Hydrometallurgy 158 (2015) 35–41

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Hydrometallurgy

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The effect of chemical additives on the electro-assisted reductive

pretreatment of chalcopyrite
G.E. Barrera-Mendoza ⁎, G.T. Lapidus
Depto. Ingeniería de Procesos e Hidráulica, Universidad Autónoma Metropolitana, Iztapalapa, D.F. 09340, Mexico

a r t i c l e i n f o a b s t r a c t

Article history: The oxidative leaching of chalcopyrite demands extreme conditions of temperature and solution potential or
Received 5 July 2014 non-aqueous solvents because of the formation of recalcitrant passivation layers. Chalcopyrite reduction suffers
Received in revised form 2 September 2015 much less from this phenomenon and therefore could provide a starting point as a pretreatment to facilitate the
Accepted 2 October 2015
subsequent leach. However, even though the electro-assisted reduction reactions occur at ambient temperature
Available online 9 October 2015
and pressure, the kinetics are slow, and consequently the power requirements are too high, to compete with con-
Keywords:
ventional technology. A further decrease in passivation for a given reduction time should enhance the formation
Chalcopyrite leaching of chalcocite and metallic copper, which should result in an improved copper extraction in the subsequent
Carboxylic acids oxidative leaching stage. This would directly impact the economy of the process.
Ethylene glycol The use of complexing agents for iron(II), sulfide and copper(I) in sulfuric acid solutions increased the amount of
TEA chalcocite and metallic copper formed in the electro-assisted reduction pretreatment of chalcopyrite compared
Reductive pretreatment with the same leaching system with only H2SO4. The improvement in the copper extraction in the subsequent
oxidative stage is probably due to the complexation of iron by the carboxylic acids and sulfur by the ethanol-
amines in the reductive pretreatment, thus avoiding the formation of a pyrrhotite (FeS) passivation layer on
the chalcopyrite surface. On the other hand, ethylene glycol stabilizes copper as the cuprous ion, facilitating
the chalcopyrite transformation and copper extraction; however, this action alone is not as effective as the
carboxylic acids and the ethanolamines in diminishing passivation.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Sulfide minerals are the main source of base metals. Approximately
70% of world's copper reserves are in the form of chalcopyrite (CuFeS2),
making it the most profitable copper mineral (Davenport et al., 2001).
Currently, copper sulfides are processed mainly by pyrometallurgy
and only 15 to 20% of copper production, mostly oxides, is extracted
by hydrometallurgical methods. Although there are two types of hydro-
metallurgical processes, oxidative and reductive, practically all of the
processes developed to extract copper from chalcopyrite use the oxida-
tive route, in the leaching stage (Dreisinger and Abed, 2002). However,
these last methods require high pressure and temperature or non-
aqueous solvents (Muir and Senanayake, 1985) to achieve quantitative
chalcopyrite dissolution. The reason for this behavior is that chalcopy-
rite is passivated by intermediate sulfides, which impede the oxidant
from reaching the chalcopyrite surface, thus preventing further reaction
(Parker and Muir, 1981; Parker and Power, 1981).
Many research teams in the last 50 years have contributed to the ex-
planation of this passivation phenomenon with the aim of finding ways
to diminish its effects. Since the reaction rate depends on the hydrogen
⁎ Corresponding author.
E-mail address: gebarreram@gmail.com (G.E. Barrera-Mendoza).
ion concentration [H+] (Hiskey and Wadsworth, 1975), the chalcopy-
rite is usually leached at highly acidic conditions, employing solutions
containing concentrated hydrochloric or sulfuric acid. Ferric chloride,
copper chloride and hydrochloric acid, as part of the chloride leaching
media, lessen the problem, but have the disadvantage of high
corrosivity. High pressure leaching and ferric sulfate leaching also
offer limited improvement. However, none have been sufficiently suc-
cessful to lower the leaching temperature to near ambient values,
which could permit a more selective copper extraction. Finally, bacterial
leaching has the disadvantage of being a slow process.
One option to avoid these problems is to employ the reductive route,
specifically electro-assisted reductive pretreatments in which chalcopy-
rite is transformed into less refractory sulfides (chalcocite and djurleite)
or copper metal. Generally, these processes do not show the same de-
gree of passivation as the oxidative ones. However, there is very little in-
formation regarding the reduction mechanism.
The nature of the chalcopyrite reduction reaction products is deter-
mined by the pH and composition of the electrolytic solution. The ther-
modynamic data in the form of Eh–pH diagrams provide a guide to
obtain information about the reactions taking place. In particular for
chalcopyrite, the products of the reduction reaction under acidic condi-
tions are expected to be hydrogen sulfide (H2S) and ferrous ion (Fe2+),
as well as bornite, chalcocite, and copper metal as solid phases, in that

http://dx.doi.org/10.1016/j.hydromet.2015.10.001
0304-386X/© 2015 Elsevier B.V. All rights reserved.
36 G.E. Barrera-Mendoza, G.T. Lapidus / Hydrometallurgy 158 (2015) 35–41
order as the potential becomes more negative (Fuentes-Aceituno et al.,
2008). In the reduction processes, iron and sulfur are extracted from the
mineral, leaving a copper rich sulfide (Biegler and Swift, 1976).
2CuFeS2 þ 6Hþ þ 2e− → Cu2 S þ 2Fe2þ þ 3H2 S:
The electrons needed for this reaction may come from a reducing
agent or from direct electrolytic reduction (because copper sulfides
have semiconducting properties). Metals, such as aluminum, iron, lead
or zinc have been used as reducing agents in acidic media (Lapidus
and Doyle, 2006). However, the problems of high reagent consumption
and toxic H2S production limit this approach. The electro-assisted re-
duction process helps minimize these problems, but has not previously
been investigated in detail.
Electro-assisted reduction of chalcopyrite is possible at ambient
temperature and pressure, with an aluminum cathode and a lead-
silver alloy anode (Martínez-Jiménez and Lapidus, 2012). According to
these authors, the reduction reactions are as follows:
5CuFeS2 þ 8Hþ þ 4Hðsurf Þ → Cu5 FeS4 þ 4Fe2þ þ 6H2 S
2CuFeS2 þ 4Hþ þ 2Hðsurf Þ → Cu2 S þ 2Fe2þ þ 3H2 S
Cu2 S þ 2Hðsurf Þ → 2CuðsÞ þ H2 S
where H ⋅ is the monoatomic hydrogen produced on the cathode
surface. The chalcopyrite to chalcocite reduction (3) is proposed as the
rate-limiting step. However, at the reaction boundary, high concentra-
tions of ferrous and sulfide ions can lead to the formation of pyrrhotite
(Fes(s)), which probably causes passivation.
In order to favor iron extraction and, consequently, lessen the
passivation problem, the addition of carboxylic acids to the reduction
pretreatment solution, as ligands for the ferrous ion, has been proposed,
(Martínez-Jiménez and Lapidus, 2012). The complexation reactions
with citrate, acetate and tartrate ions are as follows (NIST Standard
Reference Database 46, 2004):
Fe2þ þ cit3− → FeCit− log10 KFeCit ¼ 4:8
Fe2þ þ cit3− þ Hþ → FeHCit log10 KFeHCit ¼ 10:2
Fe2þ þ cit3− þ 2Hþ → FeH2 Citþ log10 KFeH2 Cit ¼ 12:8
Fe2þ þ 2cit3− þ Hþ → FeHðCitÞ2 3− log10 KFeHðCitÞ2 ¼ 13:4
Fe2þ þ CH3 COO− → FeðCH3 COOÞþ log10 KFeAc ¼ 1:4
Fe2þ þ Tar2− → FeTar log10 KFeTar ¼ 2:2 :
The same authors (Martínez-Jiménez and Lapidus, 2012) reported
metallic copper as the main reduction product, which spontaneously
reacts to copper oxide when the solids contact air. However the reaction
is still quite slow, possibly because of the difficult solid-state
transformation.
On the other hand, the copper in chalcopyrite occurs as Cu(I), but the
cuprous ion is not stable in sulfate solution, requiring the potential to be
high enough to oxidize it to Cu(II) state or, in the reduction route, to
stabilize it in the cuprous form, and to avoid disproportionation.
Nelson et al. (1961) showed that the cuprous ion solubilizes in polar
organic solvents. It has been demonstrated that polar organic solvent
solutions increase chalcopyrite dissolution under ambient conditions
(Muir and Senanayake, 1985; Solís and Lapidus, 2014) by stabilizing
the cuprous ion, thereby enhancing copper extraction.
Regarding the chalcopyritic sulfide ion, aqueous solutions of
triethanolamine (TEA) are widely employed in the petroleum industry
to remove H2S from gaseous streams and extract it into the solution,
according to the following reaction (Kumar, 1987):
C6 H15 O3 N ðTEAÞðaqÞ þ H2 SðgÞ → C6 H15 O3 NH2 SðaqÞ þ heat: ð11Þ
ð1Þ
As mentioned earlier, a high H2S concentration probably causes the
formation of pyrrhotite on the surface of the chalcopyrite, which passiv-
ates the mineral surface. By diminishing the hydrogen sulfide concen-
tration, the formation of pyrrhotite may be avoided, thus enhancing
the chalcopyrite conversion to chalcocite and metallic copper.
In this investigation, the nature of the reactions in the reduction of
chalcopyrite is studied, employing the following complexing media:
ethylene glycol for Cu(I) stabilization, triethanolamine to sequester
H2S and carboxylic acids to complex the ferrous ion.
2. Experimental materials and methods
Cyclic voltammetry and chronoamperometry were used to
determine the nature of the reactions that take place at the chalcopyrite
ð2Þ surface in the different leaching media and to characterize the solid
products formed on the surface of the mineral.
ð3Þ Because it has been reported that H2S plays an important role in the
reaction mechanism of the reduction step (Martínez-Jiménez and
ð4Þ Lapidus, 2012), electro-assisted reductive pretreatment experiments
were carried out with the same mineral to validate the chalcopyrite re-
activity shown in the electroanalytical techniques with the different
media.
2.1. Electrochemical characterization in carbon paste electrodes with
voltammetry and chronoamperometry
The electrochemical simulations of the process were performed
using cyclic voltammetry and chronoamperometry on chalcopyrite in
the form of carbon paste electrodes, in a three-electrode cell. These
experiments are the basis for determining the interaction between the
chalcopyrite and the different media.
Carbon pastes were prepared using the wet sieved −200 + 325 mesh
ð5Þ fraction (44–74 μm) of a relatively pure chalcopyrite (82.9% chalcopyrite,
11.1% pyrite and 6.0% quartz) from Kidd Creek Mine (Excalibur Mineral
Corporation, Inc.), graphite powder (Alfa Aesar 99.99% 2–15 μm) and sil-
ð6Þ
icone oil (Sigma, ρ = 0.96 g/mL) as a binder. 0.4 g of graphite powder and
0.1 g of the chalcopyrite were mixed in an agate mortar with 0.15 mL of
ð7Þ
the silicon oil to generate a homogeneous paste (Lazaro et al., 1995). The
mixture was then placed in a polyethylene syringe (0.7 cm length and
ð8Þ 0.2 cm inner diameter) and was compacted using the plunger. A
platinum wire welded to a copper wire with silver solder was used to
ð9Þ establish electrical contact for electrochemical characterization of the
surface reactions.
ð10Þ The carbon paste electrode (working electrode) was submerged in a
100 mL glass cell which contained 50 mL of the electrolyte solution at
ambient temperature, which had been previously sparged with nitro-
gen for 30 min to eliminate O2 and CO2. A reference electrode (saturated
sulfate electrode, Radiometer Analytical, Hg/Hg2SO4/K2SO4 saturated,
SSE) and a graphite counter-electrode (Alfa Aesar, 99.99%) were placed
in the cell as well. The voltammetric and chronoamperometric response
were obtained with a PARSTAT potentiostat (model 2373) coupled to a
personal computer. The surface of the working electrode was renewed
after each voltammogram to remove the products formed. The solutions
used in the experiments consisted in 1 M H2SO4 solution (electrolytic
medium) and the following substances: ethylene glycol (20% v/v),
tartaric acid (0.5 M), citric acid (0.25 M) and TEA (0.5 M).
2.2. Electro-assisted reductive pretreatment and oxidative leaching
The electro-assisted reductive pretreatment experiments were per-
formed in a single chamber electrolytic cell, which consisted of a
 G.E. Barrera-Mendoza, G.T. Lapidus / Hydrometallurgy 158 (2015) 35–41 37

500 mL beaker, a mechanical stirrer (Caframo®) with a Teflon® shaft

and a programmable power supply (BK Precision, model 1785B). A
high purity 10 ppi reticulated aluminum foam (ERG, Inc.) was used as
the cathode and a sheet of a lead-silver as the anode (Servicios
Administrativos Peñoles, S.A. de C.V.). Once the reduction step was con-
cluded, an oxidative treatment to extract the copper was carried out
with magnetic stirring in a 250 mL beaker.
For the reduction experiments, the following procedure was used:
2.5 g of chalcopyrite was charged to the electrolytic cell, along with
250 mL of H2SO4 ((J.T. Baker, 99.2%) and the complexing agent. The con-
centrate was suspended by mechanical agitation at 600 rpm to form a
homogeneous slurry. To initiate the reduction reaction, current was ap-
plied (1 A) by the power supply. During the experimentation, several
samples of the solution were taken for iron analysis by atomic absorp-
tion spectrometry (AAS, SpectraAA 220fs, Varian). Experiments were
performed at 25 °C. Once the experiment was concluded, the solid
residue was filtered, rinsed with deionized water and left to air dry.
The oxidative leaching was performed on each reduced residue to
quantify the degree of chalcopyrite transformation and to determine Fig. 2. Single-cycle voltammogram of carbon–chalcopyrite paste in 1 M H2SO4 with 0.25 M
the products of this reduction. An aqueous, acidic acetonitrile solution citric and 0.5 M tartaric acids, scanned in negative direction from the open circuit potential
at 25 mV/s, initiating from the OCP.
with cupric sulfate was selected as the medium because of its ability
to leach both metallic copper (fast) and chalcocite (slow) at room tem-
perature (Solís and Lapidus, 2012). Each reduction residue was subject-
ed to the same oxidative leach, which was performed in the following shown in Fig. 1 in 1 M H2SO4. The voltammograms (inset) show the
manner: 1 g of pretreated residue was contacted with a solution con- chalcopyrite reduction to bornite (peak I, 100 mV), chalcocite (peak II,
taining 2.5 g of pentahydrated cupric sulfate, 80 mL of 1 M H2SO4 and −290 mV) and finally metallic copper (peak III, − 430 mV) (Fuentes-
20 mL of acetonitrile. The slurry was suspended by agitation. Several Aceituno, 2010). When the potential was reversed to the positive
samples of the solution were taken at different times for copper analysis (oxidation) direction, two relatively sharp peaks were observed,
by AAS. Experiments were carried out at 25 °C. The oxidized residue was which are related to metallic copper (peak IV, − 190 mV and peak V,
filtered, rinsed and air dried for subsequent digestion to analyze copper 350 mV), followed by a broad peak which is associated to chalcocite ox-
and iron and complete the metallurgical balance. For comparison, a idation to various non-stoichiometric sulfide phases (peak VI, 600 mV)
sample of the untreated chalcopyrite was leached by this method. (Arce and González, 2002; Elsherief, 2002).
The voltammograms for the solutions with carboxylic acids and or-
ganic solvents, displayed in Figs. 2 and 3, indicate that the chalcopyrite
3. Results and discussion reactivity was modified by the complexing agents. Systems with tartaric
acid (Fig. 2) and ethylene glycol (Fig. 3) reveal larger increases in peak
3.1. Single-cycle voltammetry height compared with the other complexing agents. In the case of
tartaric acid, this could evidence the complexing reaction between
To determine the reduction and oxidation behavior of the carbon– tartaric acid and ferrous ion, favoring iron extraction from chalcopyrite
chalcopyrite paste in each of the electrolytic media, the scans were ini- and forming bornite, according to reaction (2). Additionally, with both
tiated in the negative (reduction) direction (from the OCP to −490 mV tartaric acid and ethylene glycol, the peaks related to reduction of chal-
vs NHE [normal hydrogen electrode], reversed and scanned to 1010 mV, cocite and metallic copper are larger, suggesting increased reactivity for
where the direction was again reversed and returned to the OCP), as the reduction of chalcopyrite to these products.

Fig. 1. Single-cycle voltammogram of carbon–chalcopyrite paste in 1 M H2SO4 solution, Fig. 3. Single-cycle voltammogram of carbon–chalcopyrite paste in 1 M H2SO4 with 20% v/v
scan initiated from the OCP in the negative direction at 25 mV/s. The inset reveals the ethylene glycol and with 0.5 M TEA, scanned in negative direction from the open circuit
peak corresponding to the commencement of bornite reduction. potential at 25 mV/s, initiating from the OCP.
38 G.E. Barrera-Mendoza, G.T. Lapidus / Hydrometallurgy 158 (2015) 35–41
Fig. 4. Chronoamperograms of carbon–chalcopyrite paste in 1 M H2SO4 with 0.25 M citric
acid, 0.5 M tartaric acid, 20% v/v ethylene glycol and with 0.5 M TEA at −390 mV.
The peaks corresponding to the citric acid/H2SO4 solution also show
an increase in current (peak height) compared with those of only
H2SO4. Only the TEA/H2SO4 system displays a reactivity similar to that
of only H2SO4.
It can be concluded from the analysis of the voltammograms that, in
comparison with pure H2SO4 solution, H2SO4 — ethylene glycol and
H2SO4 — tartaric acid solutions promote increased reactivity, implying
that a larger number of moles reacted in the chalcopyrite reduction
zone (from −90 to −390 mV vs NHE) (5.9 and 4.6 × 10−9 mol, respec-
tively), followed by citric acid (3.4 × 10−9 mol) and finally H2SO4 and
TEA (3.3 and 2.3 × 10−9 mol). It can therefore be assumed that ethylene
glycol and tartaric acid systems should favor the chalcopyrite–
chalcocite transformation reaction, and, thus, increase the copper ex-
traction in the subsequent oxidation step.
Because of the semiconductor nature of chalcopyrite, the leaching
systems studied possibly have a high capacitive current at the electrode
surface (which means that the current is being consumed as the system
develops its charge, in addition to the chemical reaction). To eliminate
this effect, chronoamperometric tests were carried out at − 390 mV
(chalcocite formation potential) and the area under the curve was
Fig. 5. Percentage of iron extraction versus time during the electro-assisted reduction, of a
1 M H2SO4 solution, 1 M H2SO4–0.25 M citric acid and 1 M H2SO4–0.5 M tartaric acid. Con-
ditions: 2.5 g chalcopyrite in 250 mL solution, applying a current of 1 A.
Fig. 6. Percentage of copper extraction versus time during the oxidation stage from the
electro-assisted reduction of a 1 M H2SO4 solution, 1 M H2SO4–0.25 M citric acid and
1 M H2SO4–0.5 M tartaric acid. Conditions: 2.5 g of CuSO4 in 100 mL 1 M H2SO4 solution
and 20 mL of acetonitrile. R.P. represents reductive pretreatment.
calculated in order to determine the number of moles chalcocite
formed, according to the following equation:
Z 1
I ðt Þdt
Moles Cu2 S ¼ 0
: ð12Þ
nF
In the above reaction, n equals 2, according to reaction (1). These
chronoamperograms are presented in Fig. 4.
Ethylene glycol, tartaric acid and TEA showed the largest enhance-
ment factors. This relationship is in concordance with the
voltamperometric results, except for TEA, which was similar to H2SO4
only in voltammograms. Since carboxylic acids react with ferrous ion
according to reactions (5–10), it would have a similar effect on the
overall reaction, by diminishing the iron reaction with hydrogen sulfide
to form pyrrhotite.
Fig. 7. Percentage of iron extraction versus time during the electro-assisted reduction, of a
1 M H2SO4 solution, 1 M H2SO4–20% v/v ethylene glycol and 1 M H2SO4–0.5 M TEA.
Conditions: 2.5 g chalcopyrite in 250 mL solution.
 G.E. Barrera-Mendoza, G.T. Lapidus / Hydrometallurgy 158 (2015) 35–41
Fig. 8. Percentage of copper extraction versus time during the oxidation step from the
electro-assisted reduction of a 1 M H2SO4 solution, 1 M H2SO4–20% v/v ethylene glycol
and 1 M H2SO4–0.5 M TEA. Conditions: 2.5 g of CuSO4 in 100 mL 1 M H2SO4 solution
and 20 mL of acetonitrile. Reductive pretreatment (RP).
3.2. Electro-assisted reductive pretreatment and oxidative leaching
As was mentioned earlier, the formation of H2S in the reduction step
plays an important role in the chalcopyrite transformation process be-
cause this gas and ferrous ion react to form ferrous sulfide, or pyrrhotite,
which could passivate chalcopyrite surface according to reaction (13)
(Ball and Nordstrom, 1991). Therefore, electro-assisted pretreatment
experiments with the different media were carried out as a way to cor-
roborate the results of the electroanalytical investigations.
Fe2þ þ H2 SðaqÞ → 2Hþ þ FeSðsÞ log10 KFeS ¼ −2:34 : ð13Þ
In the step-wise reduction process, iron is extracted from chalcopy-
rite, forming bornite (reaction (2)), chalcocite (reaction (3)) and metal-
lic copper (reaction (4)). The quantity of each reaction product can be
approximately determined by analyzing the solution from the
subsequent oxidation by cupric sulfate in acetonitrile: metallic copper
is instantly leached; chalcocite is leached slowly; and finally bornite
and unreacted chalcopyrite remain in the residue (Solís and Lapidus,
2012). With these criteria, the quantity of each product formed in the
reduction step can be estimated. Fig. 5 compares the chalcopyritic iron
extraction for the carboxylic acids. In the reduction step, 86% of iron is
extracted in the H2SO4 system, 93% for tartaric acid and 94% for the citric
acid. Therefore, the addition of these iron complexing agents improves
the chalcopyrite transformation to bornite and chalcocite, evidenced
by iron extraction.
Regarding copper extraction in the oxidative step, Fig. 6 shows that
H2SO4 alone in the pretreatment, promotes the extraction of only 38%
of copper, while in the presence of citric or tartaric acids in the pretreat-
ment, extractions of 70% or 79% are possible in the subsequent oxida-
tion, respectively. With H2SO4 alone, metallic copper accounts for 29%,
while the remaining 9% is copper from chalcocite. With tartaric acid
Table 1
Chalcocite moles formed in the chalcopyrite reduction step (at −390 mV vs NHE).
Medium Moles Cu2S × 108 (mol) Enhancement factor
H2SO4 3.71 1
Citric acid 4.41 1.19
Tartaric acid 4.71 1.27
Ethylene glycol 5.75 1.55
TEA 4.68 1.26
39
Table 2
Current efficiencies for the reduction stage (5 h).
Media Efficiency (%)
Tartaric acid 8.6
Citric acid 6.1
Ethylene glycol 7.1
TEA 9.1
H2SO4 6.6
and citric acid, 6% of copper was extracted from chalcocite. These results
could indicate that nearly all of the chalcocite formed according to
reaction (3) is converted to metallic copper (reaction (4)) (Solís and
Lapidus, 2012; Martínez-Jiménez and Lapidus, 2012). It is interesting
to note that although more than 80% of the chalcopyritic iron was dis-
solved (Fig. 5), less than half of the copper is extracted in the purely
acid case (Fig. 6). The remaining copper is probably present in the
form of bornite, which is stable to oxidative leaching under these
conditions (Arce and González, 2002). When untreated chalcopyrite is
subjected to the acetonitrile oxidative leach, an insignificant quantity
of copper was extracted even after 5 h. This refractory behavior was
also commented by Muir and Senanayake (1985) in their excellent re-
view of the Parker process.
In Fig. 7, the iron extracted from the chalcopyrite reduction in the
acidic solutions containing ethylene glycol (cuprous ion stabilizer) and
acidic TEA (sulfide sequestering agent) are shown. The chalcopyritic
iron extractions were 91% and 100% for the ethylene glycol and TEA sys-
tems, respectively. The efficiency in this last solution is superior starting
from the second hour, achieving a similar iron extraction to that of the
others only after 5 h. It is interesting to note that copper extraction is
the highest for TEA, while in voltammetric and chronoamperometric
tests, TEA displayed the same reactivity as H2SO4 alone. These apparent-
ly contradictory behaviors could be due to the local pH in each case;
since the TEA–H2SO4 solution has a higher pH than those of the other
ligands, the pH at the reaction interface was probably more sensitive
to the hydrogen ion consumption than in the other systems. Further-
more, in the electrochemical experiments, there was no agitation,
which probably produced a higher local pH at the reaction surface for
the TEA case. It has been demonstrated that chalcopyrite reacts more
at lower pH values (Hiskey and Wadsworth, 1975).
In the subsequent oxidation (Fig. 8), the copper extracted from the
residue of the reduction in ethylene glycol was 71% while the TEA resi-
due was 90%. Both tartaric acid and TEA promoted the formation of 74%
metallic copper during reductive step (extracted in the first 20 min of
oxidation), however copper extracted from chalcocite accounted for
an additional 6% for tartaric acid and 16% for TEA. This indicates that
Fig. 9. Percentage of iron and copper extraction versus time during the reductive and
oxidative steps from the 1 M H2SO4–0.5 M TEA leaching solution.
40 G.E. Barrera-Mendoza, G.T. Lapidus / Hydrometallurgy 158 (2015) 35–41
Fig. 10. Diffractograms of pure chalcopyrite and solid reduction residues after 5 h of
pretreatment.
conversion to metallic copper was similar in both leaching systems;
however, the generation of chalcocite (reactions (2) and (3)) from
bornite presumably was more quantitative with TEA.
A more quantitative comparison between the different chemical sys-
tems can be appreciated with the current efficiency of each in the reduc-
tion stage. This was calculated by estimating the number of electrons
required to produce the copper and chalcocite moles formed, observed
in the subsequent oxidation step, divided by the number of electron
moles supplied. These results are presented in Table 2. See Table 1
Efficiencies between 6 and 9% can be observed in these experiments
using 1% solids. The solid to liquid ratio is also an important factor in the
improvement of the efficiency since the particle/cathode contact is im-
portant for the reduction reaction. In other tests with 5 and 10% solids
(not shown here) using a different reactor design, greater efficiencies
were obtained.
Regarding the reduction time and consequently power consump-
tion, it can be noted in Fig. 7 that after 3 h the iron extraction in the
TEA system is the same as that extracted with tartaric and citric acids
after 5 h. For this reason, a 3 h electro-assisted reductive pretreatment
was performed, with an 8 h oxidative step, since chalcocite oxidizes at
a slower rate. After 3 h of reductive pretreatment, 90% of iron was ex-
tracted, indicating that some chalcopyrite did not react or was trans-
formed to bornite (Fig. 9). For the oxidative step, a total of 81% of
copper was extracted. Approximately, 9% of the copper probably was
converted only as far as bornite (reflected in the metallurgical balance).
However, although the copper extraction is 10% less than when the
chalcopyrite was reduced for 5 h, the energy savings amounted to
approximately 40% in the reductive pretreatment.
X-ray diffractograms of the solid residues with the highest copper
extractions (TEA and tartaric acid), were used to elucidate the chemical
reactions occurring in the reduction stage. The diffractograms (Fig. 10)
of these residues show djurleite (Cu31S16), chalcocite (Cu2S) and cuprite
(Cu2O) in the three pretreated systems (it should be mentioned that cu-
prite is formed when the metallic copper in the residue enters in contact
with air). With H2SO4 alone, in addition to the unreacted chalcopyrite,
the formation of bornite (Cu5FeS4) is observed, which indicates that
chalcopyrite first reduces to bornite before it forms chalcocite. As was
mentioned previously, the bornite is not leached in the subsequent
Table 3
Copper extracted in the oxidative leaching.
Medium Metallic copper (%) Copper from chalcocite (%)
H2SO4 29 9 terization. TMS, pp. 217–224.
H2SO4 and tartaric acid 73 6 Muir, D.M., Senanayake, G., 1985. Refining copper by the acetonitrile process. 14 (3),
H2SO4 and citric acid 63 6 279–293.
H2SO4 and TEA 74 16
H2SO4 and ethylene glycol 65 5
oxidation. Additionally, less metallic copper is formed, compared with
the TEA and tartaric acid systems. With this evidence, in addition to
the information provided by the oxidative leach (Table 3), it can be con-
cluded that the addition of complexing agents improves the reduction
of chalcopyrite to chalcocite and metallic copper, thus, improving
copper extraction in the subsequent oxidative leach.
4. Conclusions
The use of complexing agents, such as TEA and tartaric acid, together
with sulfuric acid was shown to increase the amount of metallic copper
formed in the electro-assisted pretreatment of chalcopyrite; hence, the
amount of copper extracted in the oxidative leach was enhanced by up
to 90% when compared with that obtained from the residue pretreat-
ment with H2SO4 alone (38%). The improvement in the copper extrac-
tion is probably due to the complexation of iron by the carboxylic
acids and sulfur by the ethanolamines, thus avoiding the formation of
a pyrrhotite (FeS) passivation layer on the chalcopyrite surface. The
passivation apparently slows the reduction of bornite to chalcocite,
evidenced by the presence of the former mineral phase in the reduction
residue.
Finally, ethylene glycol stabilizes copper as the cuprous ion, facilitat-
ing the chalcopyrite transformation and copper extraction; however,
this action alone is not as effective as the carboxylic acids and the
ethanolamines in diminishing passivation.
Acknowledgments
The authors wish to thank the Consejo Nacional de Ciencia y
Tecnologia (CONACyT) for the postgraduate scholarship granted to the
first author (Gerardo Emerson Barrera-Mendoza, Grant number:
215530).
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