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Abstract
1. Introduction
Chalcopyrite CuFeS 2 . is the most abundant primary copper ore, and as a result, the
extractive metallurgy of copper is based largely on this mineral. Traditionally, the
copper has been recovered using pyrometallurgical processes such as flash smelting. In
recent years, there has been a push to develop alternative processes that do not produce
sulfur dioxide as a by-product. Sulfuric acid leaching is perhaps the simplest alternative
)
Corresponding author.
E-mail address: matthew.jeffrey@eng.monash.edu.au M.I. Jeffrey..
0304-386Xr00r$ - see front matter q 2000 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 0 0 . 0 0 0 6 8 - 2
146 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155
to smelting, although this process has not been adopted commercially because of the
slow leaching kinetics and poor copper extraction at atmospheric pressure w1x.
The leaching of chalcopyrite is an electrochemical process involving the oxidation of
sulfide to sulfur, sulfate or other oxysulfur anions w1x. The overall electrochemical
reactions occurring during the oxidative leaching of chalcopyrite can be represented by
the half reactions:
CuFeS 2 Cu 2q
q Fe 3qq 2S q 5ey 1.
5Hqq
5
4
O 2 q 5ey 52 H O 2 2.
Thus, standard electrochemical techniques have been used to determine mechanistic
details of the leaching process. These studies have shown that the poor leaching kinetics
are a result of anodic passivation; one theory is that the passivation is caused by the
formation of an insulating layer of elemental sulfur on the chalcopyrite surface w2,3x.
Indeed, recent studies w4x have shown that sulfur is the major product formed in
long-term leaching; however, this does not necessarily imply that sulfur causes the
passivation during the initial stages of mineral oxidation.
Recently, it has been shown that other sulfides can be effectively leached using a
mixed sulfatechloride system w5,6x. The role of chloride ions is believed to limit the
extent of passivation by elemental sulfur w5,6x. The aim of the current study is to extend
this work by applying electrochemical techniques to investigate the initial oxidation and
passivation of chalcopyrite in acid solutions containing sulfate and chloride ions.
2. Experimental
Fig. 1. Schematic diagram showing the carbon paste electrode holder. 1. Stainless steel holder. 2. Teflon
coating. 3. Stainless steel screw press. 4. Carbon paste surface areas 0.2 cm2 ..
screw press that allows the paste to be compacted. For each measurement, a fresh
electrode surface was exposed by scraping a layer of paste out of the cavity and then
smoothing the surface with a spatula. The thickness of the paste for each measurement
was set at 3 mm and the electrode produced in this way had a resistance of less than 15
V.
Solutions were prepared using AR grade sulfuric acid and sodium chloride. In
addition, each solution contained 10y4 M Fe 3q and Cu2q, which kept the Fe 3q and
Cu2q ion concentrations in solution essentially constant during each experiment. The
solutions were thoroughly degassed by passing high-purity nitrogen through for 30 min
before and during each experiment. A saturated calomel electrode was used as the
reference electrode in the studies, and this was introduced via a Luggin capillary
extending to the center of the cell just below the end of the working electrode.. All
potentials are reported with respect to the SHE. A platinum wire was used as the counter
electrode. In the voltammetry experiments, a potential scan rate of 20 mV s y1 was
adopted in all cases.
Cyclic voltammetry was used to study the electrochemical leaching behaviour of the
concentrate; shown in Fig. 2 are the voltammograms for 1 M sulfuric acid in the absence
of chloride ions. These experiments were performed using a stationary electrode. The
solid line represents the voltammogram when the potential scan is started in the anodic
148 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155
Fig. 2. Cyclic voltammogram showing the oxidation and reduction of chalcopyrite in 1 M sulfuric acid. The
solid line results when the scan is initiated in the positive anodic. direction, and the dashed line results when
the scan is initiated in the negative cathodic. direction. Experimental conditions: T s 208C, 0 M NaCl, 20 mV
sy1 .
direction, and the dashed line represents the cathodic direction. These voltammograms
were found to be similar to those obtained by using massive chalcopyrite mineral
samples w7,8x. This result is not surprising, as quartz and pyrite are essentially inert in
the potential region of interest w9x. It is clear from Fig. 2 that the voltammograms exhibit
four anodic and four cathodic peaks. These peaks are discussed in detail below.
According to Price and Warren w3x peak A1 at relatively lower anodic overpotentials.
is due to the partial oxidation of chalcopyrite, as shown in Eq. 3., where y ) x.
This suggests that there is release of iron from the chalcopyrite lattice during anodic
dissolution. The structure Cu 1y x Fe1yy S 2yz is an intermediate product, which mixed
with sulfur, forms a passive electron conducting layer on the mineral surface. Parker et
al. w10x referred to the product as a polysulfide, which has semi-conducting properties. It
is worth noting that in terms of a charge balance, z must always equal x q y; otherwise,
SyII. would not be oxidised to S0..
Peaks C1 and C2 reflect the reduction of the products produced at peak A1;
otherwise, they would appear in the dashed voltammogram as well. The obvious
difference in the areas under the anodic peak A1 and cathodic peaks C1 and C2 indicate
that the reaction is not fully reversible. This observation is consistent with the results of
other investigators e.g. Lazaro et al. w2x.. Peak C3 corresponds to the reduction of the
remaining chalcopyrite to an intermediate copper sulfide phase such as talnakhite
Cu 9 Fe 8 S 16 . or bornite Cu 5 FeS 4 . Eqs. 4. and 5., respectively.. At potentials more
negative than peak C3, chalcocite is formed, and the iron is completely removed from
Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 149
the lattice, as shown in Eq. 6.. Other reactions that may occur at these negative
potentials are the reduction of Cu2q to copper metal, and the evolution of hydrogen.
Cu Fe S q Fe q 2H S
9CuFeS 2 q 4Hqq 2ey 2q
4.
5CuFeS q 12H q 4e Cu FeS q 4Fe q 6H S
9 8 16 2
q y 2q
5.
2CuFeS q 6H q 2e Cu S q 2Fe q 3H S
2 5 4 2
q y 2q
2 2 2 6.
When the potential sweep is reversed at y380 mV, it can be seen that there are three
anodic peaks: A2, A3 and A1X . Each of these peaks corresponds to the oxidation of
products produced during the cathodic sweep. Price and Warren w3x have suggested that
in the potential region of peaks A2 and A3, H 2 S is oxidised to elemental sulfur. In
addition, any copper metal that is formed in the cathodic sweep will be oxidised to Cu2q
in this potential region. Finally, the peak A1X is attributed to the oxidation of chalcocite
Cu 2 S. to non-stoichiometric sulfides Cu 2yx S. being deficient in copper w3x. Given that
the charge associated with peak A1X is almost the same as that for peaks C3 and C4, it is
likely that x will be close to 1, with covellite being formed as the main product.
Cu 2 S Cu 2yx S q xCu
2q
q 2 xey 7.
Fig. 3. Currenttime curves representing the re-oxidation of chalcopyrite at a fixed potential of 800 mV. Prior
to each experiment, the mineral was oxidised at 800 mV for 120 s and then allowed to relax for the specified
time. Experimental conditions: T s 208C, 1 M H 2 SO4 , 20 mV sy1 .
Cyclic voltammograms for the chalcopyrite concentrate in the presence and absence
of 0.5 M sodium chloride are shown in Fig. 4. It is clear from this graph that chloride
ions have a substantial effect on the electrochemical behaviour of the sulfide. In
particular, the anodic peak A1 is twice as great in the presence of chloride ions. It is also
evident from Fig. 4 that peaks C3 and C4 the reduction of chalcopyrite to chalcocite via
Fig. 4. Voltammograms representing the effect of NaCl on the oxidationrreduction of chalcopyrite. Experi-
mental conditions: T s 208C, 1 M H 2 SO4 , 20 mV sy1 .
Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 151
talnakhite andror bornite. are larger in the presence of chloride ions. Obviously,
chloride ions enhance the oxidation and reduction of chalcopyrite; such a result is
consistent with chloride affecting the surface state of the Cu 1y x Fe1yy S 2yz formed
during the positive potential scan. It has been observed that the porosity of the sulfur
formed after a long period of leaching is affected by chloride w4x; however, the role of
chloride appears to differ here since sulfur is not the dominant product. At this stage, the
mechanism by which chloride initially enhances the oxidation of chalcopyrite remains
unresolved.
Since this project is mainly concerned with the leaching of chalcopyrite in the
presence of chloride ions, it was decided to concentrate on the potential region of the
anodic peak A1. Fig. 5 shows the voltammograms that result when the anodic and
cathodic limits are lowered. Also shown is the complete voltammogram for comparison.
The most obvious feature of these curves is that when the potential scan is reversed at
100 mV, the peak A1X is much smaller than peak A1. This confirms that the passive
nature of the oxidised surface persists during the second potential cycle. Such a result is
hardly surprising, as the surface has had little time to relax the scan rate is 20 mV sy1 .
prior to re-oxidation.
Fig. 6 shows the voltammograms representing the oxidation of chalcopyrite in the
presence of chloride ions at 208C and 708C. It is immediately clear that at 708C, the
oxidation reaction is far more rapid than that at 208C. This indicates that the passive film
is much less protective at elevated temperatures, and so one expects that at higher
temperatures, chalcopyrite will leach more rapidly. Such a result is consistent with
results of direct leaching experiments, which showed that copper extraction increased
with temperature up to 858C in direct leaching experiments involving the use of oxygen
as the oxidant, as the temperature is increased, the solubility of oxygen decreases and
this affects the reaction rate.. The remaining electrochemical experiments were con-
ducted at 708C.
Fig. 5. Voltammograms that result when the anodic and cathodic limits are reduced. Experimental conditions:
T s 208C, 0.5 M NaCl, 1 M H 2 SO4 , 20 mV sy1 .
152 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155
Fig. 6. Effect of temperature on the oxidationrreduction of chalcopyrite in the presence of 0.5 M NaCl.
Experimental conditions: 1 M H 2 SO4 , 20 mV sy1 .
Fig. 7. Currenttime curves representing the oxidation of chalcopyrite at a fixed potential of 615 mV in the
presence and absence of 0.5 M NaCl. Experimental conditions: T s 708C, 1 M H 2 SO4 .
Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155 153
Fig. 8. Currenttime curves representing the oxidation of chalcopyrite in the presence of NaCl at 615 and 815
mV. Experimental conditions: T s 708C, 0.5 M NaCl, 1 M H 2 SO4 .
154 Z.Y. Lu et al.r Hydrometallurgy 56 (2000) 145155
Fig. 9. Potentialtime curves representing the oxidation of chalcopyrite in the presence and absence of NaCl at
a fixed current of 50 mA. Experimental conditions: T s 708C, 1 M H 2 SO4 .
tion of the chalcopyrite electrode at 50 mA. Like the currenttime curves, these curves
also show the formation of the passive film, with potential increases representing an
increase in the degree of passivation. However, the most important feature of these
curves is the steady-state potential; it is clear from Fig. 9 that this value is much more
positive in the absence of chloride ions. So to achieve an equivalent leaching rate, the
required mixed potential for solutions containing chloride will be much lower than that
for solutions containing no chloride.
4. Conclusions
The carbon paste electrode is a very useful means of studying the electrochemical
behaviour of chalcopyrite concentrates. The use of concentrates instead of ground
minerals allows the establishment of results that reflect potential industrial processes of
interest; in this case, the mixed sulfatechloride leaching of a Mt. Isa Mines copper
concentrate. It was shown that at low overpotentials, the mineral surface is passivated,
and the experimental results were consistent with the formation of a metal-deficient
sulfide surface. Both transient- and steady-state techniques showed that chloride ions
significantly enhance the oxidation of chalcopyrite, particularly at elevated temperatures.
The results of this study have also been found to be in a very good agreement with those
results obtained by direct leaching of the same concentrate.
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