MineralsEngineering,Vol.14,No.9, pp.

963-974,2001
Pergamon © 2001ElsevierScienceLtd
Allfightsreserved
0892-6875(01)00104-2 0892-6875/01/$- seefrontmatter

GOLD ELECTROWINNING FROM DILUTED CYANIDE LIQUORS:

PERFORMANCE EVALUATION OF DIFFERENT REACTION SYSTEMS*

L . A . D . B A R B O S A ~, L . G . S . S O B R A L ~, A . J . B . D U T R A I

§ Centre for Mineral Technology - Rio de Janeiro, RJ, Brazil. E-mail: lsobral@cetem.gov.br
~[Federal University of Rio de Janeiro, RJ, Brazil
(Received 5 January 2001; accepted 8 June 2001)

ABSTRACT

This work deals with the performance of porous electrodes by using electrolytic cells with similar
characteristics to the Zadra' s one and with mechanical devices to increase the mass transport to the
cathode. The flow-by configuration was the experimental arrangements used. Gold electrowinning
was carried out with distinct cyanide solutions, namely: pure synthetic solution and synthetic
solution with metallic impurities. This study aimed at investigating the effect of some parameters on
the direct electrowinning of gold from cyanide solutions and a comparative study of two kinds of
three-dimensional electrodes (stainless steel mesh and mild still wool). The current efficiency and
the energy consumption were also analysed considering three competing cathodic reactions: gold
deposition, oxygen reduction and hydrogen evolution. A mathematical model was also evaluated
aiming at determining, experimentally, the mass transport coefficients considering the reaction
systems under study. © 2001 Elsevier Science Ltd. All rights reserved.

Keywords
Extractive metallurgy; electrowinning; reduction

~TRODUCTION

Heap leaching with cyanide solutions became an attractive route for gold extraction from certain oxidised
ores, producing pregnant solutions in the range of 0.5 to 10 mg L-1 of gold. The current technology for gold
recovery from such diluted solutions usually involves the adsorption of the gold-cyanide complex ion on
activated carbon (Filmer, 1982; Paul et al., 1983). The gold is then stripped to produce richer gold
solutions, with concentrations ranging from 50 to 2500 mg L -~. Those solutions are then electrolysed using
steel wool as a cathode. Alternatively, small volumes of solutions, relatively rich in gold with considerable
amounts of silver, can be processed through cementation with zinc powder (Hiskey, 1983), although this
process is not commonly applied to the gold heap leaching liquors. Several authors (Sobral, 1993; Eagles et
al., 1984; Mooiman et al., 1983) have proposed a simplified flow sheet, where gold was directly
electrowon from the pregnant heap leaching solutions, eliminating, therefore, the gold complex adsorption
and desorption steps from activated carbon and its further regeneration as such.

This work deals with the performance evaluation of electrolytic cells, with three-dimensional electrodes,
for the electrowinning of gold from diluted cyanide solutions. The developed electrolytic cells present

* Presented at Minerals Engineering 2000, Cape Town, South Africa, November 2000

963
964 L.A.D. Barbosaet aL

similar characteristics to the Zadra's original design (Zadra e t al., 1952), incorporating solution re-
circulation devices in order to increase the transport of electroactive species to the cathodic surface. A
synthetic diluted gold cyanide solution was initially used to establish the best experimental conditions for
the gold electrowinning to take place. The gold deposition rate, selected impurities behaviour, current
efficiency and energy consumption of those reaction systems, incorporating the aforementioned cells, were
analysed, considering three cathodic competing reactions: gold deposition, dissolved oxygen reduction and
hydrogen evolution.

Electrochemical reactions

During gold electrowinning, the following cathodic reactions should be considered:

Au(CN)2- + e- --~ Au + 2CN- ; E ° = -0.600V (1)

0 2+ 2H20 + 4e- - ~ 4OH- ; E ° = 0.401V (2)

0 2 4" H20 + 2e- --~ OH- + HO2-; E ° = -0.065V (3)
2H20 + 2e- --~ HE + 2OH- ; E ° = -0.828V (4)

The complex Au(CN)2- is reduced to metallic gold, under diffusion control, according to Reaction (1).
Reactions (2) and (3), representing oxygen reduction in alkaline solutions, are the main cathodic reactions
competing with gold deposition and consuming a great deal of the available current on the cathode, as the
electrolyte is supposed to be saturated with oxygen. Reaction (4) represents the hydrogen evolution in
alkaline solutions, which can also occur, along with gold deposition, at more cathodic potentials.

EXPERIMENTAL

For the rotating disc test, the cell was a 250 ml glass beaker with a glass frit to separate the working and
counter electrode compartments, and an acrylic cover with roles for a nitrogen bubbler. The gold deposition
was studied in a vitreous carbon rotating disc electrode (RDE) with 3.7 x 10-5 m 2 of geometrical area. The
counter electrode was a platinum spiral wire, and as reference, a saturated calomel electrode in a Luggin
probe, just under the rotating disc. The electrode was polished, to a mirror finishing surface, with diamond
lapping compound (Hyprez Five Star Engis Ltd.) using a silk cloth and a water soluble lubricant (Hyprez
Fluid Type W). Gold was introduced into solution as KAu(CN) 2 and free cyanide added as KCN. The
solutions, used for gold deposition studies, containing 0.5M of K2SO4 as support electrolyte. The solutions
were prepared with deionised distilled water and were deaerated with oxygen-free nitrogen before
recording the steady state polarisation curves. The linear potential sweep was accomplished using a
potentiostat EG&G Applied Research, model 173. The applied potential and the resulting current were
stored in a PC computer through data acquisition software (Labtech Notebook) using a high resolution data
acquisition board (Mini-16-Strawberry Tree - - Computer Instrumentation & Controls) and subsequently
analysed.

Electrowinning tests were accomplished with diluted synthetic gold cyanide solution (10 mg L-t), and with
synthetic gold cyanide solution in the concentrations of 10 and 200 mg L -~, and metallic impurities in
concentrations similar to those found in industrial pregnant solutions. The electrolytic cell used in this
study, for the gold deposition experiments, is shown in Figure 1. It has an inner volume of 0.35 L (7.0 cm
diameter per 9.0 cm length) and is similar to the original Zadra's design, but with an auxiliary pump for
recirculating the electrolyte within the cell. The "Original Zadra Cell" denomination was used for the tests
carried out without an auxiliary pump.

Two different kinds of cathodes were tested: a mild steel wool (MSW) and a stainless steel mesh coil
(SSM). The main differences between those electrodes, as shown in Figure 2, are the steel fibres
arrangement and the surface areas. The white-greyish colour shown in Figure 2, for both electrode
materials, is relative to a thin layer of gold electrodeposited on the steel fibres during one of those
 Goldelectrotwinningfromdilutedcyanideliquors 965

electrowinning tests. As can be observed in the steel wool the fibres are quite disordered, which is not the
case of the stainless steel mesh.

]R.dm'm1R'scelectro4e
-"~t
Lua~Cqx~n'~

ln-drub6cCell

~- ---* A=d~-,7 Prop

• • l)islnlnrwor ad'Sa~buLiima
[ ] • l"mLmstiaaAJ:m,lnim~
Cmqpanrllmat
• • Cetltodb
U • l,w~pm,~,,~ b p m ' m ~ r
• 6nms~
Rueryok l:~qm4ac

Fig.1 Modified Zadra cell.

Fig.2 Scanning electron microscopy of the three-dimensional electrodes used: mild steel wool (MSW)
and stainless steel mesh (SSM). MEV, at 150x magnification.
966 L.A.D. Barbosa et al.

The 65 mesh stainless steel (AISI 304) had a surface area of 1.276 m 2 g-1 (determined by BET) and the
mild steel wool of 1.593 m 2 g-i. The anode, made out of AISI 316 stainless steel mesh, is encompassing the
cathode. The cathode was separated from the anode by a polypropylene cloth (Z10,425-6 - - Aldrich), to
avoid the electrodes short circuit and to minimise the oxygen migration, generated in the anode, to the
cathodic compartment decreasing, thus, the reoxidation of the deposited gold.

The cathodes, each one in its due course, were placed surrounding the current distributor, which consisted
of a stainless steel tube perforated along its length. In the comparative electrowinning tests, the
aforementioned cathodes, in a cylindrical configuration, were prepared considering their respective surface
areas, so that the respective current densities were the same when applied a certain current intensity. In this
case, the mass per unit volume of steel wool and stainless steel mesh cathodes were, respectively, of 0.143
g cm -3 and 0.178 g cm -3.

Two litres of synthetic gold cyanide solution were used in each test. The solution flow rates, through the
reaction system, were controlled by a peristaltic pump and varied from 0.5 L rain -l up to 1.0 L min -1.
During the electrowinning tests, samples were taken, every 15 minutes, for chemical analysis.

Energy consumption and current efficiency

At the end of each test the current efficiency (CE) was calculated considering the gold reduction reaction,
as shown in Equation 5:

n.F.V(C i C/
CE = t
- ) 100(%) (5)

f l(t)dt
o

where, V is the electrolytic solution volume used in each test, Ci the initial gold concentration in the
electrolyte, Cf the final gold concentration, F (96485 A.s.mol -l) the Faraday's constant, n the number of
electrons involved in the gold reduction (n = 1) and I the current intensity. The specific energy
consumption (EC) was calculated using the following equation:

nF
EC = E 3600.M.CFf (k Wh.kg -~) (6)

where E is the cell voltage (Volt), M the gold atomic weight, n the number of electrons involved in the gold
reduction (n = 1), F the Faraday's constant (96485 A.s.mo1-1) and CE the current efficiency (%).

Methodology of the tests carried out with synthetic impure gold cyanide solutions in Zadra's cells

The purpose of this part of the study was to simulate an industrial solution with the typical metals
associated to gold ores (Ag, Cu, Ni, Pb and Fe), in order to verify the behaviour of this solution considering
the electrolyte recirculation system, during the gold electrowinning, from aqueous cyanide solutions, in
comparison to the results obtained with pure electrolyte. The impure solution was prepared with chemicals
containing those elements. The typical composition of such solution is shown in Table 1.

TABLE 1 Composition of the synthetic impure electrolyte

Metal Concentration (nag L"1)
Au 10
g•,,
Pb 1.3
Fe 100
200
Cu 370
chr (free) 5oo
 Gold electrotwinningfromdilutedcyanideliquors 967

RESULTS AND DISCUSSION

The influence of the gold concentration on gold deposition

The influence of the gold concentration on its deposition rate is shown in Figure 3. The curves show that
the limiting current for gold deposition increases cathodically in 0.7 mA, when the gold concentration is
increased from 0.005 mol L -1 to 0.01 mol L -l. For higher free cyanide concentrations, these curves present
a similar behaviour, however, they are displaced to more negative potentials, as should be expected,
according to the equilibrium of Reaction 1. For one fold increase in the free cyanide concentration the
cathodic potential is shifted by 0.118 V, requiring, therefore, to change the potential to more negative
values, in order to assure that the process be operated at the potential corresponding to the limiting current
or slightly above it.

0.5

0.0

-1.0

-2.0
- 1.25 - l.e$ - 0.85 - 0.6a
Potential O t is. SHE)

Fig.3 Current intensity v s . electrode potential curves showing the effect of gold concentration. [KCN]:
0.03 mol L -t, rotation speed: 10Hz, potential scan rate: 0.01 V s -1.

Electrowinning tests with diluted synthetic gold cyanide solutions (Au concentration = 10 ppm)

The results of experiments accomplished with and without the solution recirculation system are shown,
aiming at investigating the effects of: i) current intensity on the cathodic potential and energy consumption;
ii) the potassium hydroxide concentration on the current efficiency and energy consumption; iii) the
electrolyte flow rate (EFR) and cell volume recirculation flow rate (RFR) on gold extraction.

The effect of current intensity on the current efficiency, cathodic potential and energy consumption
during the gold electrowinning process without solution recirculation (original Zadra cell)

The effect of the current intensity on the current efficiency, cathodic potential and energy consumption is
shown in Figures 4, 5 and 6 respectively, considering the original Zadra's cell. Figure 4 shows a maximum
in current efficiency close to -0,5 A.

The current efficiency for gold deposition can be interpreted as the result of the consumption of a fraction
of the total current by side reactions, simultaneously to the gold electrowinning process. Thus, such
efficiency can be defined by:

CE(%) = II (7)
I l + 12 + 13 + 14

where Ii, 12, 13 and 14 are the partial currents used in the cathodic reactions (from (1) to (4), respectively).
Thus, the curve shape shown in Figure 6 is an indicative of relative changes in the aforementioned partial
968 L.A.D. Barbosaet al.

currents with the applied current intensity to the reaction system, or, more specifically, with the cathodic
potential.

1.0

0.5

E
r~
o.o i i s, , I

-0.2 -0.3 -0.4 -0.S -0.6 -0.7

Current Intmsity (A)

Fig.4 Effect of current intensity on the current efficiency using a stainless steel mesh cathode with a
solution flow rate of 8.33 x 10 -6 m 3 s -1 (0.5 L min-l).

-L2

-1.0

-0.8

1 -0.6

-0.4

-0.2 I I , I I

0.2 -0.3 -0.4 -0.5 -0.6 -0.7

Current (A)

Fig.5 Effect of the current intensity on the cathode potential using a stainless steel mesh cathode and a
solution flow rate of 0.5 L min -l.

•.-, 1200

0 , , -- | ,

-0.2 -0.3 -0.4 -O.S -0.6 -0.7

Currem(A)

Fig.6 Effect of the current intensity on the energy consumption using a stainless steel mesh cathode and a
solution flow rate of 0.5 L min-1.

Aiming at verifying, in each test, the potential variation along the radius of the cylindrical cathode, the
cathode potential (stainless steel mesh) was monitored in two different positions, close to the anode and
next to the current feeder. The cathode potential values against the standard hydrogen electrode (SHE) ware
around -0.75 V for the lower current used (-0.2 A) and about -1.10 V for the higher current (-0.7 A),
when measured next to the anode. In the measurements made close to the current feeder, the potential
values were roughly 0.19 V less cathodic (-0.54 and -0.86 V, respectively) as shown in the Figure 5. This
 Goldelectrotwinningfromdilutedcyanideliquors 969

is due to the ohmic drop throughout the electrode cylinder radius. The curve of Figure 5 shows that, for the
lowest values of the cathodic current intensity, the predominant reduction reactions are the oxygen
reduction and the gold deposition. The oxygen reduction reaction occurs at limiting current and, therefore,
is no longer accelerated by increasing the cathodic potential.

The gold deposition, occurring slightly above the reversible cathodic potential, is just partially charge
transfer controlled and, therefore, the deposition rate still increases with cathodic potential. Thus, the
current efficiency in this region increases with the cathodic current until the hydrogen evolution begins,
which is intensified as the potential becomes more negative, causing a decrease in the current efficiency, as
previously shown. The gold deposition process, at more negative potentials, starts to be diffusion
controlled, and the oxygen reduction reaction keeps on occurring at the limiting current. The current
efficiency, calculated through Equation 5, decreases as the cathode potential is changed to more negative
values. These effects reflect in the energy consumption, as presented in Figure 6, which shows a dramatic
drop in the energy consumption when the cathodic current is increased up to -0.4 A.

The potassium hydroxide concentration also presents a remarkable effect on the current efficiency and
energy consumption. When its concentration is raised from 50 mol m -3 to 150 mol m -3, the current
efficiency is increased from 0.7% to 1.1% and the energy consumption drops from 140 kWh kg -~ to about
60 kWh kg -1. This behaviour should be due to the increase in the electrolyte conductivity as the ionic
strength increases. Consequently, the porous cathode area is more effective for gold reduction, and,
additionally, decreases the oxygen solubility in the electrolyte, which also enhances gold recovery.

Effect o f the electrolyte flow rate (EFR) and solution cell v o l u m e recirculation on the gold extraction
(modified Z a d r a cell)

The cell used in these experiments was the modified Zadra one. This cell was developed to provide an
uniform solution flow through the three-dimensional cathode. In this reaction system, besides the
electrolyte circulation flow, through the electrolytic cell, from the electrolyte reservoir, another peristaltic
pump was in charge of recirculating the internal solution volume of the cell to increase the mass transport.
The gold extraction is increased with the electrolyte flow rate (EFR) up to 9 x 10 -6 m3s-I, and then
decreases because there is not enough time for substantial reduction of the electroactive species of interest,
the Au(CN)2-.

Keeping constant the electrolyte flow rate and varying the recirculation flow rate, it is observed that the
gold extraction increases as the recirculation flow rate is increased, as shown in Figure 7, because the
transport of electroactive species to the cathode surface is substantially enhanced. However, although the
mean residence time does not have been affected by recirculation of the internal solution volume of the
cell, the change to more turbulent regimes resulted in a decrease of the diffusion layer thickness, decreasing
the concentration polarisation and, therefore, increasing the gold extraction rate. On the other hand, it was
verified that increasing the electrolyte flow rate (EFR) from 0.5 L min -1 to 1.0 L min -1, while varying,
simultaneously, the recirculation flow rate (RFR), there was a decrease in the gold extraction.

90
80
70
60
50 n-!
40
30
I I I
20
0 1 2 3 {x 10 "s)
Redrculstiou Flow RaCe{mJ s "I)

Fig.7 Effect of electrolyte and recirculation flow rates on gold extraction using a stainless steel mesh
cathode. Cathode potential: -0.96 V(SHE).
970 L.A.D. Barbosaet al.

Tests with gold--cyanide solutions containing metallic impurities

Figure 8 shows the influence of cathodic potential on metal recovery for solutions containing metals
usually present in gold ores (Ag, Cu, Ni, Pb and Fe). The tests were carried out in the cell with the stainless
steel mesh cathode, with and without internal electrolyte recirculation. This results indicate that the
recovery of all metals, except nickel, is increased as the potential increases cathodically (from -0.86 up to
- 1.06 V) and how effective are the gold and silver recoveries, when the recirculation system is in operation
(Figure 8B).

100 O0

0' 80

60
METALI METAL
tt A u l It Au
A Cul 40 A Cu
o Ag] ~. O Ag /
* P.bl / • Vb /

22J
2O 20

0 ~ ' " ' --

-0.8 -0.9 -L0 -LI -0.8 -0.9 -LO -LI

Potential (V m. SHE) P o t m ~ d (V ~ SHE)

(A) (B)
Fig.8 Influence of cathode potential on gold and metallic impurities recovery for the tests without (A) and
with (B) electrolyte recirculation. SSM cathode. EFR: 0.5 L min -I. RFR: 2.0 L min -l.

High gold, silver and lead recoveries with comparatively low copper recovery, but also increasing, are
observed when the cathodic potential becomes more negative. Such results show, clearly, that the
electrolyte recirculation increases the turbulence, decreasing, consequently, the diffusion layer thickness,
which intensifies the transport of electroactive species to the cathode surface, enhancing the gold recovery,
which indicates a promising way for dealing with real liquors. It was also observed that nickel was not
recovered in the potential range considered in this study, meaning that the overpotential applied is not high
enough for depositing this metal. It is also interesting to notice that copper starts to be deposited after a
certain cathodic potential (-0.86 V) being reached, where the gold is nearly completely deposited (over
90% running the electrowinning process with electrolyte recirculation and over 80 % without
recirculation). This characteristic implies that gold can be deposited, efficiently, without influence of
copper, which starts to interfere when gold removal is close to 100%.

Comparative potentiostatic gold electrowinning tests by using stainless steel mesh and mild steel wool
cathodes with and without electrolyte recirculation

The results of the comparative potentiostatic electrowinning tests are summarised in Table 2. One can see
that, at potentials of -1.06V, with the electrolyte recirculation system activated or not, and identical
experimental conditions, including the same stainless steel mesh cathode, the highest and fastest gold
(99.8% in 60 min), silver, lead and copper recoveries were obtained when the recirculation system was in
operation (Figure 9). This occurs, as expected, due to the decrease of the diffusion layer thickness, which
enhances the transport of the electroactive species to the cathode surface.
 Goldelectrotwinningfromdilutedcyanideliquors 971

TABLE 2 Metal recovery for comparative potentiostatic electrowinning tests

Te~ conditions Metal recovery after 1 hour (%)
Cathode; Potential (V vs. SHEI; RFR Au Cu Ag Ni Pb Fe
SSM~ -1.06V; 2.0 L rain" 99.80 35.62 98.92 0.00 98.89 0.00
SSM; -I.06V; no reeireulation 90.10 31.05 82.06 0.00 98.25 0.00
MSW; -1.06V; 2.0 L rnin"t 98.00 13.14 98.04 0.00 98.67 0.00
SSM; -0.96V; no reeirculation 85.99 26.10 79.91 0.00 28.57 0.00
MSW; -0.96V; 2.0 L rain"t 96.00 15.05 75.52 0.00 35.57 0.00
MSW; -0.96V; 1.0 L rain"1 61.04 12.67 60.18 0.00 30.01 0.00
MSW; -0.96V; no reeireulation 53.98 11.09 53.72 0.00 35.67 0.00
MSW; -0.86V; no reeireulation 52.42 1.32 50.32 0.00 29.63 0.00

The use of a more cathodic potential does not cause significant changes in the gold concentration decay,
when all the other process parameters are kept unchanged. This indicates an operation at limiting current
and, consequently, the gold deposition process, on stainless steel mesh and on mild steel wool cathodes, is
controlled by the transport of gold--cyanide species to the cathode surface.

400
' 0 Au * Cu
Ag • Ni
gI t~
1 -
200 i m m ,

100 a. t .
z
i
0
0 10 20 30 40 50 60 7O 0 10 20 30 40 50 60 70
T i e (mi) T~e(~n)

Fig.9 Metal concentration-time profile during electrolysis. Stainless steel mesh cathode. Cathode
potential: - 1.06 V (SHE). EFR: 0.5 L min-I. RFR: 2,0 L min -].

Determination of the mass transport coefficient (km) for gold deposition

The analysis introduced here is valid for a reactor whose size cannot be considered insignificant with
regard to the reservoir volume, where is the solution to be treated. It is considered that the reactor is being
operated under ideal plug-flow conditions, which means that does not exist axial or lateral dispersion inside
the electrode.

The objective of such analysis was to obtain an analytic solution for the concentration variation of a species
with time in the reservoir, for the particular case of the cathodic metals extraction. The proposed analysis is
generic enough and can be applied for other processes.

In this analysis it is considered the operation with electrolyte circulation (batch recycle mode). In this case
the metal concentration decreases exponentially during the electrolytic process under consideration
(electrowinning), as the electrolyte is circulated through the reactor in a plug flow regime. Equation 8 (that
can be used to show how the concentration decreases during the electrolytic process), can be used to
calculate the mass transport coefficients (kin) from the experimental concentration decay curves.

C t = Co exp {-[1 - exp(-k m A/Q)t/'r] } (8)

972 L.A.D. Barbosaet al.

where Ct is the concentration in a time t and Co is the concentration in time t = 0. Besides, t represents the
elapsed time, r = Vr / Q , is the average residence time in the solution reservoir, Vr the electrolyte volume
used in the reservoir, Q the solution flow rate and A the electrode surface area, quite difficult to be
determined due to the surface changes occurring during the electrolytic process.

The semi-log graph of C/Co against t, as shown in Figure 10, for several experiments with and without
electrolyte recirculation, can be represented by the Equation 9, obtained from the Equation 8:

Oq

i
,--.o0yx.o,6 6

• I I I I I * I
-8
0 10 20 30 40 50 60 70
t (min)

Fig.lO Logarithm of the dimensionless gold concentration against electrolysis time for the test related to
the Figure 9. Cathode potential: -1.06 V(SHE). RFR: 2.0 L min-1 and EFR: 0.5 L min -z. Stainless
steel mesh cathode.

(9)

Equation 9 predicts that a graph of In (CJCo) against t must be linear and with an angular coefficient r,
given by Equation 10, which allows the product kmA to be worked out.

r = - .~QI 1 - e x p l - - ~ ] ] (lO)
;j

A global value of kmA can be obtained through the Equation 11, that is a simple mathematical
rearrangement of the Equation 10.

kmA = -Q In(1 + rV r IQ) (11)

Although the determination of k,, value depends on the exact value of A, the cathodic surface area, the k,,,A
values lead to a very clear understanding to the comparative performance between several reaction system
configurations (stainless steel mesh cathode, mild steel wool cathode, process with and without
recirculation).

Table 3 introduces the product kmA obtained under different conditions. It is observed, for instance, that
with the configuration, where stainless steel mesh was used, with proper electrolyte recirculation, presented
the best cell performance.

When one compares, also, the process with mild steel wool cathode with the process with stainless steel
mesh cathode, under the same experimental conditions, the stainless steel mesh presented better
performance. Either using stainless steel mesh or mild steel wool the reaction system presented better
results when the recirculation system was in operation.
 Goldelectrotwinningfromdilutedcyanideliquors 973

TABLE 3 k~A product calculated through Equation 11 for different conditions

with Vr=2X 10-3 m3, Q = 3 x 10-2 m3s -1 and t =4.2 x 103s

R(~drculation Kind of r /k
System Electrode (s") (A) (In3 ~ l0 ~)
yes mesh -0.0998 -0.45 2OO
no mesh -0.0406 -0.41 81
no mesh -0.0347 -0.41 69
yes wool -0.0279 -0.37 56
yes wool -0.0292 -0.37 58
yes wool -0.0178 -0.34 36
no wool -0.0103 -0.28 21
no wool -0.0108 -0.28 22

CONCLUSIONS

This study shows the important effect of the two competing reactions with gold deposition, the oxygen
reduction and hydrogen evolution. The electrolyte recirculation device increased, significantly, the
transport of the electroactive species to the cathode surface, enhancing the gold recovery from diluted
liquors to over 99%. The aforementioned reaction system permits to operate in different configurations for
testing distinct experimental conditions considering, in addition, the use of three-dimensional electrodes.
The performance comparison among the cell configurations, shows that better results, in terms of gold
recovery, were obtained with the stainless steel mesh cathode when compared with those with mild steel
wool cathode, due, mainly, to its better surface area distribution and homogeneity, which allows a better
flow of the electrolytic solution through it, avoiding the bypass of electrolyte. The solution recirculation
system has shown to be highly efficient for the purpose of this work.

The polarisation curves provided valuable information about the electrolytic gold cyanide species reduction
process, as well as of the respective current densities, aiming at using them on industrial applications. The
correct choice of the working potential was of paramount importance considering, mostly, that others side
reactions, can be minimised and, therefore, decreasing the impact that such reactions would have on the
current efficiency and energy consumption in the gold electrodeposition process.

Considering the aforementioned experimental results one can affirm that:

It was possible to extract gold, from diluted gold cyanide liquors with recoveries higher than 99%.

The limiting current for gold deposition increases cathodically at 0.7 A, when the gold concentration
increases from 0.005 mol L -1 to 0.01 mol L -~.

The increase of free cyanide concentration changes the potential for gold deposition to more negative
values. For one fold increase in the free cyanide concentration, for instance, the potential shifts 0.118 V
cathodically.

The copper starts to be deposited only in a potential of -0.86 V (SHE), when more than 90% of the gold is
already recovered for the processes with solution recirculation and over 80 % for the process without
recirculation. This fact can be used to avoid the copper and gold co-deposition from industrial gold cyanide
solutions rich in copper.

The pH of the gold cyanide solution has a strong influence in the electrolyte conductivity (due to the
potassium hydroxide addition to the solution) and this influences, positively, the gold electrowinning and
the current efficiency for the gold extraction. For a pH higher than 13, gold recoveries higher than 99%
974 L.A.D. Barbosaet al.

were reached. The addition of 0.1 mol L- 1 raised, then, the current efficiency (in the tests with pure gold
cyanide solutions) from 0.7% to 1.05%;

The cell efficiency, with the electrolyte recirculation device in operation, is clearly evidenced when the
values of k,,A are compared. In one of the potentiostatic tests (-1.06 V), carried out with stainless steel
mesh cathode, for instance, the value of k,,,A obtained in the test with solution recirculation was 1.5 times
larger than the test carried out without solution recirculation;

The use of traditional mathematical models for calculating the mass transport coefficients, contributed,
substantially, for a clear comparison between the proposed cells configurations in this work;

The cylindrical cell performance (with regard to the gold recovery), using the stainless steel mesh cathode
is very superior to that using the mild steel wool, due to the best organisation and internal homogeneity of
such mesh, which allows a more effective flow of electrolytic solution. In the tests with identical
experimental conditions (cathode potential = -1.06 V, EFR = 0.5 L min-l and RFR = 2 L rain -1) the
following results were obtained, regarding the gold recovery: with stainless steel mesh, 99.8 % in 60 min,
and with the mild steel wool, 98% for the same 60 min.

REFERENCES

Barbosa, L. A. D., The electrowinning of gold from cyanide diluted solutions. D.Sc. thesis, COPPE,
Federal University of Rio de Janeiro, Rio de Janeiro, Brazil, 2000.
Filmer, A. O., The electrowinning of gold from carbon-in-pulp eluates. Carbon-in-pulp seminar, July, 49,
The Aus. I.M.M., Perth and Kalgoorlie Branches and Murdoch University, 1982
Hiskey, J. B., Gold and silver heap and dump leaching practice. AIME, 1983, pp. 1-7.
Mooiman, M. B. Miller, J. D. Hiskey J. B., Gold and silver heap and dump leaching practice. Hiskey, J. B.
(Ed.), AIME, 1983, pp. 101-103
Paul, R. L. Filmer, A. O. and Nicol, M. J., The recovery of gold from concentrated auro-cyanide solutions.
Proceedings of the Third International Symposium on Hydrometallurgy, SME-AIME, Atlanta, Georgia,
1983.
Sobral, L. G. S., The electrowinning of gold from dilute cyanide liquors using a three-dimensional nickel
foam. Ph.D. tesis, Imperial College, London, 1993.
Zadra, J. B. Engel A. L. and Heinen, H. J., Process for recovering gold and silver from activated carbon by
leaching and electrolysis. Bureau of Mines R14843, 1952.

C o r r e s p o n d e n c e on papers published in Minerals Engineering is invited b y e-mail to

bwills@min-eng.com