COPPER CONCENTRATE LEACHING IN CHLORIDE-SULFATE MEDIUM

J.P. Ibez, J. Ipinza, F. Guerrero, J.I. Gonzlez and J. Vsquez

Departamento de Ingeniera Metalrgica y de Materiales
Universidad Tcnica Federico Santa Mara
Avda. Espaa 1680, Valparaso, Chile.
juan.ibanez@usm.cl

ABSTRACT

The mixed leaching of a Chilean copper concentrate (predominantly chalcopyrite) was

studied by using sulfate-chloride aqueous solution under normal pressure at different
temperatures at constant pH. The use of sea water to increase the chloride concentration
was studied as well. The leaching rate in sulfate-chloride solution was faster than in sulfate
solution by a factor of ten in 7 days. The use of sea water led to a dissolution of 28% of the
total copper in the same period of time at 60 C, when the chloride concentration was
around 60 g/L the dissolution was near to 36% at 60 C. The iron content in the concentrate
was around 30%, and remains in the solid after 7 days of leaching. The brown, reddish and
yellow color solutions resulting after experiments indicate the presence of different copper
chloride complexes ions. Additional experimental work is carrying out to improve the
copper recovery by analyzing addition of sodium chloride on the copper concentrate cured
with sulfuric acid, to generate in situ hydrochloric acid.

INTRODUCTION
Chalcopyrite (CuFeS2) is the most important copper mineral [1, 2] with the highest
concentrate production, which is traditionally treated by smelting technology [3]. This
copper sulfide has a high stability in aqueous systems and it is refractory to normal
hydrometallurgical processes [4].
The leaching of chalcopyrite has been widely investigated, seeking for parameters affecting
the kinetics of the dissolution [5, 2, 6] and supporting the best theoretical mechanism to
explain the dissolution [7], for both chemical and bacterial leaching [8, 9]. The dissolution
rate of chalcopyrite concentrate in sulfate media is slower to the leaching of secondary
copper sulfide [10]; being the passivation of the mineral surface at high solutions potentials,
like a dense layer of elemental sulfur or a polysulfide CuSn, one of the widely accepted
reasons although the nature of the passivation film is still controversial [7, 11].
The dissolution of the chalcopyrite with oxygen in acidic solutions can be represented by
reaction (1). When the leaching proceeds, a ferric oxidation of chalcopyrite can be carried
out by reaction (2), being dissolved by ferric ions, producing ferrous ions which are re oxidized by oxygen in acidic solutions according to reaction (3). This last step is slow at
ambient pressure [12].
CuFeS2 + O2 + 4H + = Cu2+ + Fe2+ + 2S 0 + 2H2 O

(1)

CuFeS2 + 4Fe3+ = Cu2+ + 5Fe2+ + 2S 0

(2)

4Fe2+ + O2 + 4H + = 4Fe3+ + 2H2 O

(3)

The use of chloride ions in the leaching solution involved the action of the second redox
couple Cu2+/Cu+. It is advantageous due to the aggressive nature of the leaching and to the
stability of cuprous ions by the formation of chloro-complexes, being a more effective
process than a regular leaching in sulfate solutions with ferric ions as the oxidant agent.
Some possible reasons of these phenomena are the higher rates of electron transfer in
chloride solutions, as the reduction in chalcopyrite passivation [13, 14].
General reactions of dissolution of chalcopyrite under a sulfate chloride media are shown
by equation (4) and (5) [15]. The prevailing redox couple of copper chloride complexes are
still under discussion. It is suggested that cuprous ions are stable in the form [CuCln]1-n, and
cupric ions in the form [CuCln] 2-n [16]. The cuprous complexes are more stable than the
cupric group, being the reason for reaction (4) to occur [12].
CuFeS2 + 3Cu2+ = 4Cu+ + Fe2+ + 2S 0

(4)

4Cu+ + O2 + 4H + = 4Cu2+ + 2H2 O

(5)

The oxidative model presented above is not enough to explain a rate promotion by the
presence of ferrous and cupric ions. A reductive/oxidative dissolution model was proposed
to interpret this enhancement of chalcopyrite leaching, presented by reactions (6) (7) and
(8). The first step is the reduction of chalcopyrite by ferrous ions in the presence of cupric
ions, represented by reaction (6) and the final step is an oxidation of intermediate Cu2S by
ferric ions [17].
CuFeS2 + 3Cu2+ + 3Fe2+ = 2Cu2 S + 4Fe3+

(6)

Cu2 S + 4Fe3+ = 2Cu2+ + S + 4Fe2+

(7)

Cu2 S + 4H + + 2O2 = 2Cu2+ + S + 2H2 O

(8)

The intermediate Cu2S in reaction (6) is formed only at potentials below the critical
potential that is function of the ferrous and cupric ions concentrations. If that potential is
higher, Cu2S is not formed and reaction (1) or (2) occurs. Also, Cu2S is leached faster than
CuFeS2, increasing copper extractions at low potentials in the presence of these ions [18].
A non-oxidative/oxidative process has been proposed for the dissolution of chalcopyrite
without any oxidizing reagent by reaction (9), with the formation of soluble cupric ions and
hydrogen sulfide which are metastable products, being covellite precipitated by reaction
(10). The rate of reaction (9) is governed by a rapid dissolution to assure the equilibrium
and a diffusion of the soluble species away from the mineral surface [19].
CuFeS2 + 4H + = Cu2+ + Fe2+ + 2H2 S
Cu2+ + 2H2 S = CuS + 2H +

(9)
(10)

The non-oxidative process was extended to include H2S removal, in the presence of oxidant
agents such as Fe+3 or Cu+2 and sustain the reaction (9). This is represented by reaction (11)
[19]. Assuming that the rate of reaction (11) is rapid compared to the rate of diffusion of
H2S from the surface, the equilibrium at the surface will be perturbed by the removal of
H2S by oxidation [18].
H2 S + 2Fe3+ = S + 2Fe2+ + 2H +

(11)

As we saw on this review, there is no consensus about the nature of the rate determining
step and the mechanism involved in the dissolution. This work studies the effect of
parameters such as initial ions concentration in the leaching solution and temperature in the
dissolution of a chalcopyrite concentrate.

EXPERIMENTAL
Materials
Copper concentrate was obtained by flotation from operations in Chile, being classified into
narrow size fraction using a cyclo-sizer obtaining a 12.3 m average size. The chemical
analysis reported in the operation showed 26.8% Cu, 26.7% Fe, 31.3% S, 8.1% SiO2, 2.7%
Al2O3, 0.2% As and others elements. The chemical analysis was made by atomic absorption
spectroscopy (AAS) and the results were 24% Cu and 27.8% Fe. The salt supplied by
Sociedad Punta de Lobos (SPL) was 97.8 % NaCl and 1.4 % sulfate with a particle size of
100% -1/2".
Leaching experiments
Agitated leaching experiments were carried out in a 500 mL thermostatic jacketed glass
reactor with an effective volume of 200 mL of solution. The pulp was mechanically stirred
at 800 rpm. The lid contained ports for continuous measuring of temperature, pH and redox
potential using an Ag/AgCl reference electrode. The experimental setup is schematically
showed in Figure 1.

Figure 1 - Schematic diagram of the experimental setup. (1) vertical mixer; (2) temperature
controller; (3) glass reactor; (4) ORP & pH meter; (5) thermostatic bath; (6) plate heater.

One type of experiments consisted in to mix copper concentrate with 200 mL of acid
solution (0.2 M H2SO4). The percentage of solids in the concentrate pulp is considered
constant in 25 %. Another type of experiments consisted in to mix copper concentrate with
concentrated sulfuric acid and sodium chloride, with chemical curing times of 0 and 20 h.

The temperature was studied in the range of 40 to 70 C. The concentration of chloride ion
varied between 0 and 90 g/L using NaCl (provided by SPL).
The samples were withdrawn every 2 h, adding an equal volume of the leaching solution to
replace that removed. The filtered solutions were analyzed for copper and iron by AAS.
Measurement of the redox potential and pH, were made in the solution, immediately after
sampling of the mineral pulp.

RESULTS AND DISCUSSIONS

Effect of temperature
Figure 2 shows the results of leaching with 30 g/L Cl- at different temperatures of the
concentrate pulp. The copper extraction increases significantly by increasing the
temperature of the pulp. The difference of copper extraction between 50 and 70 C, is
highly significant in the control region by diffusion in the layer of product (sulfur) and less
important in the region of chemical control.

Figure 2 Effect of the temperature on the kinetic of copper extraction with 30 g/L Cl-.

Effect of sodium chloride concentration

The effect of different concentrations of chloride ion added directly in the mineral pulp to
70 C was studied. Figure 3 shows that the addition in the range of 40 to 80 g/L Cl-, does

not significantly change the extraction of copper, however the high temperature of the pulp.
This result shows that the concentration of chloride in the pulp does not affect the kinetic
behavior of the leaching of copper concentrate and only influences the thermodynamic
equilibrium and the distribution of the complex chloride-copper species.

Figure 3 Effect of chloride concentration on copper extraction from a copper concentrate in

NaCl-H2SO4-H2O solution.

Effect of chemical curing and conditioning time

The chemical curing consists in mixing copper concentrate with sodium chloride and a
fraction of the acid consumption, added as concentrated sulfuric acid. This mixture is
conditioned for a certain period of time to promote the sulfating of the sulfide species
content in the concentrate. In this experiment, 30 kg NaCl/ton of concentrate is mixed with
20% of the stoichiometric consumption of sulfuric acid, without and with 20 days of
conditioning at room temperature.
Figure 4 shows that the conditioning produces a 20% increase in the copper extraction,
probably due to the "in situ" formation of HCl, whose pKa= -9 is significantly smaller than
the first dissociation of sulfuric acid (pKa= -6.6).
The reaction for formation of hydrochloric acid with a temperature under 50 C is given by:
NaCl + H2 SO4 = NaHSO4 + HCl

(12)

With temperatures over 50 C, the next reaction occurs:

2NaCl + H2 SO4 = Na2 SO4 + 2HCl

(13)

The concentrate sulfating will be more efficient with reaction (13), which depends on the
heat generated by the exothermic reactions that occurs in the mixture, at expense of the
dissolution of the copper and iron sulfides.

Figure 4 Effect of chemical curing and conditioning on copper extraction from a copper
concentrate in NaCl-H2SO4-H2O solution, 30 kg NaCl/ton of concentrate,
without and with 20 days of conditioning at room temperature.

Figure 5 shows the effect on the kinetics copper extraction of sodium chloride addition
during curing and concentrated conditioning. The experiment was performed with a
conditioning time of 30 days and with acid leaching at 70 C.
It is noted that without f NaCl, the copper extraction is less than 5% after 50 h of leaching.
However, the addition of 30 kg NaCl/ton produces a complete extraction of the copper
content in the concentrate in the same period of time. By decreasing the addition to the half
reduces the copper extraction to around of 70% after 50 h, which is indicating a non-linear
relationship between dosage for curing and the leaching answer of the concentrate.

Figure 5 - Effect of sodium chloride addition during the curing and conditioning of the
concentrated, pH=2 at 70 C and conditioning time of 30 days.

Figure 6 shows the effect of conditioning time on the iron extraction from their sulfides
contained in the concentrate, with a conditioning time of 20 days and addition 15 kg NaCl/
ton for the curing. It can be seen that this leaching medium produces a significant extraction
of iron from the copper concentrate. In effect, the iron extraction increases from 5% in the
sample without conditioning time until around 50% in the sample with conditioning, in a
time period of 50 hours.
Pyrite, principal iron species in the copper concentrate, is generally not attacked during
leaching and as a consequence, the ferrous iron in solution appears by the dissolution of the
chalcopyrite. This ferrous ion is oxidized to ferric ion in presence of cupric ion,
contributing to the dissolution of the chalcopyrite. For this reason, some studies have
focused on the catalytic effect on the leaching of the initial addition of copper sulfate in the
pulp.

Effect of chloride concentration on the redox potential

Figures 7 shows comparatively the evolution of the redox potential and the copper
extraction for 15 and 30 kg NaCl/ton added for curing the concentrate for 20 days. The
agitated leach was carried out at pH = 2 and 70 C.

Figure 6 Effect of conditioning time on iron extraction from a copper concentrate in NaClH2SO4-H2O solution; 15 kg NaCl/ton concentrate at 70 C and conditioning time of 20 days.

The results show that the addition of sodium chloride in the curing has a positive and
significant effect on the kinetics of the process. In effect, with 30 kg/ton is dissolved 80%
of the copper in 45 h, whereas with 15 kg/ton reach the same copper extraction with more
than 100 h.
In both cases, the redox potential is under 700 mV, significantly less than the value
normally found in the bacterial leaching (about 750 mV). At time zero, the redox potential
is 500 mV and increases as the concentration of chloride in the pulp decreases. This
demonstrates that it is possible to control the redox potential of the pulp, adding sodium
chloride continuously during the leaching.
This condition of less oxidizing redox potential in the pulp significantly enhances the
leaching of chalcopyrite. The lower value of redox potential reached in the pulp should be
probably to the domain of the redox couple Cu2+ /Cu+ on the Fe3+ /Fe2+.

Figure 8 shows the leaching process with sea water and distilled water, at pH 2 and 70 C.
Both samples have the same kinetic behavior, increasing their redox potential according the
leaching proceeds. Other ions present in sea water, apparently, do not affect the leaching
process, being feasible the use in copper concentrate leaching.

80

650

60
600
40

550

Copper ext.
ORP

20
0

500
0

10

20
30
Time [h]

40

50

100
Copper extraction [%]

Redox potencial [mV]

700

(a)

700

(b)
80

650

60
600
40
20

550

Copper
ext.

Redox potencial [mV]

Copper extraction [%]

100

500
0

20

40

60
80
Time [h]

100

120

Figure 7 - Evolution of redox potential and copper extraction as a function of time for a
conditioning time of 20 days at pH= 2 and 70 C. (a) 30 kg NaCl/ton; (b) 15 kg NaCl/ton.

Figure 8 - Ionic force water effect on the copper extraction and redox potential in the copper
concentrate leaching.

CONCLUSIONS
The chemical curing and the conditioning time are the most relevant variables in the
kinetics of the leaching process. The addition of 15 kg NaCl/ton concentrate with 20 days
of conditioning time allow a copper extraction higher than 80% with 50 h of leaching.
The addition of sodium chloride increases significantly the kinetics of copper extraction
from the chalcopyrite concentrate, probably due to the lower redox potential of the pulp
(near to 550 mV).
The sea water does not affect the kinetics of leaching of copper concentrate. However,
recirculation of water recovered could affect the kinetics of the process.

ACKNOWLEDGMENTS
We thank InProMet (Innovacin en Procesos Metalrgicos) form the Departamento de
Ingeniera Metalrgica y de Materiales of the Universidad Tcnica Federico Santa Mara
for supporting this work.

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