Ministrio da Cincia e Tecnologia

Coordenao de Processos Metalrgicos e Ambientais

Copper electrowinning from gold plant waste

streams

Flavio A. Lemos
Luis Gonzaga S. Sobral
CETEM

Achilles Junqueira B. Dutra

COOPE/UFRJ

CT2006-024-00 Comunicao Tcnica a Revista Elsevier

Maro/ 2006
 Minerals Engineering 19 (2006) 388398
This article is also available online at:
www.elsevier.com/locate/mineng

Copper electrowinning from gold plant waste streams

F.A. Lemos a, L.G.S. Sobral b, A.J.B. Dutra a,*

a
Federal University of Rio de Janeiro, Department of Metallurgical and Materials Engineering, COPPE/UFRJ, P.O. Box 68505,
21941-972 Rio de Janeiro, RJ, Brazil
b
Centre for Mineral Technology, RJ, Brazil

Received 29 June 2005; accepted 26 October 2005

Available online 19 December 2005

Abstract

Gold mining industries produce a considerable amount of waste streams containing cyanide and small quantities of copper, gold and
other heavy metals. This euent is usually treated by the AVR process, in order to recycle the cyanide to the leaching operation, how-
ever, this process is not ecient for the treatment of stable cyanide complexes. In this paper, the feasibility of copper electrowinning, and
eventually residual gold, in a ow-by cell with nickel foam or a reticulated vitreous carbon (RVC) cathode and a cationic membrane was
investigated. This process has shown to be environmental-friendly and despite the low average current eciency and high energy con-
sumption, it permitted the recovery of about 99.6% of the copper and the recycling of 99.4% of cyanide present in the euent.

2005 Elsevier Ltd. All rights reserved.

Keywords: Copper; Gold; Cyanide; Electrowinning

1. Introduction ization) process or similar technology, as the Cyanisorb

Cyanide leaching is a very ecient process for gold
extraction, being capable of recovering more than 90% of
gold from ores containing just a few grams per metric
ton and, despite its toxicity, is used in almost all gold min-
ing operations. The success of cyanidation, for more than a
hundred years, is due to its availability and ability to dis-
solve gold through the formation of a stable complex with
Au(I). However, some environmental problems are associ-
ated with gold mining and processing. Among them, the
huge amount of tailings and spent leaching solutions con-
taining cyanide, heavy metals, such as copper (up to
300 mg/L, depending on the ore), and minor quantities of
gold, usually less than 0.3 ppm. As cyanide represent the
major cost in gold processing plants (Adams, 2001), some
mills use the AVR (acidicationvolatilizationreneutral-
*
Corresponding author. Tel.: +55 21 25628512.
E-mail address: adutra@metalmat.ufrj.br (A.J.B. Dutra).
process (where volatilization is eliminated), to recover cya-
nide, reducing its consumption (Young, 2001; Goode et al.,
2001; Fleming, 2001; Jay, 2001). However, this process is
not very ecient for treating diluted solutions of cyano-
complexes and some copper-cyanide complex remain in
solution, as well as the residual gold, or precipitate as insol-
uble cyanide compounds (Fleming, 2001). This residual
gold can be recovered by carbon adsorption if the concen-
tration of copper is not higher than about 100 mg/L (Mars-
den and House, 1992), as it interferes severely on gold
adsorption and a careful control of pH and cyanide con-
centration is required for a satisfactory gold recovery. In
conventional gold processing, copper appears as a cyanide
consuming element which is not recovered and impairs cya-
nide recycling.
There are a number of papers dealing with the electro-
winning of copper, silver and gold from cyanide solutions.
Some of them deals with gold leaching solutions, contain-
ing a hundred to a few mg/L of gold and silver and hun-
dreds of mg/L copper (Stavart et al., 1999; Reyes-Cruz
et al., 2004) and others with euents of electroplating

0892-6875/$ - see front matter
2005 Elsevier Ltd. All rights reserved.
doi:10.1016/j.mineng.2005.10.019
 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398
industry whose metals concentration are even higher (Spit-
zer and Bertazzoli, 2004). In the case of leaching solutions,
gold recovery is not total and euents containing up to
0.3 mg/L of gold and hundreds of milligrams per liter of
copper and free cyanide ions are not uncommon. The
recovery of these metals values from such a diluted cyanide
solution is a technological issue that has not been properly
addressed up to now from the electrochemical point of
view.
Electrolytic processes have been used for metals recover-
ing from cyanide leach solutions and electroplating eu-
ents and come up as an alternative to treat spent gold
leaching solutions in order to recover metals and oxidize
or even recycle the cyanide for reuse, overcoming the neg-
ative consequences of copper-cyanide reactions during gold
leaching. Lu et al. (2002a) developed a membrane cell with
graphite felt to recover copper and recycle the cyanide.
Copper recoveries up to 60% were achieved with an energy
consumption of 12 kWh/kg. Cheng et al. (2002) investi-
gated the electrochemical oxidation of copper cyanide solu-
tions and found that most of the cyanide was oxidized to
cyanate, at 0.90 V vs. Hg/HgO, using a platinized titanium
anode. Szpyrkowicz et al. (2000, 2005a,b,c) developed a
lab-scale batch electrochemical reactor with stainless steel
electrodes and demonstrated the feasibility of the destruc-
tion of copper cyano-complexes and simultaneous recovery
of copper, with an anodic potential of 0.7 V vs. SCE. They
also veried that the Cu(II)/Cu(I) oxides lms formed on
the anode exhibit electrocatalytic properties towards elec-
tro-oxidation of cyanide. Reyes-Cruz et al. (2002) studied
by cyclic voltammetry the electrochemical deposition of sil-
ver and gold from cyanide leaching solutions and veried
that Au(I) and Ag(I) were reduced despite the high concen-
tration of Cu(I) ions in solution, which did not interfere in
the gold and silver deposition. In a three-dimensional cell,
with a reticulated vitreous carbon cathode (Reyes-Cruz
et al., 2004), recoveries of 26% and 48% for gold and silver,
respectively, were obtained. Spitzer and Bertazzoli (2004)
developed a lter-press-type electrochemical reactor for
the selective recovery of gold and silver from electroplating
euents, containing gold, silver, copper, nickel, zinc and
cyanide. The cathodic current eciencies for gold and
gold-rich alloy recovered at
1.0 V vs. SCE were found
to be 15% and 23%, respectively. Stavart et al. (1999) used
carbon felt as a three-dimensional cathode for gold electro-
winning from solutions obtained after elution of loaded
carbon and as anode for the electro-oxidation of cyanide
ions present in waste streams. Gold extractions higher than
90%, with current eciency ranging from 6% to 12%, were
achieved. The cyanide concentration dropped from 250 to
10 mg/L with a current eciency of 83% and energy con-
sumption of about 10 kWh/kg CN
.
This paper aimed at evaluating the possibility of recov-
ering copper and eventually the residual gold from gold
plant waste streams by electrowinning, releasing the cya-
nide from the metal complexes to be recycled to leaching
process.
389
2. Experimental
2.1. Voltammetric measurements
An EG&G PAR model 273 A potentiostat/galvanostat
connected to a microcomputer with the M270 software
was used for the electrochemical tests. The cell was a
600 cm3 glass beaker with compartments separated by a
glass frit for the working and counter electrodes. The
working electrode was a stainless steel rotating disk (/
= 1.1 cm), polished to a mirror nishing; a platinum wire
spiral was the counter electrode and a saturated calomel
(E0 = 0.244 V vs. SHE), in a Luggin probe, the reference.
The electrolyte was prepared from analytical grade
CuCN, NaCN, NaOH and gold. The NaOH concentra-
tion was 0.1 M and the cyanide ion 0.0115 M (300 mg/
L). Prior to each test, the electrolyte was deaerated by
nitrogen bubbling for at least 2 h, to avoid the inuence
of dissolved oxygen. All the experiments were carried
out at 25 C.
2.2. Electrowinning system
A schematic of the electrowinning reactor and solution
ow circuit is presented in Fig. 1. The anode was a titanium
gore covered with iridium oxide, the cathode a
110 42 11 mm nickel foam or a reticulated vitreous car-
bon (RVC) with a porosity of 100 ppi (pores per inch), ren-
dering surface areas of 8.33 and 32.47 m2, respectively. The
anolyte and catholyte were separated by a Naon 417 cat-
ion exchange membrane. The function of the membrane is
to avoid the anodic oxidation of the cyanide ions released
during cathodic reduction of the copper or gold cyanide
complexes, enabling its recycling. The anolyte was a 0.5
molar sodium hydroxide plus a mixture of 0.125 mol K4-
Fe(CN)6/L and 0.0025 mol K3Fe(CN)6/L, to avoid the
high overpotential associated with the oxygen evolution
reaction. The catholyte, unless otherwise stated, was
0.5 mol/L NaOH solution with the specied concentrations
of cyanide and copper as cyano-complexes. During the
electrolysis, samples were periodically collected for copper
analysis by atomic absorption spectrophotometry. Cyanide
ion concentration was determined by potentiometric titra-
tion with the aid of a CN
ion selective electrode (Orion
model 9606BN), whose reproducibility is about 2%. This
analysis was carried out in a plastic beaker under moderate
and uniform stirring (without vortex in the solution). The
anolyte and catholyte reservoirs were each lled with 2 l
of electrolyte and bubbled with nitrogen, to remove the dis-
solved oxygen.
3. Results and discussion
3.1. Equilibrium calculations
Sodium or potassium cyanide salts are quite soluble in
water producing cyanide ions, which hydrolyze in water
390 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398

Fig. 1. Schematic of the electrolytic cell and solution ow circuit.

to form molecular hydrogen cyanide, with an increase in exists as free ions. As hydrogen cyanide has a relatively
pH, according to reaction (1): high vapor pressure, it readily volatilizes, causing environ-
CN
H2 O HCN OH
1 mental problems and loss of cyanide. Consequently, most

10
of the operations involving cyanide ions are carried out
Hydrogen cyanide is a weak acid (Ka = 4.89 10 ) at pH higher than 10.
whose dissociation in aqueous solutions depends on pH, Gold forms strong acid dissociable complexes with cya-
as shown in Fig. 2. At pH 9.3, just about half of the cyanide

nide, where the main complex is AuCN2 , with a stability
39
constant, b, of 2.0 10 . On the other hand, the equilib-
1.0
rium of cuprous ions in cyanide solutions can be repre-
0.9 HCN CN-
sented by reactions (2)(5), which are associated with
0.8
+
[H ] = 4.8x10 -10
([HCN]/[CN-])
their equilibrium constants K1 to K4:
0.7
Cu CN
CuCN CuCN K 1 Cu CN
 2
Molar fraction

0.6

0.5
CuCN CN
CuCN

2 CuCN


2  K 2 CuCNCN  3
0.4 CuCN

2

2 CN CuCN3
0.3

CuCN2


3  K 3 CuCN2 CN  4
0.2

0.1 CuCN2

3

3 CN CuCN4
0.0
0 1 2 3 4 5 6 7 8 9 10 11 12 13 14 CuCN3
2


4  K 4 CuCN3 CN  5
pH
These equilibrium constants are associated to an overall
Fig. 2. Distribution diagram of HCN as function of pH. formation constant, bi, according to Eq. (6):
 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398 391

b1 K 1 ; b2 K 1 K 2 ; b3 K 1 K 2 K 3 ; b4 K 1 K 2 K 3 K 4 Based on the data presented in Table 1, the diagram for

6 the cumulative distribution of cupric ion-cyanide species as
function of logarithmic concentration of CN
ion is pre-
Considering that CuCN can exists only as a solid phase, sented in Fig. 3. This diagram indicates a trend valid for
for a copper-cyanide solution with [CN
]/[Cu(I)] molar free cyanide ion concentration considerably higher than
ratio higher than 2 the presence of Cu+ and CuCN in solu- total cuprous ion concentration and high pH, otherwise
tion, at high pH, can be neglected. Then, the total copper precipitation of CuCN (Ksp = 10
20) can occur (Lu et al.,
concentration in solution, [Cu]T, can be expressed by Eq. 2002b). In this work, initial free cyanide ion concentration
(7): is higher than 10
2 M and total cuprous ion concentration
CuT CuCN
2
3
lower than 4.7 10
3 M. Furthermore, while copper is
2  CuCN3  CuCN4  7
being removed from the catholyte free cyanide ion concen-
then, the fractions a2, a3 and a4, corresponding, respectively, tration is increasing due to copper deposition. Conse-

2
3

to the species CuCN2 , CuCN3 and CuCN4 , can be quently, CuCN precipitation is unlikely to take place.
represented by Eqs. (8)(10), which are function of bi and It can be observed in the diagram of Fig. 3 that for
cyanide ion concentration: higher cyanide ion concentrations (higher than 10
2 M)
b2 CN

2 only CuCN2
3

3 and CuCN4 will be present in solution,
a2 8 while for concentrations lower than 10
4 M, CuCN2
3 ,
1 b2 CN  b3 CN
3 b4 CN
4

2


and a smaller amount of CuCN2 , will predominate.
3
b3 CN
 The inuence of pH on the copper cyanide complex species,
a3 9
2
1 b2 CN
 b3 CN
 b4 CN

3 4 for a total free cyanide concentration of 10
3 M is pre-
4 sented in Fig. 4. It indicates that for pH higher than 8.5
b4 CN
 2

CuCN3 will be the predominant species, but small
a4 2 3 4
10
1 b2 CN
 b3 CN
 b4 CN
 amounts of CuCN
3

2 and CuCN4 will also be present

The overall formation constants bi, extracted from Leao in solution. For pH higher than 12 there is no remarkable
and Ciminelli (2001), for the cuprous ion cyanide system eect of hydroxyl concentration on the predominance of
are shown in Table 1. These data, although established cuprous-cyanide species.
for zero ionic strength, are close to the used by Lu et al. Free energy data available in the literature (Bard et al.,
(2002b). 1985), permit the standard potential estimation for the
cathodic reduction of copper and gold cyanide complexes,
Table 1
as shown in Table 2.
Overall formation constants for the cuprous ion-cyanide system The rst reaction presented in Table 2 is not relevant.
b2 b3 b4
The equilibrium potentials for reactions (11)(15) strongly
depend on both cyanide ion and copper (or gold) cyanide
1.00 1024 3.98 1028 1.58 1030
complex concentrations and can be calculated through

1.0

0.9
4 3+ 4
0.8

0.7
Cumulative fraction

0.6

0.5
3- 2- -
Cu(CN)4 Cu(CN)3 Cu(CN)2
0.4

0.3

0.2

0.1

0.0
0 1 2 3 4 5 6
-log [CN-]

Fig. 3. Logarithmic diagram for the cumulative distribution of cuprous ion-cyanide species as function of free cyanide ion concentration.
392 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398

100 3-
Cu(CN)4
90

Cu(CN)x concentration (%) 80

70

60
2-
Cu(CN)3
50
-
Cu(CN)2
40
1-x

30

20

10

0
6 7 8 9 10 11 12 13 14
pH

Fig. 4. Distribution diagram for copper cyanide complexes as function of pH, for a free cyanide ion concentration of 10
3 M.

E
0:444
0:059f2 logCN

logCuCN2 g 16
Table 2

2

Free energy and standard electrode potentials for the possible reactions E
1:205
0:059f3 logCN 
logCuCN3 g 17
involving the reductions of copper and gold cyanide complexes 3

E
1:292
0:059f4 logCN

logCuCN4 g 18
Reaction DG0 (kJ mol
1) E0 (V) No.
CuCNs e
Cu CN
63.90
0.662 (11)
E
0:600
0:059f2 logCN 


logAuCN

2 g 19
CuCN


2 e Cu 2CN


42.80
0.444 (12) The inuence of cyanide concentration on the equilib-
2

CuCN3 e Cu 3CN



116.2
1.205 (13) rium potentials of copper and gold cyanide complexes,
CuCN3


4 e Cu 4CN


124.6
1.292 (14) for Cu(I) and Au(I) concentrations of 300 mg/L
AuCN


2 e Au 2CN


58.80
0.600 (15) (4.72 10
3 M) and 0.2 mg/L (1.04 10
6 M), respec-
tively, is shown in Fig. 5.
the Nernst equation and are presented in Eqs. (16)(19) It can be seen in Fig. 5 that cyanide ion concentration
respectively. presents a huge inuence on the reduction of the copper

0.2

0.0

-0.2
-
Cu(CN) 2
Potential vs. SHE (V)

-0.4
2-
-0.6 Cu(CN)3
-
Au(CN) 2
-0.8
3-
Cu(CN)4
-1.0
Au: 0.2 ppm
-1.2
Cu: 300 ppm

-1.4

-1.6
0 -1 -2 -3 -4 -5 -6
log[CN-]

Fig. 5. Equilibrium potential for the reduction of CuCN1
x

x and AuCN


2 as function of CN concentration, for a total copper ions concentration of
300 mg/L.
 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398 393

and gold cyanide complexes. Increasing concentrations of
CN
lead to lower equilibrium potentials turning the
reduction more dicult. Furthermore, it should be remem-
bered that as copper and gold are deposited on the cath-
ode, the CN
concentration at its vicinity increases
signicatively, retarding the reduction and possibly even
changing the order of the copper complex to a higher value.
These considerations match with the model of current dis-
tribution in a cuprous cyanide electrolyte proposed by
Dudek and Fedkiw (1999). Then, strong electrolyte agita-
tion should be provided in order to promote the cyanide
ions removal from the cathode neighborhood and the
increasing of limiting current density for the metals
deposition.
Fig. 5, allied to the distribution diagram for cuprous
ions (Fig. 3), indicates that gold electrowinning cannot be
carried out without some copper co-deposition due to reac-
tion (12), despite the low fraction of CuCN
2 present in
solution. For a free cyanide concentration of 300 mg/L
(1.15 10
2 M), less than 0.5% of the cuprous ions will

2

form CuCN2 , and CuCN3 will be the predominant
species (about 66%) of copper in solution, which is reduced

10
CN- : 300 ppm
9
: 1mV/s
8
Current density (mA/cm2)

4 1.0 ppm

1 0.2 ppm

-1
-200 -400 -600 -800 -1000 -1200 -1400 -1600
Cathodic potential vs. SCE (mV)

Fig. 6. Inuence of gold concentration on the cyclic voltammograms in a 0.1 M NaOH solution with 300 mg/L of CN
and 0.2 or 1.0 mg/L of gold.

10
Cu: 300 ppm
9
Au: 0.2 ppm
8 CN-: 300 ppm
Current density (mA/cm2)

7 : 1mV/s

4
Cu +
3

1 Cu+ + Au+
0

-1
-200 -400 -600 -800 -1000 -1200 -1400 -1600
Cathodic potential vs. SCE (V)

Fig. 7. Inuence of the presence of 0.2 mg/L of gold on the cyclic voltammograms in a 0.1 M NaOH solution with 300 mg/L of CN
and 300 mg/L of
copper.
394
at a potential only 15 mV below that of CuCN3
4 . This
diagram also explains the co-deposition of copper during
gold electrowinning, as veried by Barbosa et al. (2001)
in a study of the behavior of metallic impurities during gold
electrowinning. Furthermore, for copper recovering with
the liberation of free cyanide, the residual gold will be
co-deposited, as the potential for the reduction of higher
order copper complexes are much more negative than that
necessary for AuCN
2 reduction. This residual gold could
be recovered during copper electrorening in the anodic
slimes (Anderson et al., 1999).
3.2. Voltammetric tests
Cyclic voltammograms in a 0.1 molar NaOH solution
containing 300 mg/L of CN
and 0.2 mg/L and 1 mg/L
of gold are presented in Fig. 6. The rotation speed of the
stainless steel disk working electrode was 2000 rpm and
the potential scan rate 1 mV/s. The arrows indicate the


scan direction. It can be observed that AuCN2 reduction
starts around
850 mV vs. SCE, a slightly higher value
than those indicated in Fig. 5. No clear limiting current
density plateau was observed due to intensive hydrogen
evolution, which increases rapidly at potentials lower than

1100 mV. Cross over potentials in the range of
800 to

900 mV were observed for both curves.
Cyclic voltammograms in a 0.1 molar NaOH solution
containing 300 mg/L of CN
and 300 mg/L of copper ions,
with and without 0.2 mg/L of gold are presented in Fig. 7.
The conditions of the experiment were the same used in
those of Fig. 6. In the absence of gold (thicker line), a slight
increase in current density, for potentials lower than
500
Cathodic Potential: -1300 mV
450 Electrolyte flow rate: 0.43 L min-1
400
350
300
[CN-] (mg L-1)
250
200
y = 106 .52 ln(x) + 18 7.8
150
100
50
0 0
0 15
Fig. 8. Variation of copper and cyanide ion concentration with time in a potentiostatic electrolysis, at
1300 mV vs. SCE with a nickel foam cathode.
F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398

800 mV, indicates the reduction of CuCN
2 . This poten-
tial is close to the determinated in Fig. 5. A clear increase in
current density, at
1100 mV, indicates the onset of
2
3

CuCN3 and CuCN4 reduction with a limiting current
density plateau at
1200 mV, followed by intensive hydro-
gen evolution. The thinner voltammogram, indicate that
gold is deposited before most of the copper. These results
indicate that if the majority of the copper could be removed
from a waste solution by electrowinning the residual gold
will be also electrowon, and probably could be recovered
as anodic slime during copper rening.
3.3. Electrowinning tests
The concentrationtime relationships of copper and cya-
nide ion during potentiostatic electrowinning tests at

1300 and
1600 mV vs. SCE, with a nickel foam cathode,
are shown in Figs. 8 and 9, respectively. From the compar-
ison of these gures, it can be observed that cathodic
potential plays an important role in copper deposition,
since at
1300 mV vs. SCE copper concentration after
5 h of electrolysis was about 78 mg/L, while at
1600 mV
a concentration of about 5 mg/L was achieved after only
3 h. At even more cathodic potentials (
1700 mV vs.
SCE) the nal copper concentration was basically the
same, but current eciency dropped to less than 0.4%,
due to intensive hydrogen evolution. This behavior can
be attributed to the presence of dierent copper-cyanide
complexes in solution. At
1300 mV vs. SCE, the potential
is not enough cathodic to promote an eective reduction of
higher order copper complexes, while at
1600 mV vs.
SCE, copper electrodeposition is under a mass transport
400
350
300
250
[Cu] (mg L-1)
200
150
2
R = 0.98
100
y = -100.46 ln(x) + 341.68
2
R = 0.91
50
30 45 60 90 120 180 240 300
Time (min)
 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398 395

500 400
Cathodic potential: -1600 mV
450
Electrolyte flow rate : 0.43 L min-1 350
400
y = 138.08ln(x) + 177. 75 300
350 R 2 = 0.96
[CN-] (mg L-1)

250

[Cu] (mg L-1)

300

250 200

200 150
150
100
100
y = -112.82ln(x) + 225.09 50
50
R 2 = 0.96
0 0
0 15 30 45 60 90 120 180
Time (min)

Fig. 9. Variation of copper and cyanide ion concentration with time in a potentiostatic electrolysis, at
1600 mV vs. SCE with a nickel foam cathode.

control regime for the higher order complexes, CuCN2
3 a 5-h electrolysis. Copper concentration decay appears to
3

and CuCN4 . It can also be observed that cyanide ion follow a rst order kinetic, with a rate constant of
concentration increases faster in the experiment carried 0.0154 min
1. The eect of increasing current is to increase
out at the more cathodic potential. Both, copper concen- the rate constant, as shown in Fig. 11, favoring the rate of
tration decay and cyanide ion concentration increase fol- copper deposition. The reactor system behaves as a contin-
low a logarithmic function, with a correlation coecient uously stirred tank reactor under mass transport control
(R2) higher than 0.90, as presented in Figs. 8 and 9. The and may be described by the model related by Walker
nickel foam cathode has shown to be eective as a cathode and Wragg (1977), which was derived from a conventional
for copper deposition, but it presents problems for copper electrolytic cell operating in a batch recycle mode. Under
stripping. Then, a reticulated vitreous carbon cathode was these circumstances, the variation of concentration with
also tested due its superior corrosion resistance. time can be expressed by Eq. (20):
The concentrationtime relationship of copper and cya-   
Qt 1
nide ion during a constant current experiment (I = 5.0 A) is C in;t C in;0 exp
1
20
VT 1 kAaL=Q
shown in Fig. 10. A copper concentration decrease from
580 mg/L to 3.9 mg/L and a cyanide ion concentration where, Cin,t is the metal concentration in the reservoir at
increase from 120 mg/L to 780 mg/L were achieved after time t, Cin,0 is the initial metal concentration, Q is the

700 900
I: 5 A
y = -275.2ln(x) + 661.65 800
600 R 2 = 0.94

700
500
600
[Cu] (mg L )
-1

[CN-] (mg L )

400 500

300 400
-1

300
200
200
100 y = 310.23ln(x) +38.998
100
R 2 = 0.94

0 0
0 15 30 45 60 90 120 180 240 300
Time (min)

Fig. 10. Variation of copper and cyanide ion concentration with time in a galvanostatic electrolysis with a RVC cathode and a current of 5.0 A.
396 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398

6.0 is considerably faster for a ow rate of 1.75 L/min, with

a recovery around 98% after 2 h. This behavior was already
5.0 expected, since the electrolysis was carried out under a
6.0A
mass control regime, where the electrolyte ow plays an
k = 0.0168 min-1 important role. Additional recoveries are time and energy
ln ([Cu+]0/[Cu+])

4.0
3.0
2.0
1.0
0.0
0 50 100
Fig. 11. Inuence of current on the normalized copper concentration/time
behavior, for galvanostatic electrolysis with a RVC cathode, where k
represents the rate constant.
volumetric ow rate, VT the eective volume of the reser-
voir, k the rate constant, A the electrode specic surface
area, a the electrode cross sectional area and L the length
of the electrode.
The eect of the number of passes of the catholyte
through the ow-by cell on copper recovery and cyanide
recycling, for a current of 6.0 A and a ow rate of
0.43 L/min is presented in Fig. 12. It can be observed that
about 96% of the copper was recovered after 13 passes and
a [CN
]/[CNTotal] ratio of almost 90% was achieved.
The inuence of catholyte ow rate on copper recovery
for an electrowinning test with a current of 6.0 A is pre-
sented in Fig. 13. It can be observed that copper recovery
5.0A consuming, being very inecient.
k = 0.0154 min-1
The summary of the results obtained with constant cur-
rent electrolysis for an initial copper concentration of
approximately 600 mg/L and an electrolyte ow rate of
4.0A 0.43 L/min are presented in Table 3. It can be observed
k = 0.0137 min-1
that although good results for copper and cyanide ion
recoveries were achieved, the current eciency is low and
the energy consumption for copper electrowinning is high.
150 200 250 300 350 The current eciency was expected to be low, due to the
Time (min) low copper concentration, particularly at the end of the
experiment, when it drops considerably. During the rst
hour of the experiment, current eciency is three to four
times higher than at the end, after 5 h. The high energy
consumption is a consequence of the low current eciency
allied to the elevated resistivity of the RVC cathode, which
promotes an uneven current distribution throughout the
cathode thickness. Furthermore, some excessive anode
polarization also occurred. Although it is technically feasi-
ble remove copper and possibly residual gold, by electroly-
sis from gold plant waste streams additional research is
needed to improve the energy eciency of this process.
This additional research should focus the search for elec-
trode materials with low electrical resistance, low overpo-
tentials, high specic surface area and compatible with
the electrolyte. Another point to be focused is the balance
between copper recovery and energy consumption, because
as copper concentration in solution drops with time, energy

100 100
Flow rate: 0.43 L min-1
90 Current: 6.0 A 90

80 80

70 70
Copper recovery (%)

[CN-]/[CNTotal] (%)

60 60

50 50

40 40

30 30

20 20

10 10

0 0
1 2 3 4 5 6 7 8 9 10 11 12 13
Number of passes

Fig. 12. Inuence of the number of passes of the electrolyte through the cell with a RVC cathode and a current of 6.0 A.
 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398 397

100
1.75 L min -1
90
Current: 6.0 A
80
Copper recovery (%)
70

60
0.43 L min-1
50

40

30

20

10

0
0 50 100 150 200 250 300
Time (min)

Fig. 13. Inuence of catholyte ow rate on copper recovery with a RVC cathode and a current of 6.0 A.

Table 3 References
Summary of the electrolysis at constant current with a RVC cathode and
ow rate of 0.43 L/min, for an initial copper concentration of about Adams, M.D., 2001. A methodology for determining the deportment of
600 mg/L (duration: 5 h) cyanide losses in gold plants. Minerals Engineering 14 (4), 383390.
Current (A) 5.0 6.0 7.0 Anderson, C., Fayram, T., Doolin, M., 1999. The application of copper
Average current eciency (%) 1.93 1.53 1.40 metallurgy in the recovery of secondary precious metals. In: Dutrizac,
Average energy consumption (kWh/kg) 61.8 78.7 85.2 J.E., Ji, J., Ramachandran, V. (Eds.), Copper 99Fourth Interna-
Final copper concentration (mg/L) 3.9 3.3 3.5 tional Conference, vol. 3. TMS, Warrendale, pp. 529543.
Copper recovery (%) 99.3 99.4 99.6 Barbosa, L.A.D., Sobral, L.G.S., Dutra, A.J.B., 2001. Gold electrowin-
Cyanide recovery (%) 99.0 99.1 99.4 ning from diluted cyanide liquors: performance evaluation of dierent
reaction systems. Minerals Engineering 14 (9), 963974.
Bard, A.J., Parsons, R., Jordan, J. (Eds.), 1985. Standard Potentials in
Aqueous Solutions. Marcel Dekker, New York.
consumption increases exponentially, turning the process Cheng, S.C., Gattrell, M., Guena, T., MacDougall, B., 2002. The
economically prohibitive. electrochemical oxidation of alkaline copper cyanide solutions. Elect-
rochimica Acta 47 (20), 32453256.
4. Conclusions Dudek, D.A., Fedkiw, P.S., 1999. Electrodeposition of copper from
cuprous cyanide electrolyte. I. Current distribution on a stationary
disk. Journal of Electroanalytical Chemistry 474 (1), 1630.
Voltammetric tests allied to equilibrium diagrams indi- Fleming, C.A., 2001. The case for cyanide recovery from gold plant
cated that for a free cyanide concentration of about tailings-positive economics plus environment stewardship. In: Young,
0.0115 M (300 mg/L), residual gold can be electrowon C.A., Tidwell, L.G., Anderson, C.G. (Eds.), Proceedings of Cyanide:
before copper from basic cyanide solutions within concen- Social, Industrial and Economic Aspects. TMS, Warrendale, pp. 271
trations close to gold plant waste streams. 288.
Goode, J.R., McMullen, J., Wells, J.A., Thomas, K.G., 2001. Cyanide and
Electrowinning tests with copper in a ow-by cell with a the environment: Barrick Gold Corporations perspective. In: Young,
RVC cathode separated of the anode by a cation exchange C.A., Tidwell, L.G., Anderson, C.G. (Eds.), Proceedings of Cyanide:
membrane permitted the recovery of 99.6% of copper with Social, Industrial and Economic Aspects. TMS, Warrendale, pp. 257
the liberation of 99.4% of the cyanide as free ion for 270.
recycling. Jay, W.H., 2001. Coppergold cyanide recovery systems. In: Young, C.A.,
Tidwell, L.G., Anderson, C.G. (Eds.), Proceedings of Cyanide: Social,
Additional research is needed to improve the energy Industrial and Economic Aspects. TMS, Warrendale, pp. 317346.
consumption and current eciency of the cell and nding Leao, V.A., Ciminelli, V.S.T., 2001. The role of elution on the recycling of
an optimum point for the balance between copper recovery cyanide using ion exchange resins. In: Young, C.A., Tidwell, L.G.,
and specic energy consumption. Anderson, C.G. (Eds.), Proceedings of Cyanide: Social, Industrial and
Economic Aspects. TMS, Warrendale, pp. 303316.
Lu, J., Dreisinger, D.B., Cooper, W.C., 2002a. Copper electrowinning
Acknowledgements from dilute cyanide solution in a membrane cell using graphite felt.
Hydrometallurgy 64 (1), 111.
The authors would like to acknowledge CNPq and FA- Lu, J., Dreisinger, D.B., Cooper, W.C., 2002b. Thermodynamics of the
PERJ for the nancial support. aqueous copper-cyanide system. Hydrometallurgy 66 (1), 2336.
398 F.A. Lemos et al. / Minerals Engineering 19 (2006) 388398
Marsden, J., House, I., 1992. The Chemistry of Gold Extraction. Ellis
Horwood, New York.
Reyes-Cruz, V., Ponce-de-Leon, C., Gonzalez, I., Oropeza, M.T., 2002.
Electrochemical deposition of silver and gold from cyanide leaching
solutions. Hydrometallurgy 65 (23), 187203.
Reyes-Cruz, V., Gonzalez, I., Oropeza, M.T., 2004. Electro-recovery of
gold and silver from a cyanide leaching solution using a three-
dimensional reactor. Electrochimica Acta 49 (25), 44174423.
Spitzer, M., Bertazzoli, R., 2004. Selective electrochemical recovery of
gold and silver from cyanide aqueous euents using titanium and
vitreous carbon cathodes. Hydrometallurgy 74 (34), 233242.
Stavart, A., Leroy, C., Van Lierde, A., 1999. Potential use of carbon felt in
gold hydrometallurgy. Minerals Engineering 12 (5), 545558.
Szpyrkowicz, L., Kaul, S.N., Molga, E., DeFaveri, M., 2000. Comparison
of the performance or a reactor equipped with a Ti/Pt and a SS anode
for simultaneous cyanide removal and copper recovery. Electrochimica
Acta 46 (23), 381387.
Szpyrkowicz, L., Kelsall, G.H., Sout, R.M., Ricci, F., Kaul, S.N., 2005a.
Hydrodynamic eects on the performance of an electrochemical
reactor for destruction of copper cyanidePart 1: in situ formation
of the electrocatalytic lm. Chemical Engineering Science 60 (2), 523
533.
Szpyrkowicz, L., Kelsall, G.H., Sout, R.M., Ricci, F., Kaul, S.N., 2005b.
Hydrodynamic eects on the performance of an electrochemical
reactor for destruction of copper cyanidePart 2: reactor kinetics
and current eciencies. Chemical Engineering Science 60 (2), 535
543.
Szpyrkowicz, L., Ricci, F., Montemor, M.F., Souto, R.M., 2005c.
Characterization of the catalytic lms formed on stainless steel anodes
employed for the electrochemical treatment of cuprocyanide wastewa-
ters. Journal of Hazardous Materials B 119 (13), 145152.
Walker, A.T.S., Wragg, A.A., 1977. The modeling of concentrationtime
relationships in recirculating electrochemical reactor systems. Electro-
chimica Acta 22 (10), 11291134.
Young, C.A., 2001. Remediation technologies for the management of
aqueous cyanide species. In: Young, C.A., Tidwell, L.G., Anderson,
C.G. (Eds.), Proceedings of Cyanide: Social, Industrial and Economic
Aspects. TMS, Warrendale, pp. 175194.