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Hydrometallurgy
j o u r n a l h o m e p a g e : w w w. e l s ev i e r. c o m / l o c a t e / h yd r o m e t
Leaching of chalcopyrite with ferric ion. Part II: Effect of redox potential
E.M. Crdoba a, J.A. Muoz b, M.L. Blzquez b, F. Gonzlez b, A. Ballester b,
a
b
Escuela de Ingeniera Metalrgica y Ciencia de los Materiales, Facultad de Ingenieras Fsico-Qumicas, Universidad Industrial de Santander, Bucaramanga, Colombia
Departamento de Ciencia de Materiales e Ingeniera Metalrgica, Facultad de Ciencias Qumicas, Universidad Complutense de Madrid, 28040 Madrid, Spain
A R T I C L E
I N F O
A B S T R A C T
This paper reports the effect of redox potential (or Fe3+/Fe2+ ratio) on chalcopyrite leaching. The relationship
between redox potential and other variables (iron concentration and temperature) is also evaluated. Leaching
tests were performed in stirred Erlenmeyer asks with 0.5 g of pure chalcopyrite and 100 mL of a Fe3+/Fe2+
sulphate solution. The redox potential ranged between 300 and 600 mV Ag/AgCl for the solution at a pH 1.8,
180 rpm, with temperatures at 35 C or 68 C. The results show that although ferric ion is responsible for the
oxidation of chalcopyrite, ferrous ion has an important role in that it controls precipitation and nucleation of
jarosites, which ultimately causes passivation of this sulphide. Chalcopyrite dissolves through the formation
of an intermediary product (covellite, CuS) that is later oxidized by ferric ion, releasing Cu2+ ions.
2008 Elsevier B.V. All rights reserved.
1. Introduction
Chalcopyrite, the most abundant mineral in copper ore bodies, is
also the most recalcitrant to hydrometallurgical processes (Dutrizac,
1978), and for that reason copper is mainly extracted by pyrometallurgy. However, the depletion of ore deposits and declining mineral
grades has encouraged the development of hydrometallurgical
processes for the treatment of chalcopyrite.
The dissolution of chalcopyrite by ferric ion is normally depicted by
the following chemical reactions (Dutrizac and MacDonald, 1974):
CuFeS2 4Fe3 YCu2 5Fe2 2S-
89
Content (%)
Copper
Iron
Sulphur
Zinc
Lead
27.36
29.65
34.30
0.31
0.02
90
K 3Fe3 2SO2
4 6H2 OYKFe3 SO4 2 OH6 6H :
Table 2
EDS microanalysis of chalcopyrite leaching residues (results in weight percent)
Test
Chalcopyrite surface
Fe
Cu
35 C
400 mV
35 C
600 mV
68 C
400 mV
68 C
600 mV
Original
Attacked
Precipitate
Attacked
Precipitate
Attacked
Precipitate
Attacked
Precipitate
30.80
30.50
33.48
34.17
23.25
30.81
18.89
33.30
14.49
32.24
32.96
27.46
29.18
23.08
27.44
31.35
27.34
34.10
36.96
36.54
29.75
31.49
18.19
29.14
1.05
29.31
0.72
9.31
5.16
34.18
12.32
46.33
9.84
46.46
1.30
0.29
2.38
0.21
4.23
91
Fig. 5. Inuence of redox potential on the chalcopyrite leaching at 68 C and [Fe]Total = 5 g/L.
Fig. 6. SEM micrographs of the leaching residues at 68 C and [Fe]Total =5 g/L: a)Einitial =400 mV,
b) Einitial =600 mV and c) circled particle in (b) at higher magnication.
92
and goethite in the leaching residues at low potential (Fig. 6a), like in
experiments at high potentials (Fig. 6b). X-ray diffractograms of the
residues also show the presence of sulphur, although in a smaller
proportion than jarosite (Fig. 7).
The passivating nature of jarosites is in good agreement with
thermodynamic data. For the dissolution of jarosite at 25 C, Baron and
Palmer (1996) determined:
KFe3 SO4 2 OH6 6H YK 3Fe3 2SO2
4 6H2 O
11
Fig. 8. SEM micrographs of the leaching residues at 68 C, [Fe]Total = 5 g/L, Einitial = 400 mV
and short times: a) 1 h, b) 5 h and c) 1 day.
93
12
13
Nevertheless, the authors favor the idea that although this reaction
is thermodynamically possible, it does not occur because of the
hydrophobic nature of the elemental sulphur (Dutrizac and MacDonald, 1974).
Therefore, chemical reactions (8) and (12) become kinetically more
favorable.
3.2. Inuence of iron concentration
10
Table 3
EDS microanalysis of chalcopyrite leaching residues at 68 C, [Fe]Total = 5 g/L,
Einitial = 400 mV and short times (results in weight percent)
Time
1h
chalcocite
djujerite
digenite
covellite
11
5h
1 day
Chalcopyrite surface
Fe
Cu
Original
Attacked
Precipitate
Attacked
Precipitate
Attacked
Precipitate
30.80
30.16
34.06
37.32
28.99
32.84
12.39
32.24
31.99
8.87
29.64
28.76
29.74
23.91
36.96
36.33
48.76
33.04
30.38
33.05
4.45
3.92
0.65
1.52
8.31
11.87
4.37
54.68
94
Fig. 12. X-ray diffractogram of the leaching residue at 68 C, Einitial = 600 mV and
[Fe]Total = 0.5 g/L.
14
Fig. 11. SEM micrograph of the leaching residue at 68 C, Einitial = 600 mV and
[Fe]Total = 0.5 g/L.
15
Fig. 13. Inuence of temperature on the chalcopyrite leaching at Einitial = 400 mV.
95
1/3
over time.
308
319
330
341
k (days 1)
0.0006
0.0044
0.0319
00732
k (s 1)
9
6.9444 10
5.0926 10 8
3.6921 10 7
8.4722 10 7
16
In the case of pyrite, there are evidences that this sulphide only
dissolves when chalcopyrite is already passivated. Moreover, pyrite
rest potential is higher than that of chalcopyrite and, therefore, pyrite
enhances dissolution chalcopyrite through galvanic contact.
Finally, the comparison between studies on chalcopyrite leaching
is a difcult task because of differences in experimental conditions
used. However, unlike at high temperature, chalcopyrite dissolution
and ferric ion hydrolysis kinetics are very slow processes at low
temperature (35 C).
4. Conclusions
1. The redox potential is a key factor in the leaching of chalcopyrite. A
high potential at the onset of leaching provokes rapid passivation of
chalcopyrite.
2. Ferric/ferrous sulphate leaching solutions tend to reach equilibrium
when the activities of the two ions are equal, which is associated
with a critical potential of approximately 450 mV. When the redox
potential is very high initially, that tendency to equilibrium favors
rapid precipitation of ferric ion as jarosite and consequently
passivation of chalcopyrite.
3. The activation energy during chalcopyrite leaching was 130.7 kJ/
mol, which is a clear demonstration of the importance of thermal
activation in this process.
4. Increasing the iron concentration from 0.5 to 5 g/L had a positive
effect in the chalcopyrite leaching at 68 C.
5. Chalcopyrite dissolves through the intermediate formation of
covellite, CuS, which is later oxidized by ferric ion to release Cu2+
ions:
CuFeS2 2Fe3 YCuS 3Fe2 S-
Table 4
Values represented in the Arrhenius plot of Fig. 15
T (K)
1000 / T (K 1)
ln k (s 1)
3.25
3.13
3.03
2.93
18.79
16.79
14.81
13.98
References
Ammou-Chokroum, M., Cambazoglu, M., Steinmez, D., 1977. Oxydation menage de la
chalcopyrite en solution acide: analyses cintique de ractions. II. Modles
diffusionales. Bulletin de la Societe francaise de mineralogie et de
cristallographie 100, 161177.
96