6

Electrolytic Refining and

Winning of Metals
v. A. ETTEL and B. V. TILAK

1. Introduction
In electrolytic refining, the plates of crude metal are anodically dissolved
in a suitable electrolyte, while "pure" metal is deposited on the adjacent
cathodes. The electrorefining process was introduced about a hundred years
ago to produce a substitute to fire-refined copper. Today, practically all of the
world's copper production (-8,000,000 metric tons/year) is electrorefined,
constituting by far the largest electrolytic refining industry. Much smaller, but
also important, are the electrolytic refining industries producing lead, nickel,
silver, and other minor metals.
The soluble anodes in nickel refining can also be cast from nickel matte
containing -20% S. This electrolytic process, although technically very similar
to refining with a metallic anode, is not a refining process in the true sense and is
sometimes called electrowinning with a soluble anode. (1)
A process closely related to electrorefining is electrowinning with insolu-
ble anodes. In this process, the metal is dissolved chemically, e.g., by leaching
calcined ore, etc. The pure metal is then "electrowon" using insoluble anodes,
e.g., lead anodes, producing oxygen:
2H2 0 -+ O 2 + 4H+ + 4e

V. A. ETTEL • J. Roy Gordon Research Laboratory, INCO Metals Company, Sheridan Park,
Mississauga, Ontario L5K 129, Canada. •• V. TILAK • Hooker Chemical Corporation,
Research Center, Long Road. Grand h;land, New York 14072.
327

J. O. Bockris et al. (eds.), Comprehensive Treatise of Electrochemistry

© Plenum Press, New York 1981
328 v. A. ETTEL and B. V. TlLAK

Currently some 70% of the world's total zinc production (-5,000,000

metric tons/year) is made by electrowinning with insoluble anodes, and this
percentage is increasing.
Although the anodic reactions are different, most other aspects of refining
and electrowinning processes using aqueous electrolytes are similar and will be
discussed in the next section, with prime emphasis on the technological details.
Due to their specific nature, the processes employing fused salt electrolytes,
such as aluminum electrowinning, are not included in this review.

2. Electrochemical Principles of Electrorefining

and Electrowinning

2.1. Electrochemical Selectivity

In an ideal electrorefining process, the metal would dissolve "nearly
reversibly" on the anode and plate "nearly reversibly" at the cathode. The
impurities which are more electropositive (noble) than the electrorefined metal
will not dissolve at this potential and will remain in the anode slime. The
impurities which are more electronegative (common) than the refined metal
will dissolve anodically but will not deposit at the cathode, hence the accumu-
lation in the electrolyte.
As could be expected, this simple picture reflects reality reasonably well
only with the metals which exhibit low dissolution and deposition over-
potentials (Ag, Cu, Pb) and with impurities whose standard potentials are
sufficiently different from that of the refined metal.

2.1.1. Anodic Process

The selectivity of the anodic process is often helped by the refractory
nature of some impurity-containing compounds present in the anode metal
(Ag, Se, and Te are present in copper anodes as quite refractory selenides and
tellurides of silver and copper). In spite of this, a very small amount of silver still
tends to dissolve from copper anodes and plate onto cathodes. This partial
dissolution is suppressed by maintaining -30 mg/liter of Cl- ion in the copper
refining electrolyte, so that Ag + concentration in the electrolyte will not exceed
the value given by the solubility product of AgCl.
The "common" impurities which normally dissolve from the anode can
also be present in the anodes in a poorly soluble form. (Nickel is often present
in copper anodes as the refractory form of NiO, thus appearing at least partially
in the anode slime.) In sulfate-ion-containing electrolytes lead is insolubilized
as PbS04 • One component which, contrary to the simple theory, is always
found as a major component of anode slimes is the refined metal itself.
The typical behavior of anode impurities in various refining processes is
summarized in Table 1. It can be seen that in Au, Ag, Cu, and Pb refining