Kinetics of chalcopyrite leaching in

either ferric sulfate or cupric sulfate

media in the presence of NaCl

The study of leaching kinetics is particularly important for process design, Tácia Veloso, Johne Peixoto,
Michael Rodrigues and Versiane
optimization and control. Despite a considerable volume of published literature
Albis Leão. Universidade Federal de
addressing the kinetics of chalcopyrite leaching with Fe(III) and more recently, Ouro Preto, Brazil

Cu(II) solutions, there is no agreement on the rate-determining step, the ac-

tivation energy and the influence of the solution composition on the process.
Aiming at bringing further insight into these topics, the present work sought
to compare the leaching kinetics of chalcopyrite with either ferric sulfate or
cupric sulfate, in the presence of NaCl. Batch experiments were performed in
a 1 L water jacketed reactor, containing 500 mL of pulp with 0.1% solids (w/v),
1 mol/L H2SO4, at 850 min- 1. The effects of temperature (70 to 90°C) and reagent
[Fe(III), Cu(II) and Cl-] concentrations on chalcopyrite dissolution were deter-
mined. The results showed that chalcopyrite leaching is faster with cupric
sulfate than ferric sulfate and that the activation energy was 92,9 kJ/mol with
the former and around 122,3 kJ/mol with the latter. The addition of sodium
chloride to the leaching solutions increased the dissolution rate, as observed
in the experiments performed with 2 mol/L chloride and 1 mol/L ferric ion,
in which chalcopyrite dissolution approached 24%, in 180 minutes, whereas
it was only 5% in the absence of anion. When ferric iron was replaced by cupric
ions (in the presence of chloride), chalcopyrite dissolution increased to 46%
in the same period.

79
INTRODUCTION
Chalcopyrite (CuFeS2) is the most abundant copper mineral, comprising roughly 70% of the
worldwide copper reserves and its relevance to the copper industry is evident, accordingly (Kaplun
et al. 2011). Such a mineral is also a very stable copper sulphide and refractory to
hydrometallurgical processing (Aries & Leo, 2007). For this reason, chalcopyrite leaching is slow as
compared to that of other copper sulphides such as chalcocite (Cu2S) and bornite (Cu5FeS4). Thus,
numerous studies have been carried out seeking to determine the various parameters influencing
its leaching kinetics, such as temperature, particle size, stirring rate, solution type, among others
(Yévenes, Miki & Nicol, 2010).
With respect to the leaching solution, hydrometallurgical processes applied to chalcopyrite ores
and/or concentrates can be classified as nitrate, chloride, sulphate or ammonia leaching and all of
them require the presence of an oxidant agent, such as either ferric or cupric ions or oxygen. The
sulphate-based processes have some advantages because sulphate leaching is generally simpler,
better understood and the recovery of copper by solvent extraction - electrolysis is relatively
straightforward. However, there is an critical shortcoming: the leaching kinetics of chalcopyrite is
slow (Hacklet al, 1995). One way of circumventing this problem, which has been extensively
investigated, is the addition of chloride ions to the sulphate medium (Ruiz, Hills & Padilla, 2011).
According Aries & Leo (2007), the presence of chloride ions: (i) reduces chalcopyrite passivation,
whereas the presence of the Cu(I)-chloride complexes adds a second redox couple to the system,
thereby improving leaching kinetics.
Chalcopyrite oxidation by with ferric iron is given by equation (1) (Dutrizac, 1981):

CuFeS ( ) + 4Fe( ) = Cu( ) + 5Fe( ) + 2S( ) (1)

Furthermore, when chloride ions are present, stable complexes with cuprous ions are formed and
chalcopyrite oxidation can also be carried out by the Cu(II)/Cu(I) couple as represented by the
equation (2) (Carneiro & Leão, 2007). In the presence of either oxygen or ferric iron, Cu(I) is readily
converted back to Cu(II).

CuFeS ( ) + 3Cu( ) = 4Cu( ) + Fe( ) + 2S( ) (2)

The reason for the low leaching rate observed with ferric sulphate is the formation of a passivation
layer, as stated, which occurs during the oxidative leaching and that has been extensively studied.
There is still no consensus of the nature of this layer, as some authors claim that it is formed by
elemental sulphur, while others argue that it is a metal polysulfide. Regardless of its nature, such a
layer is seen as a barrier to the diffusion of the oxidant (Munoz, Wadsworth & Miller, 1979). There
is also disagreement with respect to which step controls the leaching kinetics of chalcopyrite,
chemical reaction (Hirato, Majima & Awakura, 1987a; Cordoba et al., 2008; Ruiz Montes & Padilla,
2011; Kaplun, et al., 2011) or diffusion through the elemental sulphur layer (Munoz, Miller &
Wadsworth, 1979; Bonan et al., 1981; Aries & Leo, 2007). Within such a context, the aim of the

80
present work was to determine the effects of temperature, type of oxidant (cupric or ferric ions) and
their initial concentration on the leaching rate of chalcopyrite with both sulphate and chloride ions.

MATERIALS AND METHODS

Sample preparation
The sample utilized in the leaching experiments was a chalcopyrite chunk, which was crushed and
then ground in a orbital mill. This sample was subjected to analysis in a laser particle size analyzer,
model Cilas 1064. The average particle size of the sample was 17,72μm, with d10=2.64 μm,
d50=13.56μm and d90=39.36μm. X-ray diffraction (Shimadzu, model 6000) showed that the main
mineral phase in the sample was chalcopyrite, and traces of magnetite, pyrite and calcite. Its
content of copper, iron and sulphur was quantified by acid digestion followed by analysis in an
atomic emission spectrometer (Varian, 725), which revealed the presence of 30.6% Cu, 28.2% Fe and
34.3% S, indicating that chalcopyrite represents nearly 90% of the sample.

Leaching tests
The chemical leaching tests were performed batchwise, using a 1L jacketed glass reactor.
Temperature was controlled by circulating water heated by a thermostatic bath equipped with an
external circulation pump. The glass reactor was magnetically stirred and the value of 850min-1 was
selected to ensure that the film diffusion resistance was negligible. Leaching solutions were
prepared from analytical grade chemicals (ferric sulphate, cupric sulphate, sulphuric acid and
sodium chloride) and distilled water and the effect of chloride ions (0mol/L to 2mol/L) on
chalcopyrite leaching was determined at 80°C, using 1mol/L sulphuric acid and 1mol/L ferric
sulphate. The influence of ferric iron (0mol/L to 1mol/L) was also assessed at 80°C, in the presence
of 1mol/L sulphuric acid and 2mol/L sodium chloride. Similar conditions were utilized to analyse
the effect of cupric copper (0mol/L to 0.5mol/L) on the leaching rate. Finally, temperature was
varied from 70°C to 90°C, in tests performed with 1mol/L sulphuric acid, 2mol/L sodium chloride
and either 1mol/L ferric iron or 0.5mol/L cupric sulphate.
Throughout the experiments, a 0.1% (w/v) solids concentration was utilized and 1.5mL samples
were collected regularly for chemical analysis (copper and iron), carried out in an ICP-OES (Varian,
725). In the experiments with ferric iron, copper concentrations were utilized to determine
chalcopyrite dissolution, whereas iron concentrations were used with the same aim in the
experiments with cupric sulphate and sodium chloride.

RESULTS AND DISCUSSION

Effect of chloride ions on chalcopyrite leaching

It is well known that the presence of chloride ions increases the rate of chalcopyrite dissolution in
sulphate media, but there is no agreement on what is the threshold for which copper extraction
stops to be benefited. Lu, Jeffrey & Lawson (2000) and later Ruiz, Hills & Padilla (2011) suggested
that sodium chloride significantly increases the leaching rate up to 0.5mol/L NaCl, while Palmer et
al. (1981) and Lamb & Lion (2007) set such threshold at 1.0mol/L NaCl.

81
Figure 1 shows copper extraction yields as a function of time for concentrations of chloride ions
varying from 0mol/L to 2.0mol/L. It can be observed that, in three hours of testing, copper
dissolution increased from 5% in the absence to 22% with 1.5mol/L NaCl confirming the positive
effect of chloride ions in copper extraction from chalcopyrite. Nevertheless, such improvement on
copper extraction became negligible at high chloride concentrations because when the NaCl
concentration was increased further to 2.0mol/L, the final extraction reached only 24%.
Notwithstanding, 2.0mol/L NaCl solutions were utilized throughout the kinetic study to ensure
that chloride concentrations did not limit copper extraction.

3+
1.0 mol/L H2SO4, 1.0 mol/L Fe and T= 80°C
25 Concentration of NaCl (mol/L):
0.0 1.0
1.5 2.0
Extraction of copper (%)

20

15

10

0
0 2000 4000 6000 8000 10000
Time (s)

Figure 1 Effect of concentration of NaCl on chalcopyrite dissolution ¡Error! No hay texto con el estilo
especificado en el documento.

Figure 2 depicts copper extraction from chalcopyrite for different concentrations of either ferric iron
(a) or cupric ions (b). In the absence of either oxidant, 15% copper and 14% iron were extracted,
while copper extraction increased with the ferric iron concentrations up to 0.5mol/L Fe3+. Final
extractions reached 24% and 46% copper dissolution with 1.0mol/L ferric iron and 0.5mol/L cupric
ions, respectively, in three-hour testing. Such results show that in sodium chloride-sulphuric acid
solutions, chalcopyrite oxidation by cupric ions is more effective than that achieved with ferric
sulphate. Such outcome has been ascribed to a faster and more reversible Cu2+ reduction to Cu+ (on
the chalcopyrite surface), as compared to that of the Fe3+/Fe2+ couple (Dutrizac, 1992).
Regarding the initial oxidant concentration, it was noticed that copper extractions increased from
18% to 24%, as the initial Fe3+ content varied from 0.1mol/L to 1.0mol/L, respectively (Figure 2 (a)),
i.e., a relatively small increase. According to Cordoba et al. (2008) the rate of chalcopyrite
dissolution is strongly affected by the initial ferric iron concentration, but only for values below
0.01mol/L. At higher concentrations, such effect is negligible, which is consistent with the findings
of the present study. In those tests carried out utilizing cupric ions as the oxidant (Figure 2(b)),
similar results were observed (Figure 2 (b)). Chalcopyrite dissolution in experiments with 0.125
mol/L and 0.5mol/L CuSO4 were 42% and 46%, respectively, i.e. a small increase. This implies that
the rate of chalcopyrite dissolution is not strongly dependent on the concentration of oxidizing
agent.

82
 a) 1.0 mol/L H2SO4, 2.0 mol/L NaCl and T= 80°C b)
2+
50 1.0 mol/L H2SO4, 2.0 mol/L NaCl e T= 80°C 50 Concentration of ion Cu (mol/L):
3+
Concentração de ion Fe (mol/L): 0.0 0.125
0.0 0.02 0.25 0.5
Extraction of copper (%)

40 40
0.1 0.25

Extraction of iron (%)

0.5 1.0
30 30

20 20

10 10

0 0
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Time (s) Time (s)

Figure 2 Effect of concentration of ion Fe3+ (a) and Cu2+ (b) on chalcopyrite dissolution

Kinetics of chalcopyrite leaching

Temperature is an important parameter in the dissolution of copper sulphides and, as expected, its
increase results in faster leaching kinetics and larger extraction yields. The effect of temperature on
the leaching kinetics of the chalcopyrite sample under study was investigated in the range 70°C to
90°C, so that the apparent activation energy (Ea) could be assessed for both oxidants in the presence
of sodium chloride. Figure 3(a) presents chalcopyrite leaching as a function of time for a solution
containing 1.0mol/L ferric iron, whereas Figure 3(b) shows the same results for the Cu(II)/Cu(I)
couple (0.5 mol/L cupric ions). Applying ferric ions (Figure 3(a)), copper extraction increased from
17% to 50% as the temperature varied from 70oC to 90oC. In the presence of cupric ions (Figure 3
(b)), the same parameter increased from 35% to 70%, in three hours of the experiment. Such results
emphasise the dependence of chalcopyrite dissolution on temperature. Analysing both figures, it
can be noticed that both leaching rate and extraction yields are higher when leaching is carried out
with cupric ions. Nonetheless, the performance of both oxidants approach each other at higher
temperatures, i.e. up to 80°C, the leaching rate determined in tests with cupric ions was
approximately twice as higher as that achieved with ferric ions, but at both 85°C and 90°C, it is only
1.4 times larger.
From data presented in Figure 3, the kinetics parameters related to chalcopyrite leaching were
determined by applying the shrinking core model. After reducing the film diffusion resistance, the
experimental data were fitted to both chemical reaction and ash layer diffusion controls, but the
latter described better the kinetics of the oxidative leaching of chalcopyrite (Figure 4). According to
this latter mechanism, the fraction reacted (X) and time (t) are related by equation 3, where Kd is the
rate constant (Munoz, Miller & Wadsworth, 1979):

F(X) = 1 − 3 ∙ (1 − X) + 2 ∙ (1 − X) = K ∙ t (3)

83
 1.0 mol/L H2SO4, 2.0 mol/L NaCl 1,0 mol/L H2SO4, 2,0 mol/L NaCl
70 Temperature: a) Temperature: b)
70
70 °C 75 °C 70 °C 75 °C
60 80 °C 85 °C 80 °C 85 °C
60

Extraction of iron (%)

Extraction of copper (%)

90 °C 90 °C
50 50

40 40

30 30

20 20

10 10

0 0
0 2000 4000 6000 8000 10000 0 2000 4000 6000 8000 10000
Time (s) Time (s)

Figure 3 Effect of temperature on chalcopyrite dissolution: a) 1.0mol/L Fe3+ and b) 0.5mol/L Cu2+

3+
a)
0.5 mol/L Cu
2+ b) 1.0 mol/L Fe
0.10 Temperature:
0.24 Temperature:
70 °C 70 °C
2 2
y = 2.27E-5x R = 0.99 75 °C y= 9.24E-6x R = 0.99
1-3*(1-x) +2*(1-x)

0.20 75 °C 0.08
80 °C 80 °C
1-3*(1-x) +2*(1-x)

0.16 85 °C 85 °C 2
2
y = 1.16E-5x R = 0.99 0.06 90 °C y= 4.76E-6x R = 0.99
90 °C
2/3
2/3

0.12
2
y= 8.02E-6x R = 0.98 0.04
0.08 2
2
y= 5.24E-6x R = 0.94 y= 1.88E-6x R = 0.99
0.02
0.04 2
y= 1.28E-6x R = 0.99
2
y = 3.57E-6x R = 0.93 2
y= 9.4E-7x R = 0.99
0.00 0.00
0 2000 4000 6000 8000 10000 12000 0 2000 4000 6000 8000 10000 12000
Time (s) Time (s)

Figure 4 Fit of shrinking core model for diffusion control a) 1.0mol/L Fe3+ and b) 0.5mol/L Cu2+

The application of equation 3 to data produced at different temperatures, the activation energy was
determined as 122.3kJ/mol for experiments with 1.0 mol/L Fe3+ and 92.9 kJ/mol, for 0.5 mol/L Cu2+
ion. Presented in Table 1 are activation energy values achieved in different studies and values
ranging from 75kJ/mol to 130kJ/mol are reported for ferric iron leaching in the 35°C - 100°C
temperature range (Cordova et al. 2,008; Dutrizac, 1981). Leaching with both copper and chloride
ions (from 60°C to 105°C) produced activation energy values in the range 59.5 kJ/mol to 134.7kJ/mol
(Bonan et al. 1981; Hirato, Majima & Awakura, 1987a). High values of the activation energy imply
in the need of high temperatures to achieve large copper extractions in short periods. Dutrizac
(1981) explained such differences by stressing that activation energies are affected by both the (i)
temperature, (ii) reagent concentration and (iii) the particle size range investigated as well as the
(iv) presence of impurities and other copper minerals in the chalcopyrite sample along with (v) its
origin and finally by (vi) the kinetic model selected. The values herein achieved are too high for an
ash layer diffusion-controlled system. Such a result is very likely related to the broad particle size
distribution utilized in the experiments, which results in an erroneously fitting to equation 3, even
though chemical reaction is actually controlling the leaching kinetics as discussed by Gbor & Jia
(2004).

84
Table 1 Some values of activation energy for chalcopyrite dissolution reported by literature

Medium T (°C) Ea (kJ/mol) Kinetic control Reference

Ferric Sulphate 50-94 75 Parabolic, diffusion control Dutrizac (1981)

Ferric Sulphate 60-90 83,7 Parabolic, diffusion control Muñoz et al. (1979)

Ferric Sulphate 50-78 88 Linear , diffusion control. Hirato et al. (1987b)

Ferric Sulphate +
70 - 90 122,3 Parabolic, diffusion control This work
NaCl

Ferric Sulphate 35-68 130,7 Parabolic, Chemical control Córdoba et al. (2008)

CuCl2 + NaCl 85-104 71 Parabolic, diffusion control Bonan et al. (1981)

Cupric Chloride 60-85 81,5 Linear, Chemical control Hirato et al. (1987a)

Cupric Sulphate +
70-90 92,9 Parabolic, diffussion control This work
NaCl

CONCLUSION
As suggested by the high values of activation energy, chalcopyrite leaching is highly temperature
dependent, with faster kinetics in cupric sulphate-chloride medium as compared to ferric sulphate-
chloride solutions, i.e. 50% dissolution was achieved using ferric iron and 70% with cupric ion. The
improvement provided by chloride additions is larger up to 1.0mol/L NaCl, reducing when the
concentration is increased further to 2.0mol/L NaCl. A broad particle size distribution very likely
influenced the kinetic analysis and implied in a good data fitting to the equation representing ash
layer diffusion control, despite the very large values of the activation energy achieved i.e.
92.9kJ/mol (with 0.5 mol/L Cu2+) and 122.3kJ/mol, for experiments with 1.0mol/L Fe3+.

ACKNOWLEDGEMENTS
The authors are grateful to Conselho Nacional do Desenvolvimento Científico e Tecnológico
(CNPq), Fundação de Amparo à Pesquisa do Estado de Minas Gerais (FAPEMIG), Coordenação de
Aperfeiçoamento de Pessoal de Nível Superior (CAPES) and Financiadora de Estudos e Projetos
(FINEP) for financial support. The “Conselho Nacional de Pesquisas” – CNPq scholarship to V. A.
Leão and to Peixoto, J. J. M., the “Aperfeiçoamento de Pessoal de Nível Superior” – CAPES
scholarship to T. C. Veloso are especially acknowledged.

85
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