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Electrorefining

Electrorefining

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Electrorefining
Electrorefining is anelectrolytic process that involvesanodically dissolving a metalat the positiveelectrode in acell and simultaneously re-depositing the same metal at thenegative electrode. The first patents for metal electrorefining were for copper and were granted in 1865. The firstsuccessful plant was built in Pembrey,Wales in 1869 and this was followed in1876 by the Norddeutsche plant inHamburg, Germany, which is stilloperating today and is the largestcopper refinery in Europe. The firstcommercial operation in the USA wasconstructed in Newark, New Jersey in1883. The Newark plant produced 2-3tonnes of electrolytic copper per dayduring its first year. This contrasts withthe electrorefining capacity atChuquicamata in Chile in 2003 of over 1,700 tonnes per day.Electrorefining is the final step in thesmelting 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 in2003. Smelting produces
blister copper 
, which contains about 99% copper and this iselectrorefined to
cathode copper 
that has a purity of around 99.99% copper. The positiveelectrodes for the electrorefining cell are cast from the blister produced by smeltingcopper sulfide flotation concentrates, and weigh 300 to 380 kg; the negative electrodesare the same as in copper electrowinning discussed in the previous section. Theelectrolyte contains 40 grams/liter of copper as copper sulfate and 150 to 200 g/l sulfuricacid and the refining cells operate at ~60
o
C (~140
o
F). Small quantities of glue, thioureaand chloride are added to the electrolyte; these compoundsadsorbon the copper surfaceand help to form a dense electrodeposit. Acurrent densityof ~200A/m
2
is passed between the negative and positive electrodes and this results in acell voltageof about0.28V. Theelectrical energyconsumption in the copper electrorefining cell is ~0.25 kWh/kg.Electrorefining is successful because metallic impurities that are more noblethan copper, that is, are lower in theelectrochemical series,do not enter the electrolyte when copper  dissolves at the positive electrode. These impurities include precious metals – silver, goldand the platinum group metals – which are recovered by treatment of the sludge that falls
 Fig. 6. The Xstrata copper electrorefining tankhouse at Copper Refineries in Townsville,Queensland, Australia, which developed and uses the ISA PROCESS technology. The picture shows the top of the cells and the multiplicity of electrodes. The negatives are the most visible;between each can be seen the lugs at the ends of the positives. The crane manipulating theelectrodes is automated. (Courtesy of XstrataCopper.)
 
to the bottom of the cell. Since impurities that do enter the electrolyte are less noble thancopper, that is, are above copper in the electrochemical series, do not deposit on thenegative electrode. Some metals, for example, nickel, accumulate in the electrolyte andare 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 km
2
(kilometer = one thousandmeters)of total electrode area. This corresponds to about 50,000 positive and 50,000 negativeelectrodes suspended in about 1,500 tanks occupying a total floor area of about 6,000 m
2
.Lead is also purified by electrorefiningusing the Betts process pioneered byCominco at its smelter in Trail, BC,Canada in 1902. Lead from the smelter is melted and cast into slabs, which actas positive electrodes. Refined lead iscast into thin
 starter sheets
for thenegativeelectrodeson which lead isdeposited. The electrolyte used is ~90grams/liter hydrofluorosilicic acidcontaining ~70 g/l lead as leadhydrofluorosilicate and operates at 30to 40
o
C (86-104
o
F). Glue and ligninsulfonate are included in the electrolyteto help form a smooth deposit. Acurrent density of between 160 and 200A/m
2
is used and this gives a cellvoltage of 0.35 to 0.65 V. The energy consumption is ~0.13 kWh/kg. Refining of lead isalso carried out in sulfamide media. About 20% of the world 2003 lead production of 6.6million 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 andlead smelting, is especially interesting. While the aim in other metal electrorefining processes is to produce a massive, dense product, with silver, fine, tree-likedendritesareformed deliberately. This is achieved by plating the metal onto a substrate such asstainless steel or carbon from anelectrolytethat does not complex with silver, platingfrom a quiescent electrolyte without the inclusion of additives that promote smoothdeposits, and operating at a highcurrent density. The silver dendrites formed on thenegative electrodes can be easily harvested since they do not attach strongly to theelectrode surface. The electrolyte typically contains 150 g/l of silver as silver nitrate andnitric acidto make the pH1-1.5. The cell operates at ~35
o
C (~95
o
F) and a current densityis ~400 A/m
2
. The positive electrodes are cast silver derived from the slimes formed inelectrorefining of copper or lead. The electrorefined metal contains between 99.9% and
 Fig. 7. Lead electrorefining at the Teck Cominco smelter in Trail, BC, Canada. (©Teck ComincoMetals Ltd. Reproduced with permission.)
 
99.99% silver. The anodic slimes from silver refining are further treated to recover goldand platinum group metals.The same principle applies whenions and electronsare exposed in a liquid medium to combined electric andmagnetic fields. Motion is generated, asshown in Figure 1, whose velocity is perpendicular to the direction of thegenerating fields. In a liquid solutionwith an astronomical number of ions"swimming" in a big pool of solvent(for example water), the outcome of thefield interaction might appear to bechaotic and dissipated in randomness.Fortunately, this is not what happens.Glancing again at Figure 1, imagineions, forced by the magnetic and electricfields, sweeping by the solid plate. Thesweeping motion generates considerableturbulence in the tiny liquid layer adjacent to the plate, called theinterface. This interfacial turbulence isat the bottom of most, but not all,magnetic phenomena inelectrolysis,  that is whenelectric currentflowsthrough anelectrolyte solutionin acell  held between the pole faces of amagnet. An important practical result,magnetically enhancedcathodic deposition of metals (in
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 growingnew field of scientific and technical endeavor.
 Fig. 1. Ionic movement is generated in a mediumby the coupling of an electric and a magnetic field. The direction of movement is perpendicular to the fields. The resulting "sweep" action along the solid surface generates strong local turbulence enchancing masstransport at the interface (see Appendix
 
 ).

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