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Minerals Engineering
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Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources, Gwahang-no 92, Yuseong-gu, Daejeon 305-350, Republic of Korea
Graduate School of Engineering, Hokkaido University, Kita 13 Nishi 8, Sapporo 060-8628, Japan
a r t i c l e
i n f o
Article history:
Received 30 May 2009
Accepted 15 November 2009
Available online 16 December 2009
Keywords:
Chalcopyrite leaching
Chloride leaching solution
Chlorocuprate(I)
Cuprous ion
a b s t r a c t
The effect of chloride on chalcopyrite leaching has been investigated by performing batch leaching tests
with three kinds of leaching solutions and using Hiroyoshis model, which suggests that a zone of rapid
leaching exists between the critical potential (Ec, equilibrium redox potential for the reduction of CuFeS2
to Cu2S) and the oxidation potential (Eox, equilibrium redox potential for the oxidation of Cu2S). The results
of the leaching tests show that the leaching rate in hydrochloric acid solution is the fastest and that the relationship between the Cu leaching rate and oxidationreduction potential (ORP) follows Hiroyoshis model.
Thermodynamic calculations indicate that, with an increase in the chloride concentration, the concentration of cuprous ions increases as the chlorocuprate(I) complex ions are formed and the contribution of
cuprous ions to the critical potential is greater than that of cupric ions, even though the concentration of
cuprous ions is lower than that of cupric ions. This fact suggests that the formation of chlorocuprate(I) ions
in a chloride solution may improve the chalcopyrite leaching rate by increasing the critical potential.
2009 Elsevier Ltd. All rights reserved.
1. Introduction
Chalcopyrite (CuFeS2) is the most abundant copper sulphide
occurring underground (Wang, 2005). Several hydrometallurgical
processes have been proposed for recovering copper from chalcopyrite (Hiroyoshi et al., 2002; Peacey et al., 2003; Prasad and Pandey, 1998). However, with the exception of heap and dump
bioleaching, these hydrometallurgical processes have not been
commercially successful, because chalcopyrite is one of the most
refractory materials to leach (Wang, 2005). To improve the low
leaching rate, several methods have been investigated, including
increasing the temperature and pressure (Habashi, 2006); adding
a modier such as activated carbon (Nakazawa et al., 1998), coal
(Barta et al., 1999), silver (Carranza et al., 1997), and iron powder
(Sanchez et al., 1996); grinding the chalcopyrite particles to less
than 20 lm (Balz, 2003); and adjusting the redox potential
(Hiroyoshi et al., 2002, 2004).
Hiroyoshi and co-workers studied the effect of the redox potential on the leaching rate of chalcopyrite and reported that the
leaching rate increased in relatively low redox potential ranges
(Hiroyoshi et al., 1997, 2000, 2001, 2002, 2004). From these results,
they proposed a new model that involved the formation of intermediate Cu2S at an optimum redox potential, which exists between the equilibrium redox potential for the reduction of
CuFeS2 to Cu2S (equilibrium critical potential, Ec) and that for the
oxidation of Cu2S (equilibrium oxidation potential, Eox). Further-
more, the leaching rate was found to increase at this redox potential, as shown in Fig. 1 (Hiroyoshi et al., 2007). This model was
called redox potential dependence of chalcopyrite leaching, and
the critical potential and oxidation potential were described as
according to the following equations (Hiroyoshi et al., 2000, 2001).
0:75
a 2
RT
ln Cu 0:25
F
aFe2
Ec E0c
Eox E0ox
0:5
RT
ln aCu2
F
472
Log K
CuFeS2
Cu2S
Cu2S
Cu2+
CuFeS2
Cu2+
E
Eox
Ec
E E0
RT Fe3
ln 2
F
Fe
ORP Electrode
Thermometer
Silicon cap
Water
Jacket
2. Experimental
2.1. Materials
The chalcopyrite concentrate used in this study was obtained
from the Omine Mine, Tono City, Japan. The concentrate contained
25.6% Cu, 38.1% Fe, and 2.0% Si, and its mineralogical composition
was 74.8% chalcopyrite, 22.3% pyrrhotite, and 2.9% quartz. The concentrate particles were ground with an alumina mortar and then
dry-sieved with a 200-mesh sieve. The ground particles were char-
Magnetic
bar
Magnetic Stirrer
Fig. 2. Leaching reactor.
473
Intensity
C:chalcopyrite
P:pyrrhotite
K Cu
Cutn1 Cutn
tn1 tn
n 0; 1; 2; 3; . . . ; Cut0
initial Cu concentration
ORPtn1 ORPtn
2
initial ORP
ORPAve
C
C
P
ORP / mV
11
3
2 / deg
H2SO4
HCl
n 0; 1; 2; 3; . . . ; ORPt0
Mixture
Time / minutes
Fig. 4. Variation of the oxidationreduction potential as a function of leaching time.
1
ORPrate
ORPtn1 ORPtn
t n1 tn
n 0; 1; 2; 3; . . . ; ORPt0
initial ORP
12
On the basis of Eqs. (11) and (12) and the data in Fig. 4, the relationship between ORPrate and ORPAve is shown in Fig. 7. As shown
in Fig. 7, ORPrate decreases as ORPAve decreases to around 500 mV;
10
HCl
Mixture
H2SO4
ORPAve / mV
HCl
Mixture
H2SO4
Time / minutes
Fig. 5. Variation of Cu leaching concentration as a function of leaching time.
Cu concentration / gm-3
HCl
Mixture
H2SO4
ORPAve / mV
Fig. 7. Change of ORP rate vs. average ORP.
Fe3 Fe3 0 4x
13
Fe2 Fe2 0 5x
14
4
Fe3
log(a Cu ) or log(a Ag )
dx
Fe2 dt
16
3
aAg
RT
ln
F
aFe2
Fig. 8. Critical potential (Ec(Ag+)) as a function of the logarithm of silver ion activity
and Ec(Cu2+) as a function of the logarithm of cupric ions at 298 K and 1 atm (ferrous
ion activity is 0.1) (Hiroyoshi et al., 2002).
15
Ec Ag E0c
Ec(Cu2+)
17
Cu extraction rate
!
dFe3
1 dFe2
Fe3 dt
Fe2 dt
1
When Eqs. (13) and (14) are differentiated with respect to time and
substituted in Eq. (15), we obtain the following equation:
dE RT
dt
F
Ec(Ag+)
2+
dE RT
dt
F
Critical potential, Ec / V
474
Low Ag + concentration
18
Eox
Ec(Ag+)
Adding Ag + ions
Ec(Ag+)
475
CuCl+
Table 1
Standard Gibbs free energies used.
CuCl2
Eh / V
Cu2+
CuCl
CuCl2-
CuCl43-
Species
DG (kJ mol1)
Reference
CuFeS2
Cu2S
Cu+
CuCl2
2
190.6
86.73
50.2
248.03
377.9
3
506.9
64.96
66.81
196.95
131.14
341.37
CuCl3
CuCl32-
Cu
Log a ClFig. 10. The Ehlog aCl diagram for the Cu+/Cu2+ClH2O system (Lin et al., 1991).
19
CuCl4
Cu2+
CuCl+
CuCl2
Cl
FeCl2
Table 2
Calculated standard potentials (E0c ) of critical potentials in Eqs. (2), (19)(21), (24),
and (25).
Species
2
20
21
where CuCl was not considered because of the low solubility of CuCl
(KSP = 1.72 107) (Lin et al., 1991).
The critical potentials by the cuprous ion species can be obtained according to the following equations:
Ec CuCl2
E0c
3
aCuCl2
RT
ln
F
aFeCl2 aCl 4
22
3
aCuCl2
RT
2
3
Ec CuCl3 E0c
ln
F
aFeCl2 aCl 7
23
3
aCuCl3
RT
3
4
Ec CuCl4 E0c
ln
F
aFeCl2 aCl 10
24
As can be seen in Fig. 10, cupric ions also form complex ions
such as CuCl+ and CuCl2, as the chloride ion concentration increases. The critical potentials by these complex ions can be induced by the following reactions:
Equation
Standard potential, E0c
(V)
CuCl2
CuCl3
CuCl4
Cu2+
CuCl+
CuCl2
19
1.084
20
1.124
21
1.191
2
0.681
24
0.660
25
0.684
2
3
h
i h
i h
i
2
3
CuT Cu CuCl2 CuCl3 CuCl4 Cu2
CuCl CuCl2 ;
29
where CuT represents the total copper in a leaching solution and [i]
is the concentration of species i. In this study, the activity coefcient
is assumed to be 1.
Lin et al. (1991) dened the thermodynamic equilibrium constant between copper ions and chloride ion through the following
set of equations:
Cu 2Cl CuCl2 ;
K1
CuCl2
30
Cu Cu 2
2
25
Ec CuCl
E0c
RT
a 3
ln CuCl
4F
aFeCl2 aCl
27
3
aCuCl2
RT
ln
4F
aFeCl2 aCl 4
28
Ec CuCl2 E0c
CuCl3
31
Cu Cl 3
3
3
Cu 4Cl CuCl4 ;
Critical potential, Ec / V
K2
26
2
Cu 3Cl CuCl3 ;
K3
CuCl4
32
Cu Cl 4
Ec(Cu2+)
Ec(CuCl+)
476
K4
CuCl
2
33
Cu Cl
K5
CuCl2
34
Cu2 Cl 2
CuT Cu 1 106:29 Cl 2 106:07 Cl 3 105:70 Cl 4
Cu2 1 100:089 Cl 100:52 Cl 2
E0 0:159 V
36
E E0
RT Cu2
ln
F
Cu
37
RT
Ec(Cu 2+ )
35
The relation between Cu2+ and Cu+ can be expressed in the following reaction:
Cu2 e Cu ;
Ec(CuCl 2 )
38
1 100:089 Cl 100:52 Cl 2 g
n
Cu CuT = 1 106:29 Cl 2 106:07 Cl 3 105:70 Cl 4
EE0 F
39
e RT 1 100:089 Cl 100:52 Cl 2
The concentration of cuprous ions is expressed in terms of the
total copper concentration, chloride concentration, and redox potential. The concentrations of the cuprous and cupric ion species
were obtained using the calculated cuprous ion concentration. Finally, each critical potential was determined. The critical potentials
of CuCl2 and Cu2+, which are dominant ions in the solution with
less than 0.1 kmol m3 chloride (Fig. 10), are compared and discussed below, because less than 0.1 kmol m3 chloride was used
for the leaching of chalcopyrite in this study.
Fig. 12 shows the critical potentials by CuCl2 and Cu2+ with the
concentration of total copper, calculated under the following conditions: the redox potential is 0.6 V and the concentrations of the
other species are 0.1 kmol m3. The concentration of the chlorocuprate(I) complex formed is very low, as discussed below; therefore, the chloride ion concentration is also assumed to be
0.1 kmol m3. In Fig. 12, both critical potentials increase with an
increase in the total copper concentration. When the total copper
concentration is very low, the critical potential of Cu2+ is higher
than that of CuCl2 , but the critical potential of CuCl2 becomes
higher at a total copper concentration of more than
0.001 kmol m3. The concentrations of CuCl2 and Cu2+ calculated
3
at a total copper concentration of 10 kmol m3 are calculated
to be 5.58 107 and 8.83 104 kmol m3, respectively. These
results suggest that the effect of CuCl2 on the critical potential beTable 3
Equilibrium constants of Eq. (27)(31).
Fig. 12. The comparison of the critical potentials of Cu2+ and CuCl2 as a function of
the total copper concentration (298 K and 1 atm, other ion activities are assumed to
be 0.1).
Critical potential, Ec / V
Cu2 Cl CuCl ;
Ec(Cu 2+ )
Ec(CuCl 2 )
K1
K2
K3
K4
K5
1.995 106
1.202 106
5.012 105
1.288
0.2991
Fig. 13. The comparison of the critical potentials of Cu2+ and CuCl2 as a function of
chloride ion concentration (298 K and 1 atm, other ion activities are assumed to be
0.1).
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