Centro de Tecnologia Mineral

Ministrio da Cincia e Tecnologia

Coordenao de Metalurgia Extrativa

GOLD AND COPPER ELECTROWINNING FROM A GOLD PLANT

WASTE SOLUTION

Luis Gonzaga Santos Sobral

Pesquisador Titular, PhD.

Byron Rosemberg
Bolsista

Achilles J. B. Dutra
Prof. UFRJ

CT 2002-005-00 Contribuio Tcnica ao TMS Fall 2002 16-20

June 2002, Lulea, Sweden
 GOLD AND COPPER ELECTROWINNING FROM A GOLD PLANT
WASTE SOLUTION
A.J.B. Dutra*, L.G.S. Sobral**, B. Rosemberg* and F.A. Lemos*

* UFRJ(Federal University of Rio de Janeiro - adutra@metalmat.ufrj.br)

** CETEM (Centre for Mineral Technology - Lsobral@cetem.gov.br)

Abstract

A Brazilian gold mine produces a spent leach solution from the CIL circuit with considerable
amounts of gold, copper and cyanide. The residual dissolved gold is usually recovered by
adsorption on activated carbon, but the elevated copper/gold ratio impairs the gold adsorption.
In this paper the feasibility of gold and copper electrowinning on a reticulated vitreous
carbon, in a flow-by cell, with a cationic membrane is investigated. This electrolytic process
is environmental friendly, as it permits the recovery of gold and copper and, at the same time,
the recycling of cyanide from the metal complexes, without the production of sludge.
Introduction

Heap leaching with alkaline sodium cyanide solutions has become an important method of
gold extraction, producing, typically, a liquor containing up to 5.08 x 10-5 mol dm-3 (10ppm)
of gold[1-6]. Current technology for recovering the gold from these dilute solutions employs
adsorption of gold onto activated carbon [7,8]. The carbon is subsequently stripped to produce
a concentrated solution varying from 2.54 x 10-4 to 5.08 x 10-3 mol dm-3 (50-1000mg.L-1)
from which the gold is conventionally electrowon.

It has been suggested [9,10] that heap leaching procedures could be simplified by
electrowinning gold directly from the diluted heap leach liquors. This would eliminate the
activated carbon adsorption, stripping and regeneration steps. However, the electrolytic
removal and recovery of metals ions from dilute solutions requires the use of electrodes of
high surface area[11-15] and the present technical contribution is concerned with the
performance of three-dimensional steel wool for use as material for flow-by porous cathode
having a large surface area per unit volume.

To investigate the kinetics of the gold and copper deposition processes, the first part of the
present work describes deposition studies at a vitreous carbon rotating disk electrode from
synthetic solution of alkaline gold and copper cyanides (KA u(CN)2 and K2Cu(CN)3) using a
steady-state, linear sweep technique. In the second part of this paper, the performance of lab-
scale electrowinning cell with reticulated vitreous carbon cathode for the removal of low
levels of gold (1.01x10-2 mol.m-3 or 2ppm) as a cyanide complex ions, in the first place, and
simultaneously, high copper concentration (141.70 mol.m-3 or 9g.L-1). It is demonstrated that
it is possible to process dilute gold cyanide solutions together with copper in higher
concentrations and achieve gold levels in the ppb range, with high cell performance and
current efficiencies up to 60%. Moreover, the power requirements and energy consumptions
at the laboratory scale were low and would be expected to improve further with scale-up of
the technology.

Experimental

All solutions for gold and copper deposition studies contained 0.5 mol dm-3 K2SO4 (AnalaR)
as base electrolyte. In the case of the rotating disk experiments, 0.1 mol dm-3 K2CO3 was also
added to act as a buffer against cyanide hydrolysis; gold and copper were put into solution as
Kau(CN)2 and CuCN, respectively, and free cyanide as KCN. Solutions were made up using
deionised distilled water and were de-aerated with oxygen-free nitrogen prior to the
electrochemical experiments.

The deposition of gold was studied at a gold rotating disk electrode (area=3.68 x 10-5 m2)
embedded in a Teflon holder and attached to a rotating disk assembly. The gold electrode
was polished to a mirror finish with alumina powder (1-5m particle size) just before
recording steady-state sweep curves. A conventional Pyrex cell assembly (Fig. 1) was used,
incorporating a saturated calomel reference electrode separated from the bulk solution by a
Luggin capillary; a large platinum foil in a separated compartment served as a counter
electrode.

The electrowinning reactor system (laboratory cell and flow system) is sketched in Fig.2. The
anode used was a titanium gore covered with IrO2 (iridium oxide) and the current feeder for
the vitreous carbon cathode was a gold plated copper sheet. The reticulated vitreous carbon
was a 60 ppi (pores per inch) supplied by Electrosynthesis Co.(USA).

Figure1. Experimental cell design for experiments with rotating disk electrodes: (1) reference
electrode, (2) Luggin capillary, (3) Gold rotating disk electrode, (4) Platinum foil electrode,
(5) nitrogen bubbler, (6) porous glass sinter.

Figure 2. Reactor system (electrowinning cell and solution flow circuit).

The anolyte and catholyte were separated by a Nafion 417 cation exchange membrane
(DuPont). The anolyte and catholyte reservoirs were each filled with 2 dm3 of electrolyte.
Both reservoirs were fitted with nitrogen bubblers to remove oxygen. The electrolytes were
prepared with distilled water and AnalaR reagents. The anolyte was 0.5 mol dm-3 sodium
hydroxide plus a mixture of 0.125 mol dm-3 K4Fe(CN)6 and 0.0025 mol dm-3 K3Fe(CN)6. The
anodic process was thus the oxidation of potassium ferrocyanide to ferricyanide, as follows:

Fe(CN ) 64 Fe(CN ) 36 + e (1)

The high ratio of K4Fe(CN)6 : K3Fe(CN)6 in the anolyte enables oxygen evolution at the
anode to be avoided:

4OH 2 H 2 O + O2 + 4e (2)

The extent of this subsidiary reaction depends upon process conditions and electrolyte
composition. Except where otherwise stated, the catholyte was o.5 mol dm-3 potassium
sulphate with 0.1 mol dm-3 NaOH and the specified concentrations of gold and copper.

Results and Discussion

Linear Potential Scans with a Rotating Gold Electrode

Figure 3 illustrates the form of the steady-state polarization curves measured for the cathodic
reduction of both cyanide species considered (Au(CN)2- and Cu(CN)32-) at a rotating gold
electrode. The potential scans begin at 0.80 V(SCE).

2.5

2.0
Current/ mA

1.5

1.0

Au + Cu
0.5
Au
0.0
-900 -1100 -1300 -1500 -1700
Potential/ mV(S.C.E.)

Figure3. Current vs. potential for gold and copper deposition. [Au] = 1.01 x 10-5 mol dm-3,
[KCN] = 8.4 x 10-3 mol dm-3, [Cu] = 0.14 mol dm-3. All the potential scans begin at 0.80
V(SCE). Scan rate of 3 mV s-1 and electrode rotation speed of 2000 rpm.
From the Fig.3, it can be seen that as the potential moves cathodically, for both curves, the
current rises rapidly owing to the onset of the copper and gold ions reduction transported to
the electrode surface by convective diffusion. A well-defined limiting current regions are
observed. Finally, at potentials more negative than 1.4 V(SCE), hydrogen gas is evolved at
the electrode surface.

The profile of the curve of the mixture of gold and copper shows that the presence of copper
in gold electrolytes shift the gold deposition to occur at less cathodic potentials. Copper also
suppresses the onset of the hydrogen evolution reaction

Controlled Potential Electrolysis at Reticulated Vitreous Carbon Foam Cathodes

When conditions are chosen so that the reduction of metal ions to their respective elements is
mass transport controlled over all the surface of three-dimensional cathode, the current is
given by

I L = FVe K L Ac (3)

where Ve is the volume of the cathode, A is the specific surface area (the active area/unit
volume of cathode), KL is the mass transfer coefficient and c is the metals concentration.

The reactor system shown in Fig.2 behaves as a continuously stirred tank reactor (CSTR)
under mass transport control and may be described by the model due to Pickett [16], which
was derived for a conventional electrolytic cell operating in the batch recycle mode. Under
these circumstances, the metal concentration profile at the outlet of the reactor may be
described by:

Qt 1
C in ,t = C in ,0 exp 1 (4)
VT 1 + K L AaL / Q

where Cin,t is the metal concentration in the reservoir at time t, Cin,o is the initial metal
concentration in the reservoir, Q is the volumetric flow rate, VT effective volume of the
reservoir, A the specific surface area, a cross sectional area of the cathode and L the length of
the cathode. This equation is an approximation [17], but has been shown to describe the
behaviour of other systems adequately [18]. The conditions necessary for this to be valid
include:
a) A well-stirred reservoir.
b) Vcell <<VT
c) Ideal CSTR behaviour

In the initial electrowinning experiments, the catholyte was an oxygen-free 0.5 mol dm-3
K2SO4, at pH 13 and the gold and copper concentrations as above mentioned. Typically,
controlled potential electrolysis was carried out at 1.4 V(SCE) and the depletion of gold and
copper, the cell current and voltage and the charge passed were monitored as a function of
time. The Figure 4 shows the copper and gold concentration decays with electrolysis time. As
can be observed from that plot, the gold is nearly 100% recovered within 20 minutes while
copper was only 35% recovered. Taking into consideration the cathode potential used the
following reduction reactions take place:
 10.0 2.5
9.0

Copper Concentration (g/L)

Gold Concentration (ppm)

8.0 2.0
7.0
Cu recovery: 25%
6.0 1.5
5.0
4.0 1.0
3.0
2.0 Au recovery: 70%
0.5
1.0
0.0 0.0
0 5 10 15 20 30 60 90 120
Time (min)

Figure 4. Gold and copper concentration decays with time.

Au (CN ) 2 + e Au o + 2CN (5)

Cu (CN ) 32 + e Cu o + 3CN (6)

However, apart from removing the gold very quickly from the electrolyte, which was
expected considering the cathode potential used, the current efficiency alongside the
electrowinning process was to some extent compromised due to a great deal of the available
current be consumed for evolving hydrogen.

From the above reduction reactions it is clear that the concentration of cyanide ions being
released increases, and, the Figure 5, as follows, shows this increase with time during one of
those electrowinning tests.

800
700
Concentration of- CN- /ppm

600
500
400
300
200
100
0
0 10 20 30 40 50 60 70 80 90 100
Time (min)

Figure 5. Variation of free cyanide concentration during the electrowinning test.

The current efficiency and the specific energy consumption were evaluated using the
following expressions:

V (C o C t ) 1
CE (%) = x100 (7)
1 t

nF 0 I (t )dt
where F = Faradays constant (C mol-1), n = number of electrons in the electrochemical
reaction.

It can be observed, from Figure 6, that the current efficiency, for copper deposition, decreases,
as expected, since the current consumption for hydrogen evolution increases dramatically as
the copper concentration decreases, as a result of the electrolyte decomposition.

100
Current Efficiency for Copper (%)

90

80

70

60

50

40
30
0 5 10 15 20

Time (min)
Figure 6. Current efficiency vs. electrolysis time considering the concentration decay shown
in Figure 4.

Conclusions

It has been show that it is feasible to electrowin gold, in low concentrations, along with
copper in the g dm-3 range, from cyanide solutions, to achieve gold levels of few ppb with
reasonable cell performance within few minutes. In addition, one of the advantage of such
reaction system is the possibility of recycling de free cyanide, generated during the cathodic
reactions, to the leaching process.
One has to mention that apart from removing the gold within few minutes of electrolysis,
together with high copper content, waving for the possibility of recovering it passing the
solution once through the cell, the alloy produced (Cu + Au) can be sent to a copper
electrorefining facility so as to proceed to the copper electrorefine getting the gold as anode
slime.

Acknowledgments

To CETEM/MCT (Centre for Mineral Technology) for financial support.

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