Beruflich Dokumente
Kultur Dokumente
www.elsevier.com/locate/hydromet
Helsinki University of Technology, Laboratory of Corrosion and Materials Chemistry, P.O. Box 6200, 02015 HUT, Finland
b
Outokumpu Research Oy, P.O. Box 60, 28101 Pori, Finland
Received 22 December 2005; received in revised form 12 June 2006; accepted 7 July 2006
Available online 1 September 2006
Abstract
In this study we demonstrate the kinetics of Cu2+ reduction in concentrated cupric chloride solutions. Experiments were carried
out near the boiling point of the solution ([NaCl] = 280 g/l and [Cu2+] = 140 g/l) at T = 90 C, atmospheric pressure, pH = 2.
Electrochemical methods such as cathodic polarization curves and cyclic voltammetry were used to investigate the cathodic
reactions of copper complexes. To identify the nature and the rate-controlling steps of the reactions, rotating disk electrode (RDE)
experiments were conducted. The chemical environment studied was similar to that of the Outokumpu HydroCopperTM process,
which uses a cupric chloride solution to leach copper from the mineral chalcopyrite.
The results suggest that the cathodic reactions are the reduction of [CuCl]+ to the complex [CuCl3]2, the reduction of [CuCl3]2
to solid copper and hydrogen evolution. The diffusion coefficient and the unit rate constants for the solution species were
calculated. The exchange current density and rate constant for electron transfer were also estimated. A simulation was made of the
cathodic polarization curve and it was in good agreement with the experimental data.
2006 Elsevier B.V. All rights reserved.
Keywords: Cathodic reactions; Cupric chloride; Sodium chloride; Chalcopyrite; Leaching of chalcopyrite; HydroCopper
1. Introduction
As sulfur dioxide emissions from the pyrometallurgical
industry are highly undesirable, the development of alternative hydrometallurgical process options for sulfide minerals is of great environmental importance. Chalcopyrite,
CuFeS2, is the most common copper mineral, available in
large quantities and with widespread distribution across
the globe. There is an incentive to develop economically
beneficial processes, like HydroCopper (Hyvrinen
et al., 2002), which convert the sulfur content of sulfide
minerals into elemental sulfur instead of sulfur dioxide.
0304-386X/$ - see front matter 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2006.07.002
10
2
0
CuFeS2s 3Cu2
aq 4Cuaq Feaq 2Ss
CuFeS2s 3CuCl
aq 11Claq
0
4CuCl3 2
aq FeCl2aq 2Ss
According to Gregory and Riddiford (1956) a discrepancy in the Levich equation, Eq. (3), lies in the constant
0.62, based on the I() value of 0.8934. A better estimation
of the diffusion coefficient is suggested to be given by Eq.
(5) for values of (D/v) in the range 04 10 3 cm2/s
(Gregory and Riddiford, 1956).
Il 0:8934 0:316D=v0:36
11
As the value of D 2/3 / I() remains constant, the correlation factor for the Levich equation can be taken into
account. Eq. (5) is known as the GregoryRiddiford
equation (MacHardy and Janssen, 2004).
Non-linearity of a Levich plot at low rotation rates may
be due to kinetic limitations. The KouteckyLevich equation, Eq. (6), (Bard and Faulkner, 2001) is applicable to
first order reactions and can be used to study the combined
effect of diffusion current and kinetic current (Lyons,
2002).
1=I 1=Ik 1=Id
zF3=2 A
RT 1=2
1=2
D0 C0 v
1=2
12
4. Results
The nature of cathodic reactions in the leaching process
was studied using platinum and glassy carbon electrodes.
Platinum is a strong adsorber and an excellent electrocatalyst for hydrogen evolution. The conventional voltammetric response of a polycrystalline platinum/aqueous
solution interface is usually divided into three sections: (i)
adsorption and desorption of hydrogen, b200 mV vs. Ag/
AgCl, (ii) double layer charging, 200 to 600 mV vs. Ag/
AgCl and (iii) oxygen adsorption and oxide formation,
600 to 1300 mV vs. Ag/AgCl. The shape, number and size
of the peaks caused by adsorption/desorption processes
depend on the crystal faces, electrode pre-treatment,
impurities present and the electrolyte (Bard and Faulkner,
2001; Casey, 1999; Sundholm, 1987).
Cyclic voltammetry (Fig. 1) was carried out with platinum and glassy carbon electrodes in a concentrated
sodium chloride solution ([NaCl] = 280 g/l) without cupric
ions. Neither platinum nor glassy carbon appeared to be
reactive in a concentrated sodium chloride solution (Fig. 1).
The electrochemical response of platinum suggested characteristic adsorption and desorption processes. At lower
and higher potentials high currents corresponding to gas
Fig. 3. Levich plot with cupric ion concentrations 10, 20, 30 and 40 g/l.
[NaCl] = 280 g/l, pH = 2, T = 90 C. Limiting current density taken at
0 mV vs. Ag/AgCl.
13
Table 1
Diffusion coefficient of Cu2+ ion or complex calculated from the
experimental data
Method
[Cu2+]
(g/l)
Rotation
rate (rpm)
Levich D
(cm2/s)
GregoryRiddiford
D (cm2/s)
Levich plot
Levich plot
Levich plot
Levich plot
jlim[Cu2+]
jlim[Cu2+]
jlim[Cu2+]
40
30
20
10
140
140
140
1002500
1002500
1002500
1002500
100
900
2500
8.5 10 6
8.5 10 6
7.8 10 6
8.6 10 6
8.1 10 6
8.7 10 6
8.2 10 6
9.0 10 6
9.0 10 6
8.2 10 6
9.1 10 6
8.5 10 6
9.2 10 6
8.6 10 6
14
Table 2
Unit rate constants (kT, cm/s) of cupric ions/complexes calculated from D values (Levich plot) for different cupric concentrations with varying
rotation rate
Rotation rate
(rpm)
100
400
900
1600
2500
[Cu2+] = 10 g/l
[Cu2+] = 20 g/l
[Cu2+] = 30 g/l
[Cu2+] = 40 g/l
Average
kT (cm/s)
kT (cm/s)
kT (cm/s)
kT (cm/s)
kT (cm/s)
2.1 10
4.1 10 3
6.2 10 3
8.3 10 3
10.3 10 3
1.9 10
3.9 10 3
5.8 10 3
7.8 10 3
9.7 10 3
2.1 10
4.1 10 3
6.2 10 3
8.2 10 3
10.3 10 3
2.0 10
4.1 10 3
6.1 10 3
8.2 10 3
10.2 10 3
2.0 10 3
4.1 10 3
6.1 10 3
8.1 10 3
10.1 10 3
Fig. 4. Cyclic voltammetry as a function of scan rate (10, 20, 50, 100
and 200 mV/s) for stationary glassy carbon electrode (6th sweeps,
Eocp 900 mV 200 mV). Solution: [Cu2+] = 20 g/l, [NaCl] = 280 g/l,
pH = 2 and T = 90 C.
15
16
Hackl, R.P., Dreisinger, D.P., Peters, E., King, J.A., 1995. Passivation
of chalcopyrite during oxidative leaching in sulfate media. Hydrometallurgy 39 (1), 2548.
Hietala, K., Hyvrinen, O., 2003. HydroCopper a new
technology for copper production. Alta 2003 Copper Conference,
Perth, Australia, pp. 110.
Hyvrinen, O., Hmlinen, M., Leimala, R., 2002. Outokumpu
HydroCopper process a novel concept in copper production. In:
Peek, E., van Weert, G. (Eds.), Chloride Metallurgy 2002, 32nd
Annual Hydrometallurgy Meeting. MetSoc, Montreal, Quebec,
Canada, pp. 609612.
Lobo, V.M.M., Quaresma, J.L., 1989. Handbook of Electrolyte Solutions
Part B. Elsevier, Coimbra, Portugal, pp. 377, 1603, 1615.
Lundstrm, M., Aromaa, J., Forsn, O., Hyvrinen, O., Barker, M.H.,
2005. Leaching of chalcopyrite in cupric chloride solution.
Hydrometallurgy 77, 8995.
Lyons, M.E.G., 2002. Mediated electron transfer at redox active monolayers. Part 3: bimolecular outer-sphere, first order KouteckyLevich
and adduct formation mechanisms. Sensors 2, 473506.
MacHardy, S.J., Janssen, L.J.J., 2004. The diffusion coefficient of Cu(II)
ions in sulfuric acid-aqueous and methanesulfonic acid-methanol
solutions. Journal of Applied Electrochemistry 34, 169174.
Muir, D.M., 2002. Basic principles of chloride hydrometallurgy. In: Peek,
E., van Weert, G. (Eds.), Chloride Metallurgy 2002, 32nd Annual
Hydrometallurgy Meeting. MetSoc, Montreal, Canada, pp. 759778.