Metallurgist, Vol. 47, Nos.

3–4, 2003

IMPROVING A TECHNOLOGY USED FOR THE

ELECTRO-REFINING OF GOLD

Yu. A. Voronin, V. P. Kondaurov, UDC 621.357

B. A. Spiridonov, and Yu. V. Litvinov

As is known, gold has been the monetary standard throughout the world since antiquity. Its suitability for this role
is due to its high resistance to corrosion and high electrical conductivity, its scarcity in the earth’s crust, and the difficulty of
extracting it. However, in addition to its monetary value, gold is also an important material in technology. It is widely used
in the jewelry industry, instrument construction, electronics manufacturing, the production of prostheses and chemical equip-
ment, gold-plating, and other applications.
The main sources of commercially mined gold are gold-bearing sands and polymetallic ores that contain this ele-
ment. Deposits of gold in Russia are found in the Ural and Eastern Siberia (the basins of the Aldan, Kolym, Zeya, and Amur
rivers). Large gold fields exist in South Africa, Canada, Australia, and Kazakhstan.
One of the most common hydrometallurgical methods used to extract gold from ores is cyanidation. Other methods
are also employed, including amalgamation. Nearly all of the gold recovered by the various methods is further concentrated
at refining plants. The raw material that these plants receive for processing is obtained from the smelting of mined gold-zinc
deposits, black gold obtained after amalgam separation, alluvial gold obtained from the concentration of alluvial deposits and
ores, and cathodic black gold obtained from thiocarbamide regenerators. All gold-bearing alloys have a complex chemical
composition. In addition to gold and silver, they contain copper, lead, iron, tin, nickel, mercury, arsenic, antimony, and other
elements as impurities.
Gold is currently produced using two main methods of refining – chemical and electrochemical. The chemical
method involves dissolution of gold-bearing alloys in a mixture of acids – hydrochloric and nitric (aqua regia). This is fol-
lowed by reduction of the gold with silver anhydride or sodium sulfite. Among the shortcomings of this method are the dan-
ger to the environment and the fact that it is impossible to process gold alloys with a silver content greater than 15%. One
reason for the latter lies in the difficulties connected with separating silver chloride from reduced gold, which makes it impos-
sible to obtain gold of high (99.999%) purity. Gold of this purity can be obtained by the electolytic method. To do so, anodes
of a gold-bearing alloy are immersed in a solution of hydrochloric acid. There, under direct electrical current, gold is oxi-
dized within the temperature range 50–80°C:

Au – 3e = Au3+.

In a hydrochloric acid solution, gold ions (III) form chloroauric acid HAuCl4. Dissociation of the acid results in the
formation of the anions AuCl–4, which are reduced on the cathode to metallic gold:

AuCl–4 + 3e = Au + 4Cl–.

One distinctive feature of this process is that with the use of an electrolyte having an initial gold concentration of 150–200
g/liter, the cathode and anode spaces are separated from one another during the electrolysis operation by using membranes made

Ferrit Scientific Design-Engineering Office (Voronezh, Russia). Translated from Metallurg, No. 4, pp. 49–50, April,
2003.

0026-0894/03/0304-0163$25.00 ©2003 Plenum Publishing Corporation 163

of various materials (porcelain, glass, ion-exchange films, etc.). After the necessary concentration of gold has been reached, the
membranes are removed from the electrolytic bath and a direct current of the density 10–15 A/dm2 is sent through the electrolyte.
Under these conditions, gold of high purity is deposited on the cathode (which is usually made of titanium or gold foil).
At the same time that electrolysis is taking place, the impurity metals are being oxidized and becoming concentrat-
ed in the electrolyte. When the critical concentration of an impurity metal is reached, the electrolyte is replaced by a new
electrolyte to keep that impurity from being co-precipitated with gold. The new electrolyte is prepared in a separate elec-
trolytic bath. The gold in the electrolyte contaminated by the impurity metals is reduced, for example, by the sulfite method
and precipitated.
Use of the electrolytic method is limited by the fact that it is impossible to process gold alloys that have a silver con-
tent greater than 15%. This limitation stems from the adverse effect of silver on the anode process, since a passivating film
of silver chloride forms on the surface of the anode. Transient current delivery regimes are used to destroy the film, which
makes it possible to process gold alloys with up to 20% silver. For example, an asymmetric current might be employed, with
the delivery of positive voltage to the anode being alternated with shorter periods of negative voltage. During cathodic polar-
ization, the passivating film of silver chloride loses its bond with the anode, falls to the bottom of the bath, and becomes part
of the anode slime. The reason for these events is probably the rapid and substantial change in the microstresses on the sur-
face of the anode under the influence of the polarizing current.
To allow the processing of gold alloys with a high silver content (up to 35–40%), we developed a method of elec-
tro-refining that employs pulsed bipolar current. Anodic passivation is overcome by the periodic action of current pulses,
which is realized by changing the ratio of the current pulses with positive and negative signs: n+ : n– = (20–30):(1–5), where
n is the number of pulses of the corresponding sign. These parameters are established during electrolysis as a function of the
electrochemical characteristics of the electrolytic bath, which are determined mainly by the silver content of the gold alloy.
Electrochemical studies established that the size of the passivation region on the anodic polarization curves decreas-
es significantly when the pulsed bipolar current is used under certain conditions. It might be possible to destroy the silver
chloride film if the ratio of pulse frequency to pulse amplitude is optimized so as to prevent the anode’s passivation. The
maximum benefit is obtained when the system is supplied with a packet of positive and negative pulses having different fre-
quencies and durations.
The anode process is substantially affected by lead in the presence of copper. When the system contains up to 10%
lead, 15–20% copper, and 15% silver, the rate of dissolution of the anode decreases sharply due to the formation of films of
lead and copper chloride in addition to silver chloride [1]. The chosen pulsed current regime makes it possible to signifi-
cantly alleviate passivation and speed up dissolution of the anode.
It was established that the use of ion-exchange membranes in the construction of the cathode chambers, the use of
anode chambers made of special filtering materials, and optimization of the pulsed current regime makes it possible to obtain
cathodic gold of 99.999% purity.
Russian Federation Patent No. 2122594 has been issued for the above-described method of electro-refining gold.
The method has successfully undergone commercial trials at the Kolyma Refining Plant and the Moscow Special Alloys
Factory.

REFERENCES

1. Yu. V. Baimakov and A. I. Zhurin, Electrolysis in Hydrometallurgy [in Russian], Metallurgiya, Moscow (1977).
2. V. V. Lodeishchikov, The Hydrometallurgy of Gold [in Russian], Nauka, Moscow (1980), pp. 15–18.
3. L. V. Chugaev (ed.), Metallurgy of the Noble Metals [in Russian], Metallurgiya, Moscow (1987).
4. N. T. Kudryavtsev (ed.), Applied Electrochemistry [in Russian], Khimiya, Moscow (1975).
5. V. P. Kondaurov, B. A. Spiridonov, et al., System Problems on Quality, Mathematical Modeling, and Information and
Laser Technologies: Materials of an International Conference and Russian Science Seminar, VGTU, Voronezh
(2001), pp. 66–68.

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