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Electrorefining

Electrorefining is an electrolytic
process that involves anodically
dissolving a metal at the positive
electrode in a cell and simultaneously
re-depositing the same metal at the
negative electrode. The first patents for
metal electrorefining were for copper
and were granted in 1865. The first
successful plant was built in Pembrey,
Wales in 1869 and this was followed in
1876 by the Norddeutsche plant in
Hamburg, Germany, which is still
operating today and is the largest
copper refinery in Europe. The first
commercial operation in the USA was
Fig. 6. The Xstrata copper electrorefining
constructed in Newark, New Jersey in
tankhouse at Copper Refineries in Townsville,
1883. The Newark plant produced 2-3
Queensland, Australia, which developed and
tonnes of electrolytic copper per day
uses the ISA PROCESS technology. The picture
during its first year. This contrasts with
shows the top of the cells and the multiplicity of
the electrorefining capacity at
electrodes. The negatives are the most visible;
Chuquicamata in Chile in 2003 of over
between each can be seen the lugs at the ends of
1,700 tonnes per day.
the positives. The crane manipulating the
electrodes is automated. (Courtesy of Xstrata
Electrorefining is the final step in the
Copper.)
smelting process for the recovery of
copper from sulfide ores, and this
process accounted for nearly 80% of the world copper production of 14 million tones in
2003. Smelting produces blister copper, which contains about 99% copper and this is
electrorefined to cathode copper that has a purity of around 99.99% copper. The positive
electrodes for the electrorefining cell are cast from the blister produced by smelting
copper sulfide flotation concentrates, and weigh 300 to 380 kg; the negative electrodes
are the same as in copper electrowinning discussed in the previous section. The
electrolyte contains 40 grams/liter of copper as copper sulfate and 150 to 200 g/l sulfuric
acid and the refining cells operate at ~60oC (~140oF). Small quantities of glue, thiourea
and chloride are added to the electrolyte; these compounds adsorb on the copper surface
and help to form a dense electrodeposit. A current density of ~200 A/m2 is passed
between the negative and positive electrodes and this results in a cell voltage of about
0.28 V. The electrical energy consumption in the copper electrorefining cell is ~0.25
kWh/kg.

Electrorefining is successful because metallic impurities that are more noble than copper,
that is, are lower in the electrochemical series, do not enter the electrolyte when copper
dissolves at the positive electrode. These impurities include precious metals – silver, gold
and the platinum group metals – which are recovered by treatment of the sludge that falls
to the bottom of the cell. Since impurities that do enter the electrolyte are less noble than
copper, that is, are above copper in the electrochemical series, do not deposit on the
negative electrode. Some metals, for example, nickel, accumulate in the electrolyte and
are extracted in a separate stage.

Electrorefining of copper is a large operation. For example, an average copper refinery


producing 500 tonnes of metal per day needs 0.2 km2 (kilometer = one thousand meters)
of total electrode area. This corresponds to about 50,000 positive and 50,000 negative
electrodes suspended in about 1,500 tanks occupying a total floor area of about 6,000 m2.

Lead is also purified by electrorefining


using the Betts process pioneered by
Cominco at its smelter in Trail, BC,
Canada in 1902. Lead from the smelter
is melted and cast into slabs, which act
as positive electrodes. Refined lead is
cast into thin starter sheets for the
negative electrodes on which lead is
deposited. The electrolyte used is ~90
grams/liter hydrofluorosilicic acid
containing ~70 g/l lead as lead
hydrofluorosilicate and operates at 30
to 40oC (86-104oF). Glue and lignin
Fig. 7. Lead electrorefining at the Teck Cominco sulfonate are included in the electrolyte
smelter in Trail, BC, Canada. (©Teck Cominco to help form a smooth deposit. A
Metals Ltd. Reproduced with permission.) current density of between 160 and 200
A/m2 is used and this gives a cell
voltage of 0.35 to 0.65 V. The energy consumption is ~0.13 kWh/kg. Refining of lead is
also carried out in sulfamide media. About 20% of the world 2003 lead production of 6.6
million tonnes was electrorefined.

Nickel may also be purified by electrorefining; this process competes with the carbonyl
process that exploits the volatility of nickel carbonyl.

Silver refining, which is carried out following the separation of this metal in copper and
lead smelting, is especially interesting. While the aim in other metal electrorefining
processes is to produce a massive, dense product, with silver, fine, tree-like dendrites are
formed deliberately. This is achieved by plating the metal onto a substrate such as
stainless steel or carbon from an electrolyte that does not complex with silver, plating
from a quiescent electrolyte without the inclusion of additives that promote smooth
deposits, and operating at a high current density. The silver dendrites formed on the
negative electrodes can be easily harvested since they do not attach strongly to the
electrode surface. The electrolyte typically contains 150 g/l of silver as silver nitrate and
nitric acid to make the pH 1-1.5. The cell operates at ~35oC (~95oF) and a current density
is ~400 A/m2. The positive electrodes are cast silver derived from the slimes formed in
electrorefining of copper or lead. The electrorefined metal contains between 99.9% and
99.99% silver. The anodic slimes from silver refining are further treated to recover gold
and platinum group metals.

The same principle applies when ions


and electrons are exposed in a liquid
medium to combined electric and
magnetic fields. Motion is generated, as
shown in Figure 1, whose velocity is
perpendicular to the direction of the
generating fields. In a liquid solution
with an astronomical number of ions
"swimming" in a big pool of solvent
(for example water), the outcome of the
field interaction might appear to be
chaotic and dissipated in randomness.
Fortunately, this is not what happens.

Glancing again at Figure 1, imagine


ions, forced by the magnetic and electric
fields, sweeping by the solid plate. The
sweeping motion generates considerable
turbulence in the tiny liquid layer
adjacent to the plate, called the
Fig. 1. Ionic movement is generated in a medium interface. This interfacial turbulence is
by the coupling of an electric and a magnetic at the bottom of most, but not all,
field. The direction of movement is magnetic phenomena in electrolysis,
perpendicular to the fields. The resulting that is when electric current flows
"sweep" action along the solid surface generates through an electrolyte solution in a cell
strong local turbulence enchancing mass held between the pole faces of a
transport at the interface (see Appendix). magnet. An important practical result,
magnetically enhanced cathodic
deposition of metals (in electroplating or electrowinning), created the science and
engineering of magnetoelectrolysis.

All in all, magnets exert a strong influence on electrode processes. They can modify
deposit structure, increase the rate of deposition of the reaction product(s), change flow
patterns, and increase the intensity of mixing. Magnetoelectrochemistry is a fast growing
new field of scientific and technical endeavor.
Pure metals may conveniently be deposited from electrolyte solutions or molten
electrolytes (in electroplating or electrowinning). The process is especially inviting for
precious metals (for example gold and silver) and copper, nickel, zinc, etc., although
simultaneous hydrogen evolution in a number of cases may thwart deposit quality. The
rate of deposition per unit substrate area, measured as current density, is controlled by the
electrode potential. The higher the potential, the higher the current density up to a certain
point, beyond which the current cannot increase even if the potential is increased over a
wide range. This is the limiting current density for a given depositing species, and its
magnitude depends on electrolyte properties and design features of the electrolytic cell. If
electrolysis is carried out between the pole faces of a magnet, the limiting current density
for a species increases in proportion to the strength of the magnetic field, upon proper
matching of the magnetic and the electric fields. The strength of the magnetic field may
be expressed in terms of the magnetic flux density. A typical set of experimental
observations during the magnetoelectrolytic deposition of copper indicates an essentially
linear dependence of the maximum deposition rate on the magnetic flux density, but
limiting current densities have been shown in the literature to vary with the power
(exponent) of the magnetic flux density ranging from 0.25 to 1.64, depending on cell
design, electrolyte composition and the metal species. See Table I.

Apart from increased deposition rates, magnetic fields offer the bonus of providing
evenness and excellent adhesion of the metal deposits on their substrates, even at current
densities where deposit quality would be poor in their absence.