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leaching solutions
V. Reyes-Cruz, C. Ponce-de-Leon, I. Gonzalez
*
, M.T. Oropeza
Departamento de Qu mica, Universidad Autonoma Metropolitana-Iztapalapa, Apdo. Postal 55-534, C.P. 09340 Mexico D.F., Mexico
Received 20 March 2001; received in revised form 14 November 2001; accepted 4 June 2002
Abstract
A systematic voltammetric study developed in this work allows the determination of the potential range at which the
selective deposition of gold and silver is carried out in the presence of a high content of copper. As a first approach, laboratory
solutions prepared with a high content of cyanide and copper and low values of gold and silver are used; later, the methodology
is applied to leaching solutions of industrial origin.
The chemical speciation and microelectrolysis studies showed that copper deposition occurs at more negative potentials than
deposition of gold and silver. Also, the voltammetric study of a cyanide solution containing low concentrations of Au(I) and
Ag(I), free of and with high concentration of Cu(I) was carried out. The study shows the potential range at which Au(I) and
Ag(I) are reduced despite the high concentration of the Cu(I) ions. The deposition of gold and silver was not interfered with by
the high concentration of Cu(I) ions when the leaching solution was electrolyzed in a laboratory electrochemical reactor FM01-
LC with a reticulated vitreous carbon (RVC) cathode.
D 2002 Elsevier Science B.V. All rights reserved.
Keywords: Silver cyanide; Gold cyanide; Copper cyanide; Electrochemical recovery; Cyanide leaching; RVC electrode; Electrodeposition
1. Introduction
Cyanide leaching processes have been used by the
mining industry for over 100 years in the extraction of
noble metals (Kordosky et al., 1992; Fleming, 1992).
Minerals from which most of the noble metals are
obtained are increasingly poorer (gold and silver
concentrations in the order of 15 ppm), so the
leaching solutions from these processes do contain
Au(I), Ag(I) and Cu(I), with copper in concentrations
typically over a hundred times higher than the other
two metals. This high concentration of Cu(I) might
interfere during the selective recovery of gold and
silver (Jha, 1984), and the use of ion exchange resins
or activated carbon to remove the Cu(I) ion is often
necessary to obtain a concentrated solution of Au(I)
and Ag(I). The following stage after the removal of
interfering ions is the recovery of noble metals. Two
traditional methods have been used: cementation and
electrolysis (Fleming, 1992; Jha, 1984). The electrol-
ysis method has been used in concentrated solutions
in electrochemical reactors with plane electrodes (e.g.
electrodeposition of copper or zinc); however, with
dilute solutions, the efficiency is low (Jha, 1984;
Reyes, 1998). Works reported in the literature have
shown that the high surface area found in porous
0304-386X/02/$ - see front matter D 2002 Elsevier Science B.V. All rights reserved.
PII: S0304- 386X( 02) 00083- X
*
Corresponding author. Fax: +52-5804-4666.
E-mail address: igm@xanum.uam.mx (I. Gonzalez).
www.elsevier.com/locate/hydromet
Hydrometallurgy 65 (2002) 187203
electrodes increases the efficiency when used with
diluted solutions (Bennion and Newman, 1972;
Coeuret, 1976; Coeuret et al., 1976; Trainham and
Newman, 1977; Olive and Lacoste, 1980; Coeuret and
Storck, 1981). Most gold plants actually use stainless
steel wool as cathode. The recovery of Au(I) and
Ag(I) at concentrations between 11 and 30 ppm has
been recently studied (Waterman et al., 1984; Reyes et
al., 2002; Stavart et al., 1999). However, the recovery
of Au(I) and Ag(I) from solutions containing high
concentration of Cu(I) in cyanide solutions has
received less attention.
Since the metal with the highest concentration
would be expected to be the first deposited, the
presence of large amounts of Cu(I) is likely to
influence the selective recovery of gold or silver.
Preliminary studies performed on stainless steel 304,
vitreous carbon and Ti showed that vitreous carbon is
the most adequate material for performing Ag(I)
deposition from a diluted silver solution (11 ppm)
with a high content of copper (Reyes, 1998).
The solution used in this preliminary study (0.1
M Cu(I), 0.5 M CN
and 10
4
M Ag(I)) differs
significantly from the solutions from industrial
leaching processes with cyanides; nevertheless, the
conditions of high copper and cyanide concentra-
tions allowed the realization of an electrochemical
study on a vitreous carbon electrode where the
recovery of silver was shown to be possible without
the deposition of copper, despite the fact that the
concentration of Cu(I) was 100 times higher than the
concentration of silver (Reyes et al., 2002). The
study showed that the Cu(I) deposited at potentials
more negative than Ag(I) and that the cyanide
species of Cu(I) modified the capacitive current
densities of the media (CN
), making favorable
the deposition of silver. On the other hand, in this
study, a systematic methodology is established to
determine the potential range at which the selective
silver deposition takes place. For that reason, it
confronts the problem of faradaic current density
response from the reduction process of a low silver
concentration (11 ppm) masked by the capacitive
current of cyanide. Thus, a part of information of a
previously performed study (Reyes et al., 2002) is
taken up again and the same methodology is applied
in order to study the model solutions containing (a)
Au(I) and (b) Au(I) with Ag(I) in the presence and
absence of Cu(I) (laboratory solutions). This allows
later analysis validation of the results obtained in the
study of an industrial leaching solution containing
low concentrations of copper and cyanide and much
lower concentrations of noble metals (of the order of
15 ppm).
Firstly, speciation and voltammetric studies of a
cyanide solution with a high concentration of Cu(I)
and low concentrations of Au(I) (laboratory solution)
were carried out. The purpose of this study was to find
out whether the high concentration of copper inter-
feres with the selective deposition of gold. After this
experiment, a voltammetric study of the cyanide
solution containing the three metallic ions (high
Cu(I) concentration and low concentrations of Au(I)
and Ag(I), laboratory solutions), was carried out in
order to determine if the interaction between the three
metal ions changes the potential range at which the
selective reduction of Au(I) and Ag(I) occurs. After-
wards, the same methodology was applied to the
industrial leaching solution.
Once the potential range of the Au(I) and Ag(I)
reduction was established, an electrolysis of the cya-
nide leaching solution containing the three metallic
ions was carried out in an electrochemical FM01-LC
laboratory reactor.
2. Experimental
A 100-ml Pyrex cell with a three-electrode system
and nitrogen inlet was used in the voltammetric study.
The working electrode was a vitreous carbon rod with
geometric area of 0.07 cm
2
. The electrode surface was
polished with 0.3-Am alumina powder/water and
rinsed with deionised water followed by ultrasonic
bath for 5 min to remove traces of alumina, grease and
a final rinse with deionised water. The reference and
counter electrodes were saturated calomel and graph-
ite, respectively. The solutions were:
Laboratory solutions for methodology validation
(a) Cyanide solution 0.5 M KCN
(b) Cyanide solution
of Cu(I)
0.1 M CuCN and
0.5 M KCN
(c) Cyanide solution
of Au(I)
10
4
M KAuCN
2
and
0.5 M KCN
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 188
All solutions except the industrial leaching solution
were prepared with deionised water 18 MV
1
cm
1
and analytical grade reagents. The pH was held
constant at 10 for laboratory solutions and the solu-
tions were deoxygenated with nitrogen for 10 min
prior to cyclic voltammetry experiments. A flux of
nitrogen previously saturated in a CN
solution was
held on the surface of the solution during the experi-
ments without disturbing the electrolyte.
The electrolysis of the selective reduction of Au(I)
and Ag(I) in the presence of high concentrations of
Cu(I) was carried out using an industrial leaching
solution on a filter press electrochemical reactor,
FM01-LC. A full description of this reactor has been
outlined in the literature (Brown and Plecher, 1992;
Brown and Plecher, 1993; Brown and Plecher, 1994).
A cationic NafionR membrane NX550 divided the
anodic and cathodic reactor compartments. The cath-
ode used was a reticulated vitreous carbon (RVC)
electrode with 60 pores per inch (ppi), filling a
volume of 31 cm
3
(Electrosynthesis). Copper plates
glued by conductive carbon paste made the electrical
contact with the RVC electrode. The anode was an
A304 stainless steel plate.
The industrial solution was re-circulated through
the anolyte and catholyte compartments using two
centrifugal pumps obtained from Cole Palmer. A
potentiostat EG and G model PARC 273A with a
Booster KEPCO (020 A and 020 V) and the M270
software were used in the voltammetric and macro-
electrolysis experiments. The determination of total
Au(I), Ag(I) and Cu(I) concentrations was carried out
by atomic absorption spectroscopy (AAS) (Varian
model Spectr AA-20).
3. Results and discussion
3.1. Laboratory solutions
3.1.1. Chemical speciation study
A chemical speciation study was performed in order
to establish the nature of the electroactive species of
gold, silver and copper in cyanide solutions. A Pour-
baix type diagram (Fig. 1) was constructed using the
thermodynamic data for soluble and insoluble species
of gold, silver and copper reported in the literature
(Ringbom, 1963; Zhang et al., 1997; Caroli and
Sharma, 1978), taking into account the laboratory
solution conditions ( pCNV=log[CNV] = 0.222,
pAuV= log[AuV(I)] = 4, pAgV= log[AgV(I)]=4 and
pCuV(I)= log[CuV(I)] = 1) using the method proposed
by Rojas et al. (1991, 1993). The MV(I) corresponds to
the generalized chemical species of the metallic ion in
solution (Rojas et al., 1991, 1993).
The full lines in Fig. 1 represent the conditional
potential change of the system MV(I)/M(0) with pH.
The dotted lines represent the limit of the pH range
where a particular metal ion species predominates
(high molar fraction) with respect to the other
cyanide species of the same metallic ion (generalized
chemical species), or in the other case, the solubility
limit for CuCN
(s)
. Fig. 1 shows that under the
chemical conditions of leaching solutions, there are
four copper, two silver and one gold species of
cyanide.
Fig. 1 shows that, at any pH, the redox potential
of the couple CuV(I)/Cu(0) has more negative values
with respect to the potential of the couples AuV(I)/
Au(0) and AgV(I)/Ag(0). These results indicate that
under thermodynamic considerations, the copper
species should not interfere with the selective reduc-
tion of Au(I) and Ag(I) under experimental condi-
tions of laboratory solution used to validate the
methodology.
(d) Cyanide solution
of Au(I) and Cu(I)
0.1 M CuCN,
10
4
M KAuCN
2
and 0.5 M KCN
(e) Cyanide solution
of Au(I),
Ag(I) and Cu(I)
0.1 M CuCN,
10
4
M KAuCN
2
,
10
4
M AgNO
3
and 0.5 M KCN
Industrial leaching solution
(f) Industrial leaching
solution
0.025 M (400 ppm)
free CN
,
8 10
3
M
(500 ppm) Cu(I),
5 10
6
M
(1 ppm) Au(I),
3 10
5
M
(3 ppm) Ag(I),
0.015 M (615 ppm) Ca,
0.025 M (575 ppm) Na
and 3 10
4
M
(17 ppm) Zn at pH 11
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 189
The calculated potentials associated with the elec-
trochemical reactions AuV(I)/Au(0), AgV(I)/Ag(0) and
CuV(I)/Cu(0) at pH= 10, pCNV = 0.22, pAuV = 4,
pAgV = 4 and pCuV = 1 are:
AuCN
2
1e
!Au
0
2CN
!Ag
0
3CN
!Cu
0
4CN
with 10
4
M Ag(CN)
3
2
without Cu(CN)
4
3
and (d) 10
4
M Au(CN)
2
with 10
4
M Ag(CN)
3
2
in the presence of 0.1 M Cu(CN)
4
3
.
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 194
solution containing the three metallic ions, Fig. 5a
and c. The presence of Cu(I) in the cyanide solution
with Au(I) and Ag(I), shifts the reduction of water
towards more negative potentials (E
85 AA cm
2 =
1494 mV vs. SCE). This indicates that the Cu(I)
ion has an important effect on the reduction of water
and on the process of cyanide and gold adsorption.
On the other hand, the reduction of gold and
silver is masked by the capacitive current densities
(see inset of Fig. 5b and c). However, in the reverse
scan, there is only one oxidation peak at 600 mV
vs. SCE in both solutions (Fig. 5b and c). This
behavior could be attributed to the Ag/Au codeposit,
since this oxidation peak is present at more positive
potentials than the oxidation peak of silver deter-
mined in the previous paper (Reyes et al., 2002) and
at more negative potential than that corresponding to
the oxidation of gold (peak II). It is important to
note that the peak I, which appears when the gold
deposit takes place in the presence of copper (Fig.
2d), is not observed in this case; this is an additional
argument for the fact that a codeposit of Ag/Au is
taking place. The oxidation peak in 600 mV vs.
SCE is slightly higher when Cu(I) ion is in solution,
indicating that there is either more deposit of Ag/Au
or codeposit of copper on this new surface (see
below).
In order to establish the potential at which the
deposition of gold and silver without copper takes
place, a voltammetric study was carried out chang-
ing the switching potential E
k
towards negative
values.
Fig. 5. Typical cyclic voltammograms obtained from laboratory solutions containing 0.5 M CN
, 10
4
Ag(CN)
3
2
and (c) 10
4
M
Au(CN)
2
, 10
4
Ag(CN)
3
2
and 0.1 M Cu(CN)
4
3
. The inset shows the voltammetric responses at low current densities and the current density
E
85 AA cm
2 chosen for the analysis of water reduction.
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 195
3.1.5. Influence of the negative switching potential
(E
k
)
Fig. 6 shows the voltammograms obtained when
the negative switching potential E
k
was changed
towards negative values for the following solutions:
cyanide solution with Ag(I) and Cu(I) (curve a), from
a previous work (Reyes et al., 2002), cyanide solution
with Au(I) and Ag(I) without Cu(I) (curve b) and with
Cu(I) (curve c).
In Fig. 6a, from E
k
= 1400 mV vs. SCE, there
is an oxidation peak of Ag(0) to Ag(I) at 675 mV
vs. SCE; the current density associated with the
Fig. 6. Partial view of typical cyclic voltammograms obtained on a vitreous carbon electrode (0.07 cm
2
) at 25 mV s
1
from 0.5 M CN
without Cu(CN)
4
3
and (c) 10
4
M Ag(CN)
3
2
and 10
4
M Au(CN)
2
, 3 10
5
M Ag(CN)
2
and 8 10
3
M Cu(CN)
4
3
in 0.025 M CN
2
1e
!Au
0
2CN
2
1e
!Ag
0
2CN
!Cu
0
4CN
,3 10
5
MAg(CN)
2
, 8 10
3
MCu(CN)
4
3
and0.025MCN
and(b)laboratorysolutioncontaining:10
4
MAu(CN)
2
Au(CN)
2
with 10
4
M Ag(CN)
3
2
in the presence of 0.1 M Cu(CN)
4
3
and 0.5 M CN
.
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 199
metallic ions of Au(I), Ag(I) and Cu(I) and a lower
concentration of cyanide in the solution.
On the other hand, in Fig. 8, it is observed that the
oxidation peaks of industrial leaching solution are
wider with regard to laboratory solution and they
change their shape rapidly with increase in the switch-
ing potential. This indicates how complicated it would
be to develop the methodology to identify where the
Ag/Au codeposition takes place without the deposi-
tion of copper from the industrial leaching solution.
The statement above justifies the need to use higher
copper and cyanide concentrations to develop the
methodology used in this study.
With the purpose of determining the potential
range at which the deposition of Au(I) and Ag(I) free
of copper from the industrial leaching solution takes
place, the quantitative study of the voltammetric
curves was carried out through the charge associated
with E
k
-dependent oxidation peaks (Qa). Fig. 9
compares the Qa vs. E
k
curves of an industrial
leaching solution (curve a) in relation to that of the
previously obtained and discussed more concentrated
cyanide solution of Au(I), Ag(I), Cu(I) and CN
(curve b).
In Fig. 9, the behaviors of the slopes of the Qa vs.
E
k
curves of the cyanide solution, for the laboratory
solution prepared in the prior section, and the indus-
trial leaching solution are observed to be quite similar.
On the other hand, it can be seen that for the industrial
leaching solution, there is a potential displacement
towards less negative values with regard to more
concentrated cyanide solution of Au(I), Ag(I), Cu(I)
and CN
, because of the
nucleation processes of these metals on the vitreous
carbon electrode and the fact that, at lower over-
potentials, less gold and silver is deposited. However,
at E
k
V1400 mV vs. SCE, the changes in the
slopes of the Qa vs. E
k
curves of the industrial
leaching solution are similar to the slope changes of
the more concentrated cyanide solution of Au(I),
Fig. 10. Change in the normalized concentration of cyanide metallic species in the catholyte compartment with time during the electrolysis of an
industrial leaching solution. Concentration profile of (a) Au(I), (b) Ag(I) and (c) Cu(I) at electrolysis potential of 1400 mV vs. SCE. The
electrolysis was carried out in an FM01-LC electrochemical laboratory reactor using an RVC of 60 ppi at a linear flow rate of 19 cm s
1
.
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 200
Ag(I), Cu(I) and CN
, it is possible to determine
the potential at which the codeposition of Ag/Au takes
place without the deposition of copper. However, just
like in the study of the more concentrated cyanide
solution of Au(I), Ag(I), Cu(I) and CN
, it is not
possible to determine the potential at which the gold
and silver deposit independently. In order to confirm
the results from the previous experiments, an electrol-
ysis study of an industrial leaching solution was
carried out.
3.2.3. Electrolysis study
The potential at which Cu(I) does not interfere
with the electrochemical deposition of gold and
silver has been established from the experiments
above. Taking this into account, an electrochemical
deposition of the species Au(I) and Ag(I) in a batch
re-circulation reactor using the industrial leaching
solution (solution f) was carried out.
The electrolysis was at constant potential on a
reticulated vitreous carbon electrode (RVC) for 25
min at a linear flow velocity of 19 cm s
1
. The
concentration change of Au(I), Ag(I) and Cu(I) in
the catholyte compartment during the electrolysis
was analyzed by atomic absorption spectroscopy.
Fig. 10 shows the depletion of Au(I) (curve a),
Ag(I) (curve b) and Cu(I) (curve c) as C
t
/C
0
vs.
time, at a constant potential of 1400 mV vs. SCE,
where C
t
and C
0
are, respectively, the concentrations
of the metal ion at time t and at the beginning of the
electrolysis.
Fig. 10 shows the evolution in the concentration of
the three metal ions with time when the electrolysis
was carried out at 1400 mV vs. SCE. Depletions in
the concentration of Au(I) and Ag(I) were up to 48%
and 71%, respectively, from their original concentra-
tions (Fig. 10a and b). The concentration of Cu(I) was
Fig. 11. Scanning electron microscopy (SEM) image of 60 ppi of the RVC electrode after 25 min of the electrolysis of the industrial leaching
solution containing: 5 10
6
M Au(CN)
2
, 3 10
5
M Ag(CN)
2
, 8 10
3
M Cu(CN)
4
3
and 0.025 M CN
at pH 10 for an
electrolysis potential of 1400 mV vs. SCE.
V. Reyes-Cruz et al. / Hydrometallurgy 65 (2002) 187203 201
constant during the first 10 min of electrolysis, how-
ever, in the following 25 min, the concentration of
Cu(I) fell 12% (Fig. 10c). This indicates that metallic
copper would be on the surface of the reticulated
vitreous carbon (RVC).
In order to analyze the morphology and composi-
tion of gold, silver and copper deposits on the RVC,
scanning electron microscopy (SEM) and X-ray dif-
fraction studies on the electrode surface were carried
out. Fig. 11 shows the SEM image of the RVC
electrode after the electrolysis at constant potential
of 1400 mV vs. SCE. In this figure, the metallic
nuclei on the RVC surface could be attributed to gold,
silver and copper deposits. Fig. 12 shows the X-ray
diffractogram obtained for the electrode surface after
the electrolysis at 1400 mV vs. SCE; this diffracto-
gram shows signals that correspond to gold, silver and
copper. The copper signal agrees with the depletion of
this ion observed after 25 min of electrolysis (Fig. 11).
It is important to stress that when the concentra-
tions of Au(I) and Ag(I) diminish in the solution, the
deposition of Cu(I) becomes energetically favorable.
Under these conditions, the electrolysis should be
stopped before the deposition of copper begins if a
quantitative separation of gold and silver is wanted.
The above analysis allows us to propose the recovery
of gold and silver at an applied potential of 1400
mV for the first 10 min of electrolysis in the electro-
chemical batch reactor with an RVC electrode.
The reduction of gold and silver in the electro-
chemical reactor FM01-LC is a preliminary study that
proves that gold and silver can be selectively
removed. However, further studies, such as current
efficiency, mass transport and spacetime yield are
necessary to design an efficient electrochemical reac-
tor for the recovery of gold and silver from leaching
process solutions.
4. Conclusions