Hydrometallurgy 111-112 (2012) 35–45

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Hydrometallurgy
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The role of galena associated with silver-enhanced pyrite in the kinetics of

chalcopyrite leaching during the Galvanox™ process
G. Nazari ⁎, D.G. Dixon, D.B. Dreisinger
Department of Materials Engineering, University of British Columbia, Vancouver, BC, Canada V6T 1Z4

a r t i c l e i n f o a b s t r a c t

Article history: The effects of silver ions, galena, and pyrite on the kinetics of chalcopyrite leaching have been studied. In
Received 16 May 2011 addition, the effects of galena and pyrite pretreated with silver ions have been investigated. It has been
Received in revised form 14 September 2011 found that the addition of silver ions, pyrite, and pyrite pretreated with silver ions accelerates the rate
Accepted 30 September 2011
of chalcopyrite leaching significantly. The addition of galena has minimal effect on the kinetics of chalcopyrite
Available online 12 October 2011
leaching. Considering the high cost of silver, the possibility of recycling these catalysts was also examined. The
Keywords:
results indicate that direct recycling of silver ions as a catalyst is not feasible; however, silver-enhanced pyrite
Galvanox™ process can be efficiently recycled to subsequent leaching tests. Secondary Electron Microscopy and Electron
Chalcopyrite Diffraction X-ray techniques were applied to study the morphology and elemental composition of residues
Pyrite after completion of leaching experiments. In this study, formation of a porous sulfur layer around chalcopyrite
Galena was observed in both the presence and absence of catalysts indicating that acceleration of the rate of chalcopyrite
Silver leaching in the presence of catalysts is not due to the alteration of morphology of sulfur around chalcopyrite.
Atmospheric leaching © 2011 Elsevier B.V. All rights reserved.
Kinetics
Morphology

1. Introduction al. (1986) indicating that a porous sulfur layer containing Ag 0 and
Ag2S forms on the surface of chalcopyrite instead of an impermeable
Hydrometallurgical processing of primary copper concentrates in sulfur layer. In spite of positive catalytic properties of silver toward the
ferric sulfate media has become an increasingly important process extraction of copper from chalcopyrite, given the high cost of silver and
in the treatment of these concentrates due to its lower capital cost, the difficulty of recovering silver from sulfur residues, the industrial
ease of operation, simplicity of leaching reactions, and environmental application of silver-catalyzed techniques has been limited (Ballester
friendliness. However, the rate and extent of chalcopyrite leaching in et al., 1990). Recovery of silver from residues is possible but at
ferric sulfate leaching processes can be very low (Hackl et al., 1995). the expense of several additional and inconvenient process steps,
The reasons for this have not been clearly established. Initial reaction including melting and filtering elemental sulfur from the leach residue,
rates have been noted to decline rapidly with time, leading many leaching the sulfur-free residue in acidic brine, and recovering an
investigators to conclude that a passivating layer forms on the mineral elemental silver product by cementation (Palencia et al., 1998).
surface. Hence, extensive research in developing an efficient hydro- In addition, it has been found that the addition of pyrite to the
metallurgical process to extract copper from chalcopyrite has been leach slurry in ferric sulfate media increases the rate of chalcopyrite
conducted. leaching (Berry et al., 1978; Dixon et al., 2008; Mehta and Murr,
The catalytic properties of silver on chalcopyrite leaching in both 1983; Munoz et al., 2008; Nowak et al., 1984). Pyrite provides an
chemical and biological systems have been demonstrated before. It alternative surface for cathodic reaction (ferric reduction). Therefore,
has been proposed that in the presence of silver ions, a porous sulfur the rate of the oxidation reaction (chalcopyrite leaching) must increase
layer forms on mineral particles instead of the deposition of a tenacious to generate electrons and compensate the electron consumption
and protective sulfur layer (Miller et al., 1981). In the work of Miller et (Tshilombo, 2004). Considerable variation has been reported in the
al., it has been suggested that, in the absence of silver ions, reaction semiconducting properties of natural pyrite which can be attributed
kinetics are strongly influenced by the formation of a protective to variations in its chemical composition (Abraitis et al., 2004). Pyrite
layer that inhibits the transport of reactants to the chalcopyrite lattice typically contains several minor and trace elements, such as Ag, As,
through the sulfur layer. Similar conclusions were drawn by Price et Au, Bi, Pb, Zn, and Mo. Minor and trace elements within the pyrite
lattice can significantly change the semiconducting properties of pyrite.
Chalcopyrite leaching is an electrochemical process involving the
⁎ Corresponding author. Tel.: + 1 604 822 0119. oxidation of sulfide to sulfur or sulfate and the reduction of ferric
E-mail address: [email protected] (G. Nazari). to ferrous; hence, the rate of chalcopyrite leaching depends on

0304-386X/$ – see front matter © 2011 Elsevier B.V. All rights reserved.
doi:10.1016/j.hydromet.2011.09.011
36 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45

electron transfer between anodic and cathodic sites located on the Pyrite was pretreated with silver according to the following proce-
mineral surface. Thus, any factor which increases the conductivity dure: 500 mL of solution containing the desired amount of silver,
of the mineral can improve the kinetics of the process (Ballester added as silver nitrate solution, was prepared. The solution was well
et al., 2007). Accordingly, in the Galvanox™ process, it has been mixed using a magnetic stirrer. 50 g of ground pyrite were added
noted that pyrite samples from different sources influence the and allowed to react with the silver until no silver was detected in
kinetics of chalcopyrite leaching differently. Recently, extensive the solution. The behavior of silver was studied by following the silver
research has been conducted to improve the catalytic properties of concentration in the aqueous phase before and after addition of pyrite
pyrite such that all pyrite samples accelerate the rate of copper at various time intervals. Silver content was determined by atomic
extraction from chalcopyrite regardless of the source of pyrite absorption spectroscopy. Pulp density was held at 10% to ensure a
samples (Nazari et al., 2011). It has been shown that the catalytic high degree of mixing by the magnetic stirrer in the glass beaker.
properties of pyrite can be improved by pretreating ground samples After treating the pyrite with silver ions, the solid residue was filtered
of natural pyrite with miniscule amounts of silver ions. and rinsed several times with water to wash any unadsorbed silver off of
In this study, the morphology and elemental compositions of the pyrite surfaces. The same procedure was followed for pretreatment
pyrite samples were analyzed after pretreatment with silver ions. of galena with silver.
It has been noted that silver could only be detected in association The leach reactor was filled with 1.5 L of solution with the required
with galena. In addition, it has been reported that the dissolution concentration of sulfuric acid, corresponding to 150% of the stoichio-
of chalcopyrite is favored in the presence of galena (Nova and metric requirement based on the following overall leach reaction:
Gonzalez, 2006). In their study, the electrochemical behavior of
0
pure chalcopyrite and chalcopyrite concentrate containing galena CuFeS2 þ O2 þ 2H2 SO4 ¼ CuSO4 þ FeSO4 þ 2H2 O þ 2S : ð1Þ
were compared and it was observed that the dissolution current
was significantly higher in the concentrate containing galena. The reactor was then sealed and the condenser, stirring motor and
Therefore, it was a subject of interest to examine the effect of galena oxygen tube were installed. Before adding the concentrate, the solution
on accelerating the rate of chalcopyrite leaching in both the absence was heated to the desired temperature using a recirculating water bath.
and presence of pyrite and silver in the leaching slurry. Based on the Ferrous and ferric salts (21 g total iron) were added after reaching the
detection of silver in galena, it was also important to determine desired temperature, and the agitation speed was set to 1200 rpm.
whether chalcopyrite oxidation could be accelerated by pretreating Before starting the leach test, the pH probe was calibrated using buffer
galena with silver ions. solutions at pH 1 and pH 4. The redox potential probe was also placed
In another study (Cruz et al., 2005), the galvanic effects of galena in a standard solution (470 mV vs. Ag/AgCl at 25 °C) to ensure that it
and pyrite have been investigated. Previously, electrochemical studies was working properly. Then, the copper concentrate and pyrite were
were carried out to analyze the reactivity of pyrite associated with added to the reactor. Slurry samples of approximately 1 mL were
galena. It has been indicated that galena has negative influences taken periodically for analysis. Samples were filtered and assayed for
on the electrochemical reactivity of pyrite. This behavior has been copper content by atomic absorption spectroscopy.
attributed to the lower rest potential of galena relative to the rest The feasibility of recycling pyrite for treating subsequent charges of
potential of pyrite (Cruz et al., 2005). For semiconductive and con- concentrate was also examined. In each of the tests, upon completion
ductive minerals, contact of different minerals with dissimilar rest of the first test, the supernatant solution was decanted from the
potentials in an oxidizing condition initiates the galvanic effect reactor while retaining the residue. Then, new solution containing
where the mineral with the higher rest potential acts as cathode the desired amount of sulfuric acid was added. This new solution
and the one with lower rest potential acts as anode, with oxidation was heated to 80 °C and then the desired amounts of ferric and
of the latter favored due to the flow of electrons from areas with ferrous sulfate and a new charge of fresh concentrate were added.
lower potential to those with higher potential. At the end of each test, the contents of the reactor were emptied to
a flask and filtered. The solid residue was collected for analysis by
multiacid digestion and induction coupled plasma (ICP) spectroscopy.
2. Experiments The dried residue was weighed, then coned and quartered to obtain a
representative sample for analysis. Solid assays were conducted by a
Batch leaching experiments were conducted in a sealed 2-L local commercial laboratory (Inspectorate, Richmond, BC).
jacketed glass reactor. The temperature was maintained at 80 °C XRD analysis was carried out on a Rigaku Rotaflex 200 diffractometer
with a circulating water bath. In a previous study (Dixon et al., using Cu Kα radiation at 40 kV and 20 mA, scanning from 10° to 90° (2θ)
2008), it has been shown that the optimum copper extraction was with the scanning rate of 0.02° (2θ).
achieved at 80 °C. The reactor was equipped with three baffles made In this study, a copper concentrate containing 27% copper, two pyrite
of 316 stainless steel and a six-bladed Rushton turbine impeller with a samples containing 97.6% and 99.99% pyrite from two different sources,
motor and speed controller manufactured by Applikon Dependable and pure galena (99.5%) were used. Mineralogical and elemental
Instruments (ADI). Impeller speed was maintained at 1200 rpm. compositions of the copper concentrate and pyrite samples are summa-
Each reactor was connected to a multi-channel digital controller rized in Tables 1 and 2, respectively. The copper concentrate was leached
(ADI 1030 Bio-controller). A pH probe, a redox potential probe and in the as-received condition. A Malvern Mastersizer was used to obtain
a thermocouple were connected to the controller and inserted into
the reactor. The outputs of these probes were recorded to a computer Table 1
from the controller. In each experiment, the solution potential was set Rietveld XRD analysis of copper concentrate and pyrite samples.
to a specific value. The controller was also equipped with two analog
Mineral Ideal formula Copper conc Pyrite #1 Pyrite #2
outputs. When the solution potential fell below the set point, an analog
(%) (%) (%)
signal was sent to a digital gas mass flow meter (Aalborg GFCS), upon
Pyrite FeS2 15.9 97.6 99.99
which oxygen from a cylinder flowed into the reactor through a sparger
Chalcopyrite CuFeS2 78 – –
until the potential set point was reestablished. The rate of oxygen flow Quartz SiO2 1 0.6 –
decreased as the potential approached the set point. Each reactor was Biotite K(Mg,Fe2+)3AlSi3O10(OH)2 1.8 – –
also equipped with a condenser, which allowed excess oxygen to exit Dolomite CaMg(CO3)2 1.1 – –
while condensing the associated water vapor and returning it to the Plagioclase NaAlSi3O8–CaAl2Si2O8 2.2 – –
Anhydrite CaSO4 – 1.8 –
reactor.
 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45 37

Table 2 100%
Elemental analysis of copper concentrate and pyrite samples.

Element Copper conc Pyrite #1 Pyrite #2 80%

Copper Extraction
Cu 27.00% 0.13% 44 ppm
Fe 31.14% 45.43% 46.51%
S 36.70% 52.62% 53.40% 60%
Mg 0.27% 0.04% –
Co 0.16% – 20 ppm 1
Pb – 0.14% b2 ppm 40%
As 130 ppm – 6 ppm
Ag 15.5 ppm 21 ppm 1.4 ppm
Ca 0.47% 0.56% 0.03% 20%
Al 0.51% 0.02% –
Zn 0.01% – 159 ppm
Si 1.14% 0.28% – 0%
0 50 100 150 200 250
Time (h)

Fig. 1. Chalcopyrite leaching in ferric sulfate media at a potential set point of 450 mV
particle size distributions of the samples. The copper concentrate and
and 80 °C (T1).
galena were not ultrafine, with an 80%-mass-passing size (P80) of
46 μm and 51 μm. The pyrite particles were considerably larger, with
a P80 of 290 μm, giving the consistency of fine sand. of the silver from solution in just a few minutes. Leaching experiments
were conducted at a pyrite-to-chalcopyrite ratio of 2, a silver-to-pyrite
3. Results and discussion ratio of 100 ppm, and a solution potential set point of 450 mV (T6 and
T8). The effectiveness of recycling pyrite was also examined (T7 and
A number of experiments were conducted in order to evaluate the T9). In the recycle tests, solid residues from the previous tests were
effects of addition of silver-enhanced pyrite with and without galena recycled with fresh charges of copper concentrate and an additional
on the kinetics of chalcopyrite leaching. Table 3 presents a matrix, 10% of the silver-enhanced pyrite (17.5 g) to make up for any silver
containing the experimental conditions of all the tests. and pyrite lost during the first experiments. All results are presented
The first test was conducted in order to observe the rate of copper in Fig. 2.
extraction in ferric/ferrous sulfate solution at 450 mV (all redox Obviously, a dramatic improvement in the leaching kinetics of
potentials are reported vs the KCl-saturated Ag/AgCl reference chalcopyrite was observed as a result of pretreating pyrite with minor
electrode) in the absence of added pyrite. The solution potential amounts of silver ions. The morphology and elemental composition of
set point of 450 mV was selected based on a previous study pyrite after pretreatment with silver ions were studied using a Hitachi
which showed this provided the maximum copper extraction. S-3000N Scanning Electron Microscope (SEM). Energy Dispersive
Very slow kinetics and incomplete copper extraction under these X-Ray spectroscopy (EDX) was used to determine the chemical compo-
conditions were observed as shown in Fig. 1. sition of samples. The main purpose of this analysis was to detect silver
Two tests were conducted to examine the effect of adding two on pyrite samples.
pyrite samples on the kinetics of chalcopyrite leaching. Upon com- According to the EDX analysis, shown in Fig. 3(b) and (c), the
pletion of the first tests, recycle tests were conducted to examine detected silver was mostly associated with lead. Silver was not
the effectiveness of recycled pyrite. As shown in Fig. 2, both added detected on pyrite #2 which had a very low amount of lead (Fig. 4).
pyrite samples accelerated the rate and extent of copper extraction, It is important to note that the concentration of silver on the pyrite
but relatively long leach times were still required. sample was very low (100 ppm) and this value is lower than the
In order to enhance the catalytic properties of pyrite, samples detection limit of EDX. Hence, silver could only be detected on
were pretreated with silver ions. The finely divided pyrite adsorbed all those areas where the silver concentration was higher than 1% and

Table 3
Experimental conditions.

Test ID Cu concentrate mass Pyrite mass Galena associated with Py Galena mass Ag concentration of pyrite Ag (g)/kg Cu Comment
(g) (g) (g) (g) (ppm)

T1 105 0 0 0 0 0
T2 105 175 0.283 0 0 0
T3 105 17.5 0.0283 0 0 0 Used residue from T2
T4 105 175 0 0 0 0
T5 105 17.5 0 0 0 0 Used residue from T4
T6 105 175 0.283 0 100 0.61
T7 105 17.5 0.0283 0 – 0.061 Used residue from T6
T8 105 175 0 0 100 0.61
T9 105 17.5 0 0 – 0.061 Used residue from T8
T10 105 0 0 0.283 0 0
T11 105 0 0 81.88 0 0
T12 105 0 0 0.283 0 0.61
T13 105 0 0 0.0283 – 0.061 Used residue from T12
T14 105 0 0 0 0 0.51 14.5 g silver were added
T15 105 0 0 0 0 0.051 Used residue from T14
T16 105 175 0 2.26 – 0.61
T17 105 17.5 0 0.226 – 0.061 Used residue from T14
T18 105 0 0 0 0 0 Added 5 mg silver after 140 h
T19 105 0 0 0 0 0.61
38 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45

100%
a
80%
Copper Extraction

60%

40%
Pyrite #1, Ag/Py = 100 ppm, Ag = 0.61 g/kg Cu (T6)
Pyrite #2, Ag/Py = 100 ppm, Ag = 0.61 g/kg Cu (T8)
Pyrite #1, Py Recycle (T7)
20% Pyrite #2, Py Recycle (T9)
Pyrite # 1 (T2)
Pyrite #2 (T4)
Pyrite #1, Py Recycle (T3)
Pyrite # 2, Py Recycle (T5)
0%
0 20 40 60 80 100 120
Time (h)

Fig. 2. Effect of addition of pyrite (T2 and T4), silver-enhanced pyrite at a silver-to-
pyrite ratio of 100 ppm (T6 and T8), and the recycled pyrite (T3, T5, T7, and T9) on copper
extraction using two different pyrite samples at a potential set point of 450 mV and 80 °C.
b
this cannot occur if the silver is uniformly dispersed. As shown in
Fig. 4, no silver was detected on pyrite #2 which can be attributed
to the homogenous distribution of silver on pyrite.
It might be hypothesized that when a pyrite sample includes some
amount of lead mineral, silver is mostly adsorbed to the lead mineral
rather than pyrite. Hence, it was important to examine the effects of
galena with and without added silver on the kinetics of chalcopyrite
leaching.
Two experiments were conducted to study the effects of galena at
two different concentrations. The amount of galena associated with py-
rite #1 was obtained and corresponded to 0.283 g ([239.26 (g/mol) /
207.2 (g/mol) × 0.0014 g/ g × 175 g]) at a pyrite-to-chalcopyrite ratio
of 2. Then, the same amount of galena was added but with no pyrite
(T10). Another test was also conducted at a higher ratio of galena to
chalcopyrite; specifically, a galena-to-chalcopyrite ratio of 1 (T11). The
results, shown in Fig. 5, clearly indicate that galena has no effect on
the kinetics of chalcopyrite leaching. c
Elements Concentration (wt%)
As mentioned above, when galena is present in pyrite samples, it
Carbon 49.56
has been observed that silver is preferentially adsorbed on galena
Oxygen 11.81
instead of pyrite. In one experiment, the same amount of galena
Sulfur 8.60
that was present in pyrite #1 with the same amount of added silver
Iron 3.87
was introduced into the reactor (without pyrite) (T12). After pretreating
Silver 2.17
galena with silver for 30 min, a charge of copper concentrate was added.
Upon completion of the first test, the residue was collected and recycled Lead 23.99
into the subsequent test to recover copper from a new charge of copper
Fig. 3. (a) SEM micrographs, (b) EDX maps, and (c) elemental analyses of pyrite #1
concentrate (T13). The results are shown in Fig. 6 and indicate that the pretreated with silver at a silver-to-pyrite ratio of 100 ppm.
rate of copper extraction has been accelerated by the addition of silver.
However, the copper extraction in the presence of the recycled residue
was considerably slower than the first test, indicating that silver in the 3.1. Interaction of silver with galena
leaching residue does not maintain its catalytic properties. The results
of recycling the residue in Fig. 6 shows that after about 40 h, the rate In order to understand the effect of added silver and galena on the
of reaction gradually increases. Silver mainly remains in the residue in rate of leaching, the rate and extent of the interaction of silver with
the form of Ag2S particles embedded in elemental sulfur. This silver galena were examined. 2 g of galena were pretreated with silver
cannot be recycled directly; hence it does not maintain its catalytic in solutions containing silver in its soluble form at different silver
properties. The EDX analysis of the residue also showed the presence concentrations. In this experiment, silver could either exist in the
of silver on lead mineral (mostly anglesite). The acceleration of the rate solution or on galena samples. Hence, the silver concentration on
of chalcopyrite leaching after 40 h is attributed to the gradual dissolution galena was determined by following and analyzing the silver concentra-
and release of silver ions from lead mineral to the solution. This would tion in the aqueous phase at various time intervals as described earlier.
increase the availability of silver ions in the solution which would also Galena was added 1 s after starting the experiment (i.e. at time t = 0,
enhance their catalytic properties. It is also important to note that unlike galena had not yet been introduced to the system). Given these condi-
recycling the pyrite residue, recycling the lead residue is not a tions, [Ag]t / [Ag]0 = 1 at the beginning of the experiment where [Ag]0
convenient process step. Due to the reaction of galena with sulfuric and [Ag]t represent the initial and instantaneous silver concentrations
acid in the oxidizing condition of the experiment, fine particles of in solution, respectively. The results are shown in Fig. 7.
anglesite are formed. Separation of these fine particles from the Fig. 7 shows very rapid interaction of silver ions with galena and
chalcopyrite residue (mainly sulfur) and recycling them to the indicates a high affinity for silver adsorption. After 1 min at initial silver
subsequent test cannot be achieved conveniently. concentrations of 100 ppm and 1000 ppm, almost no silver was
 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45 39

100%
a
80%

Copper Extraction
60%

40%

Galena = 0.283 g, 0.61 g Ag/ kg Cu T(12)

20%
Silver = 14.5 mg, No Galena (T14)
Residue T12 Recycle (T13)
Residue T14 Recycle (T15)
0%
0 20 40 60 80 100 120
Time (h)

Fig. 6. Effect of silver-pretreated galena (T12), silver (T14), recycled galena (T13), and
recycled silver residue (T15) at a potential set point of 450 mV and 80 °C.

b detected in the solution. At 5000 ppm, complete adsorption of silver

onto galena occurred after about 30 min. At 10,000 ppm, adsorption
was incomplete even after 30 min.
[Ag]t / [Ag]0 attained values of 16.44% and 54.42% after 1 min at initial
silver concentrations of 5000 ppm and 10,000 ppm, respectively.
Assuming homogeneous distribution of silver on galena, these values
are equivalent to silver concentrations of 4178 ppm (5000 × [100%−
16.44%]) and 4558 ppm (10,000 × [100% − 54.42%]), suggesting that
this particular galena sample adsorbed silver to a concentration of
roughly 4600 ppm very rapidly (in less than 1 min).
In the experiment shown in Fig. 6 (T12), 0.283 g of galena were
pretreated with 17.5 mg silver and after 30 min copper concentrate
was added. This pretreatment scenario was investigated separately,
with solution samples taken at various time intervals. The results
are shown in Fig. 8. The results indicate that in the experiment with
0.283 g galena, [Ag]t / [Ag]0 is 92.64% after 1 min. This is equivalent
to a silver concentration of 4551 ppm ([17.5 mg/0.283 g] × 1000 g/kg ×
[100% − 92.64%]) on galena. This concentration increased to
10,593 ppm ([17.5 mg/0.283 g] × 1000 g/kg× [100 − 82.87%]) and then
became constant. This value probably represents the maximum amount
of silver that can be adsorbed onto the galena. Therefore, 14.5 mg
c (82.87% × 17.5 mg) of the added silver were still dissolved in the solu-
tion at the beginning of the leach test (T12) shown in Fig. 6.
Elements Concentration (wt%)
Another experiment was conducted and 14.5 mg of silver was
Sulfur 51.49 added in the absence of galena (T14). After completion of the first
Iron 48.51 test, the residue was recycled (T15). The results are shown in Fig. 6.
The results indicate that the rate of copper extraction in experiment
Fig. 4. (a) SEM micrograph (b) EDX map (c) elemental analysis of pyrite #2 pretreated T12 and T14 are almost identical.
with silver at a silver-to-pyrite ratio of 100 ppm.

100%
100%
10,000 ppm

80% 5,000 ppm

80%
Copper Extraction

1,000 ppm

60% 100 ppm

[Ag]t /[Ag]0

60%

40%
40%

20%
Galena = 0.283 g, Galena/Cp = 0.0034 (T10) 20%
Galena = 81.88 g, Galena/Cp = 1 (T11)
0%
0 20 40 60 80 100 120 140 0%
Time (hour) 0 5 10 15 20 25 30
Time (min)
Fig. 5. Effect of galena addition on copper extraction at two different galena to chalcopyrite
ratios of 0.0034 (T10) and 1 (T11) at a potential set point of 450 mV and 80 °C. Fig. 7. Rate of interaction of silver ions with galena at various silver concentrations.
40 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45

100%
Considering this analysis and the results of adding silver in the
absence of galena in test T14, clearly, the increased rate of chalcopyrite
80% leaching in the presence of galena and silver in test T12 is due to the
direct catalytic effect of silver ions on the rate of chalcopyrite leaching.
Therefore, unlike pyrite, galena samples pretreated with silver ions
[Ag]t /[Ag]0

60% have no beneficial effect on the kinetics of chalcopyrite leaching.

The rapid interaction of silver with galena observed in this study is
40% in agreement with previous studies by Scaini et al. (1995, 1997), who
report the rapid interaction of silver ions with galena to form metallic
Ag 0 and Ag2S according to Reactions 2 and 3:
20%
þ 2þ
PbS þ 2Ag ¼ Ag2 S þ Pb ð2Þ
0%
0 5 10 15 20 25 30 þ 2þ 0 2− þ
2PbS þ 10Ag þ 4H2 O ¼ 2Pb þ Ag2 S þ 8Ag þ SO4 þ 8H : ð3Þ
Time (min)

Fig. 8. Rate of interaction of 17.5 mg silver ions with 0.283 g galena. The morphology and elemental compositions of the leach residues
were analyzed. Samples mounted in epoxy were polished with
1200 grit SiC (silicon carbide) and rinsed with water to reveal cross

c
Elements Concentration (wt%) Elements Concentration (wt%)
Carbon 37.45 Carbon 38.43
Oxygen 21.55 Oxygen 17.09
Sulfur 8.23 Sulfur 8.52
Silver 1.67 Silver 3.53
Lead 31.11 Lead 32.43

Fig. 9. (a) SEM micrographs (b) EDX maps (c) elemental analyses of completely leached chalcopyrite in the presence of galena and silver (T12).
 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45 41

100%
sections. Fig. 9 shows the morphology of chalcopyrite residue and
galena after leaching (T12). The results shown in these micrographs
indicate the preferential adsorption of silver onto the lead compound 80%

Copper Extraction
(mostly anglesite) rather than the sulfur residue.
In addition, X-Ray Diffraction (XRD) analysis was performed on
the solid residue of reacted chalcopyrite in the presence of galena 60%
(T11). The diffraction pattern was compared with the XRD of the
galena samples used in these experiments. The results are shown 40%
in Fig. 10.
The XRD pattern shown in Fig. 10(b) reveals several new peaks.
These peaks (denoted “X”) match well with anglesite (lead sulfate). 20%
Galena = 2.26 g, Py/Cp = 2, Ag = 0.61 g/Kg Cu (T16)
None of the galena peaks, presented in Fig. 10(a), were observed on
Residue recycle T(17)
the XRD pattern of the residue after the leaching experiment. This 0%
analysis indicates that due to the oxidizing condition of the experiment, 0 5 10 15 20 25 30 35
galena was transformed into anglesite according to the following Time (h)
reaction:
Fig. 11. Effect of silver-pretreated pyrite and galena (T16) on copper extraction and
0
recycled pyrite and galena (T17) at a potential set point of 450 mV and 80 °C.
PbS þ Fe2 ðSO4 Þ3 ¼ PbSO4 þ S þ 2FeSO4 : ð4Þ

This reaction for the dissolution of galena in acidic iron sulfate (8 times higher) than was naturally present (0.14%) in pyrite #1
solutions in the range of 80–110 °C was proposed in a study by Markovich (T16). The results, shown in Fig. 11, indicate the slower rate of reaction
and Ptitsyn (1998). The XRD pattern also displays the characteristic in the presence of galena. As explained earlier, silver is preferentially
reflections of chalcopyrite and sulfur (S8). adsorbed to galena rather than to pyrite. Galena has no catalytic effect
In addition, the pH of the solution in experiment T11 was followed on chalcopyrite oxidation, as already established. Hence, the reason
and a dramatic increase was noted. Since oxidation of chalcopyrite for the slower kinetics in T16 and T17 than T6 and T7, respectively,
was slow, this increase in pH is attributed to the oxidation of galena may be attributed to the adsorption of some silver ions to galena rather
to anglesite. This observation is in agreement with the XRD analysis. than pyrite. Fig. 11 shows that the total leach time in the recycle test
was similar to the first test, indicating that the silver-enhanced pyrite
maintained its catalytic properties.
3.2. The catalytic effects of galena in the presence of pyrite and silver
3.3. Interaction of galena and pyrite with silver ions
An experiment was conducted to examine the effect of galena in
the presence of pyrite and silver. In this experiment, pyrite was In order to examine our hypothesis regarding adsorption of a
added at a pyrite-to-chalcopyrite ratio of 2 and a silver-to-pyrite lower amount of silver onto pyrite in the presence of galena, a new
ratio of 100 ppm (similar to tests T6 and T7). To highlight the effect set of experiments was designed. In the previous experiment shown
of galena on the kinetics, galena was added at a higher concentration in Fig. 11, after preparing the desired silver solution, galena and pyrite

X: Anglesite (lead Sulfate)

Cp: Chalcopyrite
S8: Sulfur
X
X
X

X Cp
X

b X
X
X X X

X X
X X Cp X X X
X S8 S8
X Cp Cp X X X X
S X X X X X X X X X X X X X
X S S X X Cp S8 X X X
Cp

10 20 30 40 50 60 70 80 90
2θ (°)

Fig. 10. XRD patterns of (a) the galena sample and (b) reacted chalcopyrite concentrate (T11).
42 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45

100%
Galena = 2.27 g, Ag =17.5 mg
and Portillo, 1979; Price et al., 1986), it has been stated that in the
absence of catalysts, an impermeable sulfur layer forms on the
Pyrite = 175 g, Ag =17.5 mg
80% surface of chalcopyrite and inhibits the diffusion of reactants to the sur-
face of chalcopyrite. These studies also indicate that the morphology of
the sulfur layer is modified in the presence of catalysts such as silver
[Ag]t /[Ag]0

60% ions (Ahonen and Touvinen, 1990; Cordoba et al., 2008; Romero et al.,
1998; Sukla et al., 1990). The higher rate of copper extraction has there-
40% fore been attributed to the formation of a porous and non-protective
sulfur layer which allows the diffusion of reactants to the chalcopyrite
core.
20% In order to compare the morphology of partially leached chalcopyrite
particles in the absence and presence of catalysts, 105 g of copper
concentrate were leached in the absence of catalysts. It was observed
0%
0 5 10 15 20 25 30 that after 140 h, chalcopyrite leaching proceeded very slowly, as
Time (min) expected. 5 mg of silver ions were added to the system after 140 h
(T18). The results are shown in Fig. 13. A rapid increase in the rate
Fig. 12. Rate of interaction of 17.5 mg silver ions with 2.27 g galena and 175 g pyrite. of chalcopyrite leaching was observed after 140 h, when the silver
ions were introduced to the leaching reactor.
were added simultaneously. Pretreament continued for 30 min and Samples were taken after 140 h (before adding the silver) and
samples were taken at various time intervals. The silver concentrations after 165 h (after complete copper extraction). Samples were studied
of samples were determined by atomic adsorption spectroscopy. by SEM and the results are shown in Figs. 14 and 15. Fig. 14 shows the
Although galena and pyrite were pretreated with silver for 30 min morphology of partially leached chalcopyrite particles in test T18
before introducing the chalcopyrite concentrate, no silver was after 140 h before introducing silver ions to the leach solution.
detected in the solution after 1 min. In another experiment, 175 g Fig. 14(a) shows the formation of a thin non-porous sulfur layer
of pyrite was added to the same silver solution and the silver concen- around chalcopyrite particles. Fig. 14(b) presents the thicker sulfur
tration was followed. The same experiment was repeated with 2.26 g layer around chalcopyrite particles. Fig. 14(b) clearly shows the porosity
galena (8 × 0.283 g galena). The results are shown in Fig. 12. of the sulfur layer in both cases. However, it is interesting to note that in
This analysis also confirms that in the presence of pyrite, the silver
concentration of the solution reached zero after 1 min. The silver con-
centration on galena after 1 min was 4533 ppm. It was shown above
that this particular galena sample attains a silver concentration of
roughly 4600 ppm during the first minute of its interaction with silver.
a
Since the rest potential of galena is lower than that of pyrite, silver
reacts with galena preferentially. Therefore, the silver concentration Sulfur
of galena increases to about 4533 ppm (17.5 mg / 2.27 g × 1000 g/
kg × [100% − 41.19%]). The reaction of silver with pyrite is also
rapid so that unreacted silver ions quickly react with pyrite. According
to this analysis, the concentration of silver on pyrite was about 41 ppm
([41.19% × 17.5 mg] / 175 g). The silver concentration of pyrite was Chalcopyrite
100 ppm in the absence of galena. This analysis further confirms our
hypothesis that the rate of reaction in tests T16 and T17, shown in
Fig. 11, is slower in the presence of galena due to the reaction of
some amount of silver with galena rather than pyrite.

3.4. Morphology

The morphology of chalcopyrite samples after leaching under

different conditions was studied using SEM. In previous studies (Miller b
100%

80%
Copper Extraction

60%
Chalcopyrite
40%

Sulfur
20%

0%
0 20 40 60 80 100 120 140 160 180
Time (h)
Fig. 14. SEM micrographs of chalcopyrite particles partially leached in the absence of
Fig. 13. Effect of adding silver after chalcopyrite passivation at a potential set point of catalysts, test T18 after 140 h, cross-sectioned and epoxy mounted, covered by (a) a
450 mV and 80 °C (T18). thin non-porous and (b) a thick porous sulfur layer.
 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45 43

100%
a
80%

Copper Extraction
Sulfur
60%

40%
Chalcopyrite

20%

0%
0 10 20 30 40 50
Time (h)

Fig. 16. Effect of adding silver on chalcopyrite leaching at a potential set point of
450 mV and 80 °C (T19).

b clearly show that the morphology of the sulfur layer is independent of

the presence or absence of catalysts. In Fig. 17(a) and (b), relatively
non-porous and relatively porous sulfur layers are shown, respectively,
even though all particles were leached under the same conditions.
SEM micrographs of chalcopyrite residues leached in the presence
of galena are also presented in Fig. 18. These images again show that
relatively porous and non-porous sulfur layers can be formed around
Sulfur chalcopyrite particles regardless of the presence or absence of

Chalcopyrite
Fig. 15. SEM micrographs of chalcopyrite particles leached in the presence of silver as a
catalyst, test T18 after 165 h, cross-sectioned and epoxy mounted, covered by (a) a thin
non-porous, and (b) a thick porous sulfur layer.

Chalcopyrite
spite of the formation of a porous layer on the surface of chalcopyrite,
the leaching reaction had ceased. Sulfur
Fig. 15 shows the morphology of chalcopyrite in test T18 after
165 h. Comparing Figs. 14 and 15, it can be concluded that the
morphology of sulfur layers on the surface of chalcopyrite is similar
in the absence and the presence of the catalyst. In Fig. 15(a), one
might report a non-porous protective sulfur layer; while in fact,
b
this observation can be attributed to the formation of a thin layer.
Due to the low copper and iron dissolution of this chalcopyrite
particle, the sulfur layer is not thick enough to reveal the dendritic
shape of the interstitial regions between the sulfur layers and if
the leaching had proceeded further, it might have been seen as a
porous layer. In addition, the sulfur layer was not observed on two
sides of the particle shown in Fig. 15(a). A review of the literature
reveals that the formation of localized sulfur layer has been
Chalcopyrite Sulfur
reported in previous studies (Biegler and Swift, 1979; Jones and
Peters, 1976; Venkatachalam, 1991). However, samples were
mounted and polished, hence there is a possibility of destruction
of this layer during polishing.
Fig. 16 shows the rate of copper extraction in the silver catalyzed
leaching process at 450 mV and 80 °C. In this experiment, 0.61 g Ag/kg
Cu was added (T19). The results show that although silver accelerated
the rate of copper recovery, with the same amount of silver, the rate
Fig. 17. SEM micrographs of chalcopyrite particles leached in the presence of silver, test
was significantly slower in the absence of pyrite (T6 and T8). T19, cross-sectioned and epoxy mounted, covered by (a) a thin non-porous, and (b) a
SEM micrographs of samples from this test are shown in Fig. 17, which thick porous sulfur layer.
44 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45

a a

Sulfur

Chalcopyrite
Sulfur

Chalcopyrite

b b

Chalcopyrite
Sulfur

Sulfur Chalcopyrite

Fig. 18. SEM micrographs of chalcopyrite particles leached in the presence of galena, test Fig. 19. SEM micrographs of non-polished partially leached chalcopyrite particles from
T10 after 140 h, cross-sectioned and epoxy mounted, covered by (a) a thin non-porous, (a) test T18, and (b) test T10 after 140 h.
and (b) a thick porous inner and a non-porous outer sulfur layer.

catalysts. Fig. 18(b) clearly shows that the outer layer of the sulfur layer. Conversely, in the presence of catalysts, the extents
chalcopyrite particle is completely non-porous, but due to the of chalcopyrite dissolution are considerably higher which leads to
progress of copper extraction through inner layers, the formation the formation of a thicker sulfur layer. Hence, the porous structure
of a porous sulfur structure is observed. can be clearly observed.
SEM micrographs of samples of partially leached chalcopyrite
particles in the absence of catalysts and the presence of galena are
shown in Fig. 19(a) and (b), respectively. To avoid destruction of 4. Conclusions
the sulfur layer around the particles, SEM samples were prepared
without mounting or polishing. This figure shows that leaching of In this study, the influences of galena and pyrite on the rate of
chalcopyrite occurs along preferential directions. This observation chalcopyrite leaching have been investigated. Pyrite and galena
is in agreement with previous studies (Biegler and Swift, 1979; samples were pretreated with silver ions. It has been noted that in
Jones and Peters, 1976; Venkatachalam, 1991). the presence of both pyrite and galena, silver reacts with galena
Fig. 20 shows the SEM micrographs of non-polished leached preferentially. However, galena pretreated with silver does not enhance
chalcopyrite particles in the presence of silver, from test T19. Particles the kinetics of chalcopyrite leaching, whereas silver ions, pyrite, and
shown in Fig. 20(a) have been completely leached from all sides while pyrite pretreated with silver ions all accelerate the rate of chalcopyrite
in Fig. 20(b), almost pure elemental sulfur was observed at some leaching significantly. The process of using silver to accelerate copper
surfaces and clean, unleached chalcopyrite was observed at other extraction is costly unless silver can be efficiently recovered from the
surfaces. Fig. 20 also validates our previous observation that leaching residue and recycled. In this study, it has been shown that direct recycle
of chalcopyrite occurs in preferential directions. of the silver catalyst is not feasible; however, silver-enhanced pyrite can
It has been observed that, under leaching conditions described be efficiently recycled to subsequent tests.
earlier, both porous and non-porous sulfur layers form on the SEM and EDX techniques were applied to study the morphology and
surfaces of chalcopyrite regardless of the absence or presence of elemental composition of residues after completion of experiments. The
silver catalyst. The observation of only a non-porous sulfur layer in the results indicate that both porous and non-porous layers form on
absence of catalysts, reported in previous studies, can be attributed to the surface of chalcopyrite regardless of the presence or absence
low copper extraction under this condition which leads to the of catalysts. Hence, acceleration of the rate of chalcopyrite leaching
formation of only a thin sulfur layer on the surface of chalcopyrite. in the presence of catalysts is not due to the alteration of morphology
However, continued leaching leads to the formation of a porous of sulfur layers around chalcopyrite particles.
 G. Nazari et al. / Hydrometallurgy 111-112 (2012) 35–45 45

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Engineering Research Council of Canada (NSERC) (Idea-to-Innovation SEM, and electrochemistry. Geochim. Cosmochim. Acta 59, 2733–2747.
Grant I2IPJ 350268-07). Scaini, M.J., Bancroft, G.M., Knipe, S.W., 1997. An XPS, AES, and SEM study of the
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