
the data of Fig. 1 using Eq. (12) (Greef et al., 1993) in the Origin
peak found at −300 mVSHE (peak Ox2, Fig. 1), this can be related to the
software ®, considering the use of baselines in oxidation-reduction
re-oxidation of second reduction product formed at −600 mVSHE. As
signals to eliminate the residual current from the charge calculations
reported earlier the metallic copper can be produced at a cathodic
(Wang, 2001; Bagotsky, 2006; Bard and Faulkner, 2001). It is worth
potential of −600 mVSHE in the sulfuric acid media (Martínez-Gómez
mentioning that contribution of residual current related to the oxida-
et al., 2016). Therefore, it is probable that in HCl media also, metallic
tion and reduction of impurities contained in the electrolytic medium
copper is produced from the sequential reduction of chalcopyrite to
was avoided while bubbling N2 to eliminate the dissolved O2 and CO2,
chalcocite and finally to metallic copper, according to Eqs. (2) and (3),
as mentioned in the experimental section. Contribution of residual
respectively. Actually, the anodic peak found at −300 mVSHE (peak
current related to non-faradaic or capacitive processes was insignificant
Ox2, Fig. 1), is associated with the re-oxidation of metallic copper in the
compared to the faradaic current. Therefore Eq. (12) was used to cal-
presence of hydrogen sulfide to chalcocite, according to Eq. (13)
culate the charge transferred in faradaic processes at a constant po-
(Elsherief, 2002; Fuentes-Aceituno et al., 2008b):
tential sweep.
2Cu + H2 S = Cu2 S + 2H+ + 2e− (13)
Q = 1/ ν ∫ j∗ dE (12)

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Fe and S (Fig. 2c), besides Cu, Cl and O, which can be related to the
unreacted chalcopyrite. In fact, the electrons beam employed in the EDS
can penetrate a depth of 1–1.5 μm, which means that the Fe and S can
be detected below the layer of Cu-Cl-O compound. Furthermore, at this
cathodic potential (−600 mVSHE) the evolution of molecular hydrogen
and hydrogen sulfide occurs massively, which can promote the partial
isolation of the unreacted chalcopyrite, and consequently the formation
of a thin layer of the Cu-Cl-O compound.

3.2. Electro-assisted reductive leaching of chalcopyrite using an electrolytic

cell with anionic separator

Having studied the different solid species that can be formed during
the electrochemical reduction of chalcopyrite in HCl solutions, the
electro-assisted reductive leaching of chalcopyrite was assessed in an
electrolytic cell with HCl solution in the cathodic compartment while
varying the current density, acid concentration and pulp density. H2SO4
solution was employed in anodic compartment to decrease the possible
Fig. 3. Comparison of the recovery of chalcopyritic and pyritic iron during the evolution of chlorine gas. The characterization of the Cu-Cl-O com-
electro-assisted reductive leaching of the chalcopyrite concentrate at 0.7 A in pound mentioned in the previous section was further examined.
2 M HCl or 2 M H2SO4. Pulp density-10 g/L chalcopyrite concentrate or pyrite
in 250 mL HCl or H2SO4 at 200 rpm and room temperature without a nitrogen
3.2.1. Characterization of solid residues obtained from the electro-assisted
atmosphere (open reactor).
reduction of chalcopyrite in HCl
It is worth mentioning that the electro-assisted reductive leaching of
An analysis of the charge density transferred during the cathodic chalcopyrite can be followed by the amount of ferrous ions released
scan at −600 mVSHE and in anodic peaks Ox2 and Ox1 was carried out from the mineral into the bulk solution (Fuentes-Aceituno et al., 2008a;
employing Eq. (12). The results reveal that the charge transferred Martínez-Gómez et al., 2016). As mentioned in Section 2 the chalco-
corresponds to 0.455 c or 2.32 c/cm2, 0.0633 c or 0.323 c/cm2 and pyrite concentrate used in the electro-assisted reductive leaching ex-
0.269 c or 1.372 c/cm2 for the total cathodic scan, anodic peak Ox2 and periments contains pyrite, which could be dissolved in the HCl-elec-
anodic peak Ox1, respectively. As can be seen, total cathodic charge is trolytic system. Therefore, it is important to evaluate the amount of iron
higher than the addition of anodic charges of peaks Ox2 and Ox1, ions which could also be leached from the pyrite. Fig. 3 shows the re-
which suggests that a part of the cathodic current (0.186 c or 0.949 c/ lease of pyritic iron vs time using a pure pyrite sample in 2 M HCl at 0.7
cm2, approximately) is employed to perform another electrochemical A and 25 °C. This figure reveals that pyrite is practically insoluble
reaction, e.g., the hydrogen evolution reaction. It is worth mentioning during 300 min. Therefore, it is concluded that iron released during the
that the evolution of bubbles was evident on the working electrode at electro-reductive leaching of the chalcopyrite concentrate can only be
−600 mVSHE. The rest of cathodic charge was employed to carry out related to the chalcopyrite species.
the reduction of chalcopyrite to chalcocite (0.206 c or 1.05 c/cm2) and It is also possible to observe in Fig. 3 a comparison of the release of
metallic copper (0.0633 c or 0.323 c/cm2), according to Eqs. (2) and chalcopyritic iron vs time in 2 M HCl or H2SO4 in the cathodic com-
(3), respectively. The charge transferred at anodic peak Ox1 (0.269 c or partment of the electrolytic cell operated with carbon electrodes at
1.372 c/cm2) is higher than that of the chalcocite formed during the 0.7 A and 25 °C. Thus almost 95% of chalcopyritic iron is obtained in
cathodic scan (0.206 c or 1.05 c/cm2), this difference is related to the ~120 min in the HCl system compared to 84% of iron under the H2SO4
formation of chalcocite at peak Ox2. Therefore, charge transferred at in the same period. The result clearly reveals that the electro-assisted
anodic peak Ox1 corresponds to the oxidation of chalcocite formed reduction of chalcopyrite in HCl is kinetically faster than that of H2SO4.
during the cathodic scan and at peak Ox2. Furthermore, according to Martínez-Gómez et al. (2016), when the
In order to complement the last result, a linear voltammetry was H2SO4 is used as the electrolyte in the cathodic compartment of elec-
repeated from OCP to −600 mVSHE for the fresh chalcopyrite electrode trolytic cell operated with aluminum as cathode, 87% of chalcopyrite
and at the end of the polarization test, the chalcopyrite electrode was can be reduced in the same processing time and current intensity. The
withdrawn without applying any rinsing. The surface of this electrode experiment with 2 M HCl and carbon electrodes was repeated to ex-
was characterized using EDS, and analysis is presented in Fig. 2c. The amine the effect of rinsing the solid residues obtained from the leaching
presence of Cu, Cl and O on the modified surface of electrode is pre- on the type of copper compound obtained. At the end of experiments
dominantly observed. It is relevant to emphasize the presence of O and the leach solutions were filtered. In one case, the solid residues were
Cl on the surface of the solid residue, which are commonly not found in only filtered without rinsing while the solid residue obtained in the
the reductive processes, thus suggesting the occurrence of a similar second experiment was rinsed with deionized water. Both solid residues
phenomenon as observed in the sulfuric acid system (Martínez-Gómez were air dried. In order to elucidate the copper species which can be
et al., 2016). The metallic copper formed during the chalcopyrite re- formed in both experiments, the solid residues were characterized by
duction (inside the reactor, Eqs. (3) and (4)) is a very reactive species, the X-ray diffraction technique. The XRD patterns corresponding to the
which on withdrawing from the reactor, reacts easily with oxygen (air) solid residue filtered without rinsing (Experiment 1) and the residue
producing copper oxides or even copper sulfates. In the case of HCl rinsed with deionized water (Experiment 2) are displayed in Fig. 4a and
medium, the polarized electrode was not rinsed at the end of the test. b, respectively.
Therefore, the metallic copper is formed during the polarization test The XRD analysis (Fig. 4a) of the solid residue filtered without
and is confirmed at the anodic peak found at −300 mVSHE (peak Ox2, rinsing shows the presence of oxidized copper hydroxychloride species
Fig. 1). The metallic copper reacted with the residual HCl on the (Cu2Cl(OH)3), commonly known as atacamite, which has not been re-
electrode surface and also with oxygen of the air producing a Cu-Cl-O ported before in this type of reductive systems. This result is in good
compound, which was not reported before. This mineral phase will be agreement with the EDS characterization shown in Fig. 2c. As men-
identified in the next sections. tioned before, metallic copper formed during the reductive stage is
It is interesting to mention that the EDS also showed the presence of easily oxidized when the solid residue is withdrawn from the

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Fig. 4. X-ray diffraction pattern of the solid residues obtained in Fig. 3 with the electro-assisted reductive leaching of chalcopyrite in HCl, (a) without rinsing and (b)
rinsed with deionized water (JCPDS file no. is shown against each species).

electrolytic reactor, and atacamite is obtained by oxidation of metallic

copper in the presence of oxygen, HCl and water (Eq. (14)).

2Cu0 + O2 + HCl + H2 O → Cu2 Cl(OH)3 (14)

On the other hand, when the solid residue is filtered with rinsing
using deionized water, the XRD analysis (Fig. 4b) shows the presence of
cuprite (Cu2O). The presence of cuprite is related to the aerial oxidation
of metallic copper (product of the chalcopyrite reduction) when the
residue is withdrawn from the reactor; this result is similar to that of
sulfuric acid system (Martínez-Gómez et al., 2016).
It may also be mentioned that no lead compound is found in the
solid residues (Fig. 4a and b). This indicates that lead from galena
dissolved in HCl, is either present in the leach solution or on cathode of
the electrolytic reactor. In the case of the sulfuric acid system, galena is
however, transformed to the anglesite, which is practically insoluble in
sulfate containing solutions (Martínez-Gómez et al., 2016).

3.2.2. Effect of the applied current Fig. 5. Recovery of chalcopyritic iron during the electro-assisted reductive
The effect of the applied current was evaluated on the chalcopyrite leaching of the chalcopyrite concentrate employing different galvanostatic re-
reduction kinetics in 2 M HCl at room temperature, and results of gimes, in the presence of 2.5 g chalcopyrite concentrate in 250 mL 2 M HCl at
chalcopyritic iron dissolution vs time are shown in Fig. 5. Increase in 200 rpm and room temperature, without a nitrogen atmosphere (open reactor).
the applied current from 0.3 to 0.7 A promotes the chalcopyrite re-
duction kinetics; e.g., a chalcopyritic iron recovery of 30, 58 and 85% is chalcopyrite particles (Fuentes-Aceituno et al., 2008a), an increase in
obtained after 60 min for the experiments carried out at 0.3, 0.5 and the kinetics of monoatomic hydrogen formation (Eq. (5)) therefore,
0.7 A, which correspond to the applied cathodic current density of favors the chalcopyrite reduction kinetics (Eq. (6)). The cathode po-
0.004, 0.007 and 0.01 A/cm2, or initial specific current of 0.12, 0.2 and tentials recorded for the experiments performed at 0.3, 0.5 and 0.7 A
0.28 A/g of CuFeS2 concentrate, respectively. Apparently increase in correspond to −620, −700 and − 750 mVSHE. According to the ther-
the applied current enhanced the chalcopyrite reduction kinetics be- modynamics of the Cu-Fe-S-H2O system, all the experiments were op-
cause of the possibility of favored rate and amount of monoatomic erated in the potential zone where the metallic copper predominates.
hydrogen generated on the carbon cathode due to the increase in the Metallic copper is produced at these cathode potentials as shown in
cathodic potential. This is in tune with earlier report in which increased cyclic voltammetry experiments (Fig. 1). However, according to the
rate of generation of monoatomic hydrogen on carbon surface at the characterization results shown in Figs. 2c, 4a, and b, metallic copper
higher cathodic potential is noticed (Fuentes-Aceituno and Lapidus, produced in the reactor is a very reactive species which is easily oxi-
2012). Furthermore, the formation of monoatomic hydrogen on carbon dized when it is withdrawn from the reactor.
surface is feasible even at underpotential conditions (El-Deab and Comparing the results of the applied current in HCl (Fig. 5) with
Saleh, 2003; Fuentes-Aceituno and Lapidus, 2012). Considering the that of H2SO4 under the same conditions of applied current, pulp
monoatomic hydrogen as a reducing agent for different particles (Pham density, acidity and temperature (Martínez-Gómez et al., 2016), the HCl
et al., 2012; Huang et al., 2017; Domingues et al., 2013) including the

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Fig. 7. Recovery of chalcopyritic iron during the electro-assisted reductive

Fig. 6. Cumulative current efficiency versus recovery of iron for three different
leaching of the chalcopyrite concentrate employing 250 mL at different HCl
applied currents in 250 mL 2 M HCl, 2.5 g chalcopyrite concentrate at 200 rpm
concentrations, in the presence of 2.5 g chalcopyrite concentrate at 200 rpm,
and room temperature.
0.7 A and room temperature, without a nitrogen atmosphere (open reactor).

system presents higher chalcopyrite reduction kinetics than the latter.

and 25 °C. Results for the chalcopyritic iron dissolution illustrated in
For an instance, the experiment performed at 0.3 A yields the chalco-
Fig. 7 clearly show that chalcopyrite reduction kinetics is favored when
pyritic iron recovery of 85% and 65% for the hydrochloric acid systems
the HCl concentration is increased from 0.5 to 2 M. As the rate of
and sulfuric acid in 300 min (Martínez-Gómez et al., 2016), respec-
generation of monoatomic hydrogen (Eq. (5)) depends on the con-
tively. This further reflects that chalcopyrite suffers lesser passivation in
centration of protons in the leach solution, therefore, increase in the
HCl compared to that of H2SO4 during the electro-assisted reductive
acidity is expected to favor the generation of monoatomic hydrogen, a
leaching.
reducing agent, which would increase the chalcopyrite reduction ki-
Fig. 6 shows the effect of cumulative current efficiency (CE) at any
netics (Fuentes-Aceituno et al., 2008a). However, it is also possible that
time for the experiments performed at 0.3, 0.5 and 0.7 A versus chal-
increase in the acidity favors the kinetics of reactions shown in Eqs. (2)
copyrite conversion using Eq. (9) (Martínez-Gómez et al., 2016). The
and (3) which are related to a direct electron transfer mechanism.
current efficiency for the experiment carried out at 0.7 A was the
The cathode potentials recorded in the experiments (Fig. 7) corre-
highest of all tests. As mentioned before, increase in the applied current
spond to −621, −700 and − 750 mVSHE at the applied currents of 0.3,
intensity from 0.3 to 0.7 A increased the kinetics of hydrogen evolution
0.5 and 0.7 A, respectively. From a thermodynamic viewpoint, the
reaction (HER). Consequently, the generation rate of monoatomic hy-
electro-assisted reductive leaching was operated in a potential zone
drogen is a fundamental part of the HER mechanism as per Eq. (5).
where the metallic copper was predominantly formed, and reduction of
Therefore, chalcopyrite reduction kinetics is also favored at 0.7 A than
chalcopyrite till metallic copper at these cathode potentials is clearly
at 0.5 or 0.3 A, due to increase in the monoatomic hydrogen generation
reflected in Fig. 1.
rate. It is also possible that increase in the applied current promotes
Based on the results of Fig. 7, the current efficiency was calculated
direct charge transfer (electrons) from the carbon electrode to the
and results are presented in Fig. 8 as a function of chalcopyritic iron
chalcopyrite particles when these are momentously in touch. Actually,
recovery. It is evident that the most efficient system corresponds to the
it is possible to recover 84% of chalcopyritic iron with a current effi-
ciency of 70 and 40% approximately at 0.7 and 0.3 A, respectively
(Fig. 6). Another interesting characteristic relates to the decrease in
current efficiency found in all experiments at conversions higher than
80% (Fig. 6). This phenomenon can be related to the predominant
consumption of monoatomic hydrogen in the evolution of molecular
hydrogen. When the electro-assisted reduction of chalcopyrite is carried
out, the amount of unreacted chalcopyrite is decreased with time, and
the monoatomic hydrogen available is in excess to perform the chal-
copyrite reduction. Therefore, the excess of monoatomic hydrogen is
preferentially consumed by the evolution of molecular hydrogen (Eqs.
(7) and (8)).
A comparison of results at 0.7 A (Fig. 6) with that of H2SO4 under
the same conditions (Martínez-Gómez et al., 2016), shows that the
current efficiency is considerably decreased in H2SO4 at chalcopyritic
iron recoveries higher than 20%; e.g., the values (CE) being 70 and 30%
with HCl and H2SO4, respectively at a chalcopyritic iron recovery of
84%. This reveals that chalcopyrite reduction can be performed with
more efficient energy consumption in HCl than in H2SO4.

3.2.3. Effect of the HCl concentration Fig. 8. Cumulative current efficiency versus recovery of iron for three different
The effect of the hydrochloric acid concentration on the chalco- HCl concentrations in 250 mL, 2.5 g chalcopyrite concentrate at 200 rpm and
pyrite reduction kinetics was assessed at a pulp density of 10 g/L, 0.7 A room temperature.

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acid concentration of 2 M followed by 1 and 0.5 M. Thus, the current

efficiency at a chalcopyritic iron recovery of 84% corresponds to 71, 50
and 13% for an acid concentration of 2, 1 and 0.5 M, respectively.
Furthermore, the current efficiency is ~90% at the acid concentration
of 2 M for chalcopyritic iron extractions lower than 80%. The increase
in the current efficiency at the higher acidity is consistent with the
chalcopyrite reduction mechanism where the monoatomic hydrogen is
the reducing agent. Therefore, increase in the acidity promotes the
monoatomic hydrogen generation which is partially employed to carry
out the chalcopyrite reduction. At conversions higher than 80%, de-
crease in the current efficiency is related to the predominant con-
sumption of monoatomic hydrogen by the evolution of molecular hy-
drogen (Eq. (8)). Decrease in the current efficiency could also be related
to a significant change in the specific current (A/g of chalcopyrite
concentrate) at conversions higher than 80%, therefore, the excess of
current is predominantly used to evolve molecular hydrogen and other
possible parasite reactions.

Fig. 10. Cumulative current efficiency versus recovery of iron for three dif-
3.2.4. Effect of the pulp density ferent pulp densities in 250 mL 2 M HCl, 0.7 A at 200 rpm and room tempera-
One of the main limitations of electro-reductive leaching of chal- ture.
copyrite with sulfuric acid is related to its inefficiency to treat pulp
densities of 100 g/L or higher due to the passivation phenomenon
is observed at chalcopyritic iron recoveries higher than 60% for the
caused by elemental sulfur (Martínez-Gómez et al., 2016). Fig. 9 dis-
three pulp densities studied; the decreased current efficiency is ap-
plays the chalcopyrite reduction kinetics at varying pulp densities (10,
parent when the pulp density is increased from 10 to 100 g/L. This
50 and 100 g/L) with 2 M HCl at 0.7 A and 25 °C. Results reveal that
decrease of current efficiency can be related to the consumption of
increasing the pulp density from 10 to 100 g/L decreases the chalco-
monoatomic hydrogen to evolve molecular hydrogen, as well as to the
pyritic iron extraction.
possible consumption of energy in other electrochemical events, such as
A comparison of the results shows that practically 100% of chal-
those relating to the other mineral phases present in the chalcopyrite
copyrite can be reduced at 10 g/L pulp density, as against the release of
concentrate, or probably due to the formation of some elemental sulfur.
57% of chalcopyritic iron at 100 g/L pulp density, in 300 min. The
The solid residue obtained in the electro-assisted reduction of
chalcopyrite reduction at 100 g/L pulp density presents a higher ki-
chalcopyrite at 100 g/L was characterized by XRD phase analysis
netics and conversion in the HCl than in H2SO4 in view of release of
(Fig. 11). This residue does not contain elemental sulfur unlike the
55% and ~30% of chalcopyritic iron, in respective systems (Martínez-
sulfuric acid system (Martínez-Gómez et al., 2016). Thus, an advanced
Gómez et al., 2016). Furthermore, the chalcopyrite reduction kinetics at
electrolytic system can be devised which can operate at a higher pulp
100 g/L pulp density in HCl presents a linear behavior during the entire
density (100 g/L), since no elemental sulfur is formed on the unreacted
test (Fig. 9), which suggests that the passivation of chalcopyrite is not
chalcopyrite surface, thereby decreasing the passivation considerably.
dramatic in HCl unlike that observed in H2SO4.
According to Martínez-Gómez et al. (2016), it was suggested that the
Fig. 10 illustrates the calculated current efficiency as a function of
formation of elemental sulfur takes place from the interaction of hy-
iron recovery for the experiments shown in Fig. 9. It seems possible to
drogen sulfide (secondary product of the chalcopyrite reduction) with
obtain high current efficiencies (~90%) with the three pulp densities.
the oxygen present in the system. In the case of the system operated
This result is interesting because it is possible to treat a pulp density of
with HCl, presence of sulfur was not observed (Fig. 11). A possible
100 g/L with a current efficiency around 90%, releasing a 57% of
explanation to this difference can be related to the occurrence of an
chalcopyritic iron, approximately. A decrease in the current efficiency

Fig. 9. Effect of pulp density in the electro-assisted reductive leaching of Fig. 11. X-ray diffraction pattern of the solid residue obtained in the electro-
chalcopyrite concentrate in 250 mL 2 M HCl at 0.7 A, 200 rpm and room tem- assisted reductive leaching of Fig. 9 for 100 g/L (JCPDS file no. is shown against
perature, without a nitrogen atmosphere (open reactor). each species).

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alternate mechanism for the oxidation of H2S species to ‘S’. For an in-
stance Wang et al. (2002) showed that sulfate contained in sulfuric acid
system can form a galvanic cell with H2S producing S and SO2 as in Eq.
(15):
H2 S + H2 SO4 → S + SO2 + 2H2 O (15)

Hydrogen sulfide species can also react with sulfur dioxide produ-
cing sulfur, according to Eq. (16):
2H2 S + SO2 → 3S + 2H2 O (16)

These reactions (Eqs. (15) and (16)) can also take place during the
electro-assisted reductive leaching of chalcopyrite in H2SO4 solutions.
Furthermore, this sulfuric acid system is sensitive to the presence of
oxygen producing more elemental sulfur as reported by Martínez-
Gómez et al. (2016). This suggests that SO2 produced in Eq. (15) can
also react with oxygen to regenerate partially sulfate species (Eq. (17)).

SO2 + 1
2 (O2 ) + H2 O → H2 SO4 (17)

H2SO4 produced in Eq. (17) can be used in Eq. (15) to accelerate

production of elemental sulfur.
In HCl system, there is no possibility to produce sulfur by a similar
mechanism as that shown in Eqs. (15)–(16) (17). In fact, Pourbaix
Fig. 13. Pourbaix diagram for the S-H2O system, at 1 atm, 25 °C and 2 M sulfate
diagram for the Cl-H2O system (Fig. 12) shows that producing S by a
using the software Medusa®.
galvanic reaction with Cl− and H2S present in the system is unlikely.
Thus Cl− cannot be reduced (Fig. 12) to promote the oxidation of H2S
(Fig. 14). As can be seen in Fig. 12, chlorine gas (Cl2) or chlorate 0.00
(ClO3−) are the only chloride species which can promote the oxidation
of H2S (Fig. 13), and they are not produced in the cathodic compart- -0.05
ment. This result is consistent with the absence of elemental sulfur in
i (A/cm2)

-0.10
the solid residue (Fig. 11).
Elemental sulfur is a known hydrophobic and non-conducting spe-
-0.15 (a) Electrode pre-treated with Na2S in
cies which promotes passivation phenomenon in an electrochemical HCl
system as observed in the electro-assisted reductive leaching of chal- -0.20 (b) Electrode without pre-treatment
copyrite in sulfuric acid (Martínez-Gómez et al., 2016).
In order to further confirm that the electro-assisted reductive -0.25
leaching of chalcopyrite in HCl does not generate elemental sulfur, -700 -500 -300 -100 100 300
cathodic polarization of electrode pre-treated in H2S was assessed. E (mV vs SHE)
Fig. 14 illustrates the cathodic linear voltammetry carried out with
chalcopyrite electrode with and without pre-treatment at 25 mV/s with Fig. 14. Effect of CuFeS2 pre-treated in H2S/HCl medium on the electro-
2 M HCl. For the pre-treatment, the polished chalcopyrite electrode was chemical reduction of chalcopyrite in HCl solution. Cathodic polarization of a)
Electrode pre-treated with Na2S in an open reactor and b) fresh chalcopyrite
electrode without pre-treatment. Pre-treatment of chalcopyrite electrode:
50 mL of 2 M HCl, 11.4 g of Na2S at 25 °C during 120 min in an open reactor.
Linear voltammetries with and without pre-treatment: solution 2 M HCl,
sweeping rate of 25 mV/s at 25 °C and 200 rpm.

immersed in a 50 mL solution containing 2 M HCl and 11.4 g Na2S for

120 min in an open reactor. It may be mentioned that the addition of
Na2S in the acid solution promotes the formation of H2S (in-situ)
(Martínez-Gómez et al., 2016). The pre-treated chalcopyrite electrode
immersed in 2 M HCl solution was run for linear voltammetry from OCP
to the cathodic direction at 25 mV/s. The study shows that electrode
pre-treated with H2S in HCl behaves similar to the fresh chalcopyrite
electrode without pre-treatment. This result suggests that elemental
sulfur is not formed on the chalcopyrite in HCl, which is clearly re-
sponsible for decreased passivation compared to that of sulfuric acid in
the cathodic compartment. The absence of elemental sulfur on the
chalcopyrite surface with HCl system can be studied further in future
works employing advanced characterization techniques (e.g., FESEM,
XPS, ToF-SIMS, etc).
As regards the copper products obtained at 100 g/L, Fig. 11 displays
the presence of atacamite (Cu2Cl(OH)3) which is formed by the oxi-
dation of metallic copper on withdrawing the solid residue from the
reactor (Eq. (14)). The presence of chalcopyrite in the residue shows
Fig. 12. Pourbaix diagram for the Cl-H2O system, calculated at 1 atm, 25 °C and
that conversion of reduction reaction of chalcopyrite is not 100%.
2 M chloride using the software Medusa®.

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V.J. Martínez-Gómez et al. Hydrometallurgy 181 (2018) 195–205

Table 2
Energy consumption to produce 1 kg Cu by the electro-assisted reductive leaching with a pulp density of 100 g/L in HCl or H2SO4. The electrorefining step is not
considered in these processes.
Process Energy cost, kWh/kg CO2 emissiona, kg CO2/kg Cell voltage, V Applied current, Time, h Conversion, %
Cu Cu A

Electro-assisted reductive leaching in HCl 4.22 2.97 4 0.7 5 57

Electro-assisted reductive leaching in H2SO4 (Martínez- 8.48 5.96 4.77 0.7 5 34
Gómez et al., 2016)

a
CO2 emitted during the production of energy (electricity). According to the EPA (2017) 1 kWh ~ 0.703 kg CO2.

The absence of any lead species in the residue is interesting • The formation of elemental sulfur during the electro-assisted re-
(Fig. 11), contrary to the sulfuric acid system where anglesite was also duction of chalcopyrite is not observed in the system operated with
found (Martínez-Gómez et al., 2016). This reveals that lead contained HCl at a pulp density of 100 g/L unlike the one for the sulfuric acid
in galena was leached during the electro-assisted reduction of chalco- system. In the HCl medium the passivation of the chalcopyrite
pyrite, promoting the formation of a lead-poor residue. From an en- during the electro-assisted reduction is minimal, while obtaining a
vironmental viewpoint, lead dissolution could be a problem due to its chalcopyritic iron recovery of ~57% in 300 min.
toxicity. However, the current applied could partially be utilized to • The electro-assisted reduction of chalcopyrite performed in HCl is
electrodeposit lead on the cathode surface (results not shown here). more efficient in terms of energy consumption than in H2SO4 and
The surface of the cathode (carbon) was examined after completing the conventional pyrometallurgical process. It is also possible to
the electro-assisted reduction of chalcopyrite at 100 g/L. A change in operate the system with a current efficiency higher than 90% with a
the color of the cathode surface from black to gray suggests the elec- chalcopyritic iron recovery of 57% at a pulp density of 100 g/L.
trodeposition of lead on the carbon surface. • Chalcopyrite reduction kinetics and current efficiency are favored
According to Figs. 9 and 10, the current efficiency is affected when when the HCl concentration is increased from 0.5 to 2 M since: a)
the pulp density is increased from 10 to 100 g/L, specifically at chal- chalcopyrite reduction reaction depends on the concentration of
copyritic iron recoveries higher than 60%. The decrease in the current protons, and b) the kinetics of the monoatomic hydrogen generation
efficiency could probably be also associated with the electrodeposition (reducing agent) is increased.
of lead on the cathode. It is also likely that the electrodeposited lead can
modify the kinetics of the hydrogen evolution reaction, promoting the Acknowledgements
recombination of monoatomic hydrogen (a reducing agent for chalco-
pyrite) to molecular hydrogen. These issues will be discussed in part-II The authors are grateful to CONACyT (México) for the postgraduate
of this research related to the role of galena on the electro-assisted scholarship awarded to Víctor Martínez-Gómez. Also, the collaboration
reductive leaching of chalcopyrite. of Sergio Rodríguez Arias in this investigation is duly recognized.

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