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استخلاص المعادن بطريقه الكهرباىيه - نسخة
استخلاص المعادن بطريقه الكهرباىيه - نسخة
استخلاص المعادن بطريقه الكهرباىيه - نسخة
Except for iron alloys and recycled metals, electrochemical reactions are used in producing much of the world’s metals. Copper and
aluminum are examples. World production of aluminum in electrolytic cells totaled 49.3 million metric tons in 2014 (Bray, 2015)
with China, Russia, and Canada being the major producers. Measured in tons, aluminum’s use exceeds that of all other metals
except iron and its alloys.
Worldwide copper production was 18.7 million metric tons with most of this production being electrorefined or electrowon
(Brininstool, 2015). Chile is the biggest producer of copper (31% of global production).
Other metals that are produced partially by electrolytic processes include cadmium, chromium, cobalt, lithium, manganese,
magnesium, nickel, and zinc.
This contribution describes the fundamental electrochemistry, thermodynamics, kinetics, and engineering phenomena that
govern electrometallurgy.
Electrochemical Reactions
Electrochemical reactions entail the transfer of electrons to or from a molecule, atom, or ion at an interface between an electronic
conductor, the electrode (through which the electrons reach or leave the interface), and an ionic conductor (through which the
ions travel). For example, copper can be deposited from aqueous solutions by the reaction
As illustrated on the left of Figure 1, addition of electrons to a species is reduction in the chemist’s terminology and reaction [1]
is termed a cathodic one; while this reduction is occurring at an electrode we term it a cathode. Reaction [1] can be reversed by
raising the potential of the electrode on which the copper has been deposited, whereupon oxidation (removal of electrons from
copper atoms to produce copper ions) occurs and this is then an anodic reaction occurring at an anode.
Current Density
Electrochemical reactions occur at interfaces; they are inherently heterogeneous and an appropriate measure of reaction rate is the
number of ions reduced (or produced) per unit interface area per unit time. From Faraday’s law (see below) this is directly linked
to the current per unit area, i.e., the current density, expressed in mA cm2 or A m2. It will be seen subsequently that this
heterogeneous nature is the bane of electrometallurgy; to produce a metal by an electrochemical route a very large electrode surface
area must be provided.
☆
Change History: April 2015. J.W. Evans updated the production statistics in the first two paragraphs (along with references). New figure (Figure 6) is included.
‘Energy consumption’ and ‘magnesium production’ have been updated. New reference is included and minor editorial changes made in the article.
External
circuit
2ε- 2ε-
Oxygen
bubble
Electrolyte
Cu2++ 2ε-= Cu
Figure 1 Schematic diagram of an electrolytic cell in which copper is being deposited at a cathode and oxygen generated at an anode.
there is no net reaction so that equilibrium exists. We expect the solution to have the same potential everywhere if its composition
and temperature are uniform, except very close to the electrode where its presence would disturb this potential. The potential
difference between electrode and solution will still depend on the electrolyte and composition but, if the temperature is 25˚C and
the only cation present is copper at a concentration of one mole per kilogram of water (a one molal solution), then the potential
difference is fixed at 0.34 V (metal potential electrolyte potential). This is the ‘standard half cell potential,’ or ‘standard electrode
potential,’ for copper and values for other metals in contact with one molal solutions are given in Table 1.
E0 (V)
3þ
Au þ 3e ¼Au 1.50
O2 þ 4H þ þ 4e ¼2H2O 1.23
Hg2 þ þ 2e ¼Hg 0.80
Ag þ þ e ¼ Ag 0.80
Cu þ þ e ¼Cu 0.52
O2 þ 2H2O þ 4e ¼40H 0.40
Cu2 þ þ 2e ¼Cu 0.34
H þ þ e ¼1/2H2 0.000
Fe3 þ þ 3e ¼Fe 0.04
Pb2 þ þ 2e ¼Pb 0.13
Sn2 þ þ 2e ¼Sn 0.14
Ni2 þ þ 2e ¼Ni 0.23
Co2 þ þ 2e ¼Co 0.27
Cd2 þ þ 2e ¼Cd 0.40
Fe2 þ þ 2e ¼Fe 0.44
Cr3 þ þ 3e ¼Cr 0.74
Zn2 þ þ 2e ¼Zn 0.76
Cr2 þ þ 2e ¼Cr 0.91
Mn2 þ þ 2e ¼Mn 1.05
Al3 þ þ 3e ¼Al 1.66
Ti2 þ þ 2e ¼Ti 1.75
Mg2 þ þ 2e ¼Mg -2.38
Na þ þ e ¼Na 2.71
Ca2 þ þ 2e ¼Ca 2.84
K þ þ e ¼K 2.92
Li þ þ e ¼Li 3.01
Note that in Table 1 there are nonmetallic electrodes. Oxygen can be reduced in an aqueous solution when the oxygen is
bubbled across the surface of an electronic conductor. Usually this conductor is catalytic (e.g., a strip of platinum) for the
reduction reaction and also serves as an electrical connection between the bubbles and the outside world. Similarly the hydrogen
ion can be reduced to produce hydrogen gas on a strip of platinum. More commonly this reaction is used in reverse with hydrogen
bubbled across the surface of the platinum. The platinum catalyzes
If the solution is at 25 1C and one molal in hydrogen ions, with hydrogen bubbles at atmospheric pressure, then we have a
standard hydrogen electrode (SHE) and the platinum has the potential in Table 1. This last potential is exactly zero! This results
from an arbitrary choice. It is impossible to use a voltmeter to measure the potential between a metal and an electrolyte without
immersing a second electronic conductor into the electrolyte. Therefore only differences in half cell potentials can be measured.
This difficulty is resolved by arbitrarily making the half cell potential of the SHE zero, whereupon all the entries in Table 1 are
potential differences between the metal electrode and the SHE.
Nernst’s Equation
What of the potential of a metal electrode under conditions where the solution is not one molal in the corresponding ion? The
answer is provided by Nernst’s equation
RT aO
E ¼ E0 þ ln ½3
nF aR
Here E is the potential of the electrode (electrode potential – solution potential), E0 is the standard electrode potential, R the
gas constant (8.3144 J mol1 K1), T absolute temperature, n the number of electrons in the reduction reaction (n ¼ 2 for reaction
[1], for example), F is Faraday’s constant (96 484 C mol1), aO is the activity of the oxidized species (e.g., activity of cupric ions in
the solution in the case of reaction [1]), and aR the activity of the reduced species. In the case of the deposition of metals aR is the
activity of the solid or liquid metal and, if the metal is close to pure this activity can be taken as unity.
For the present purposes it will be sufficient to regard the activity as equivalent to a concentration.
For reactions that are not the simple deposition of a metal, more complicated forms of Nernst’s equation apply. For example,
for the oxidation of water to produce oxygen
RT pO2 a4Hþ
E ¼ E0 þ ln ½5
4F aH2 O
Here oxygen activity is taken as its partial pressure in atmospheres (pO2 ). The activity of water, aH2 O can be approximated as
unity provided the aqueous solution is not too concentrated.
An Electrochemical Cell
Consider the system sketched in Figure 1. The solution is one molal in Cu2 þ ions and H þ ions; oxygen bubbles are in contact with
an inert metal (say lead) at one atmosphere pressure. The copper and inert metal are connected via an external circuit that could be
a simple resistor or a DC power supply. If that circuit is merely an open one (e.g., a voltmeter with a very high internal resistance),
then no current flows and both electrodes are in equilibrium with the solution and at their standard electrode potentials.
Consequently
Oxygen electrode potential Copper electrode potential ¼ 1:23 V 0:34 V ¼ 0:89 V ½6
Clearly the oxygen electrode is at a higher voltage than the copper and, if we replaced the open external circuit with a resistor,
current flows from the oxygen electrode to the copper electrode, or if the external circuit is of electronic conductors, electrons pass
from the copper to the oxygen electrode. These electrons originate from
This couple of reactions is consuming rather than producing copper. If we wish to produce metallic copper from a copper
bearing solution we need to reverse them. A DC power supply must be used in the circuit to reverse the current flow so that
electrons pass from the oxygen electrode to the copper. The DC power supply must achieve at least 0.89 V between its terminals
(more if the solution is more dilute in Cu2 þ than 1 molal or if it is more acid than 1 molal in H þ ions). It is now apparent why
the production of metals by electrometallurgy consumes significant electricity. Each cell must be supplied with current at a voltage
exceeding that of the difference of two half cell potentials. The rate (Watts) at which the electrical energy is consumed is the
product of that voltage and the current.
Reaction Kinetics
So far this treatment has been largely thermodynamic, concerned with equilibrium potentials between an electrode and a solution.
Practical electrochemical reactions are seldom close to equilibrium and consideration of electrode kinetics is appropriate. An
important parameter in kinetics is the ‘overpotential,’ Z, the amount by which the potential of an electrode exceeds the equilibrium
potential. For many electrochemical reactions the rate can be expressed by the Butler–Volmer equation:
anF ð1 aÞnF
i ¼ i0 exp Z exp Z ½9
RT RT
where i is the current density at the electrode, i0 is a (concentration dependent) constant, known as the ‘exchange current density,’ a
is a second constant (the ‘transfer coefficient’), and n is the number of electrons in the reaction. Cathodic overpotentials are
negative (electrode potential less than equilibrium value) and the current density at a cathode is positive.
At large (positive or negative) overpotentials one of the exponential terms on the right of this equation is insignificant and [9]
reduces to the Tafel equation
Z ¼ a þ blni ½10
These equations are usually satisfactory provided the transfer of an ion to the electrode provides no limitation to reaction.
However, it is impossible to react an ion more rapidly than it can be transferred and this imposes a ‘limiting current’ on the
electrode. Some of these features are illustrated in Figure 2 which is for two reactions: the cathodic deposition of a metal and a
second reaction, generation of hydrogen, which is frequently a competing reaction. The negative of the electrode potential is used
as the abscissa and EH4EM, the former being the equilibrium potential for hydrogen generation and the latter for metal
deposition. The corresponding rates (current densities) are iH (broken line) and iM (solid line). Both reaction rates accelerate as the
potential is moved more negative than E. The rate of metal deposition accelerates more rapidly than hydrogen evolution but
eventually reaches a limiting current (density), iLM. The current density for hydrogen increases without limit in the range sketched.
iH
Current (density)
iM
EH EM
Negative of potential
Figure 2 Sketch of the dependence of current density on potential for two cathodic reactions: the generation of hydrogen and the deposition of
metal. EH and EM are the equilibrium potentials for those reactions and iH and iM are the respective current densities. Note the limiting current
displayed by the metal deposition reaction.
Introduction and the Significance of Electrometallurgy 5
It is apparent from this figure that there is an optimum potential where the fraction of the current used to deposit metal reaches a
maximum. This fraction is increased by increasing the mass transfer of the cation to the electrode.
where
Ni is the flux of ion i
Zi is the charge on ion i (negative for anions)
ui is the mobility of ion i
F is Faraday’s constant
ci is the concentration of ion i (moles per unit volume)
is the potential
Di is the diffusivity of ion i
v is the solution velocity.
The first term on the right in eqn [11] is the migration of ion i driven by a gradient in potential, f; the second is diffusion driven
by concentration gradients; and the third is the convection of the ion due to the movement of the electrolyte. In concentrated
solutions additional terms arise.
A similar equation to [11] describes the flux of other ions and a significant fact is that the fluxes are linked, even in the case of
dilute solutions, by the equations. One notable effect of this linkage is that of the ‘supporting electrolyte.’ This is a chemical
species, for example, sulfuric acid solution in the case of aqueous electrolytes, which might not participate in either reactions but
serves to lower the cell potential. For example, in electrorefining of copper the electrolyte contains sulfuric acid. Figure 3 shows the
calculated potential and concentration gradients for a cell with planar parallel electrodes; the horizontal axis is distance from the
cathode. Parameters have been chosen to be representative of copper electrodeposition at low current density and the right hand
figure shows distributions with no supporting electrolyte (H2SO4) present. Even though the sulfuric acid is not participating in the
reaction at either electrode (and there is zero flux of H þ or SO42 ions), the acid lowers the potential difference across the cell by
its effect on the first term on the right in eqn [11].
8
30
7
25
6
5 20
4
15
3
10
2
5
1
0 0
0 0.5 1 1.5 2 0 0.5 1 1.5 2
Distance from cathode, cms Distance from cathode, cms
Figure 3 Potential and concentration distributions calculated from dilute solution theory for a cell in which copper is anodically dissolving at one
electrode (on the right) and depositing on the cathode 2 cm away. C3 is the concentration of copper ion.
6 Introduction and the Significance of Electrometallurgy
(a) an electrochemical side reaction, such as the reduction of H þ ions from aqueous solution;
(b) an electronic conduction path between electrodes, for example, when two electrodes are on a support with a nonzero
conductivity; and
(c) chemical destruction of the metal deposited at the cathode, for example, by a chemical species.
The ratio of the amount of metal produced to that anticipated from Faraday’s law is known as the current efficiency or Faradaic
efficiency of the cathodic reaction (usually expressed as a percentage). The productivity of a cell is maximized when its current
efficiency is 100% and in the electrowinning of metals, particularly zinc electrowinning where hydrogen production occurs at the
cathode, much attention is paid to this measure of performance. For the common case sketched in Figure 4 the current efficiency
passes through a maximum as the cell current is raised (see Figure 2).
Another measure of cell performance is the energy efficiency, the ratio of the electrical energy thermodynamically required for
the desired reaction to the actual energy consumption. This efficiency is dependent on the cell voltage, which increases as cell
current is increased and, as sketched in Figure 4, the energy efficiency typically shows a maximum, although not at the same current
as the current efficiency maximum.
In many electrochemical reactions, for example, oxidation of organic species in solution to other species in solution, the electrode
is unchanging. In the case of metal deposition however, the very cathode surface is the metal deposited. Even starting with a
perfectly planar electrode, it would be unusual for a planar surface to be sustained as deposition proceeds. The development of
surface irregularities has both theoretical and practical significance. A uniform deposition implies a uniform current density and
(local) current efficiency; neither is likely.
Energy
consumed per
unit of
production
Voltage
Current
efficiency
Figure 5 Sketch of the deposition of a solvated ion from solution onto a growing metal deposit. Arrival of the adion at the surface is followed by
diffusion across the surface to a step and thence to a kink site (after Bockris and Reddy, 1970).
8 Introduction and the Significance of Electrometallurgy
A secondary distribution is one allowing also for electrode kinetics. In the case of the plane parallel electrodes discussed above
this allowance brings the edge current density to a finite value but one still greater than in the center of the electrode, unless the
reaction kinetics are slow.
The tertiary distribution is one with an additional allowance for mass transfer to the electrode. If mass transfer to the surface is
uniform, then this limitation provides a leveling influence on the deposition. However, in many cases, for example, near a leading
edge, there are significant variations in mass transfer with position and the tertiary distribution is nonuniform. At high current
densities, near the limiting current density, nonuniform deposits are the norm.
We have treated deposit morphologies at the nanoscale and at the length scale of the electrode. Now consider what happens on
the intermediate scale of deposit surface roughness. A protuberance on the surface of a deposit will grow preferentially when the
primary current distribution holds. The current lines can converge on the tip of the protuberance, increasing the current density
and the deposition rate there. Preferential growth also occurs when convective mass transfer controls the deposition. Then a
concentration boundary layer exits near the electrode surface and protuberances, sitting higher in the boundary layer, experience
higher concentrations of the depositing ion. This suggests that operation near the limiting current results in rough deposits or the
occurrence of dendrites (such as shown in Figure 6). Preferential deposition on certain crystal faces can also contribute to dendrite
formation.
Nucleation can have a major impact on deposit morphology. At high overpotential the electrode will experience a high
nucleation rate, compared to the subsequent growth rate of the nuclei. The deposit will be fine-grained but, if the high over-
potential, near the limiting current, is maintained then the irregular deposits described above will occur. Consequently there has
been much use of conditions where the overpotential is varied (pulsed deposition and periodic current reversal), particularly in
electroplating. In industrial electrodeposition of metals, such as copper, organic additives (animal glues for example) are used as
‘leveling agents’; probably the mechanism of action of these agents is one retarding the kinetics of the growth.
Electrometallurgy distinguishes between electrowinning and electrorefining. In electrowinning, the chemical species yielding the
metal enters the cell as a compound, for example, in a solution pumped into the cell. In contrast, in electrorefining, the metal
enters the cell as its element (in impure form) and forms the anodes within the cells.
Copper Electrowinning
Typical of electrowinning from aqueous solutions is copper electrowinning. The electrolyte entering the cells contains 25–60 g l1
of copper, 50–180 g l1 of sulfuric acid, and 5–10 g l1 of iron salts (Habashi, 1998). It is produced by leaching of copper ores,
with solution purification by solvent extraction.
The desired cathodic reaction is reaction [1] and the anodic reaction is [4] so that both oxygen and acid are generated at the
anode and electrolysis results in the replacement of copper ions by hydrogen ions. A cathodic side reaction is hydrogen generation
by
This reaction is thermodynamically unfavorable compared to copper deposition, as indicated by Table 1 and, in terms of
Figure 2, EM would lie well to the left of EH. Consequently little side reaction occurs and copper electrowinning cells operate at
Figure 6 Zinc dendrites produced by electrodeposition from an aqueous potassium Zincate electrolyte (from Keist, 2013).
Introduction and the Significance of Electrometallurgy 9
Figure 7 Sketch of a copper electrowinning cell from Evans and DeJonghe (2002). The cell is seen from the side and in section with
interspersed anodes and cathodes suspended into the electrolyte.
close to 100% current efficiency. The anodes are of a lead alloy that is intended to be inert although traces of lead are typically
present in the copper cathodes. In recent years titanium anodes with a platinum group coating that is catalytic for oxygen
evolution have been introduced at many plants (see Section Emerging Technologies). A sketch of a typical copper electrowinning
cell appears as Figure 7. The anodes and cathodes (seen edge on in Figure 7) are approximately 1 to 2 m2 and are interleaved as
shown. The cathodes in a cell are electrically in parallel, as are the anodes. Each cell is in series with adjacent cells with the cathodes
of one cell connected to the anodes of the next cell. The cathodes are placed in the cell as ‘starter sheets,’ i.e., thin sheets of copper.
These sheets grow until they are of the order of 1 cm thick, whereupon they are harvested by an overhead crane and replaced with
new starter sheets. Starter sheets are made in separate cells by depositing copper onto stainless steel cathodes from which it can be
pealed. This has led to an alternative technology without starter sheets where the electrowinning cells have ‘cathode blanks’ of
stainless steel. When the copper deposit on the cathode blank is thick enough the blank and copper are withdrawn from the cell,
the two separated mechanically and the blank returned to the cells. Cathodes are subsequently melted and cast into ‘wirebars’ or
coiled rod for sale.
One major difficulty of copper electrowinning is the low current densities at the electrodes (typically 200–300 A m2). This,
and Faraday’s law, results in the need for enormous electrode surface areas, large numbers of cells and large buildings (‘tank-
houses’) with resulting large capital costs. The result is that the electrowinning step is the most capital intensive in many copper
plants.
A second difficulty is the mechanical harvesting of the cells and placement of starter sheets (or cathode blanks) adding
significantly to capital and operating costs.
A third difficulty is the ‘acid mist’ above the cells generated from droplets of electrolyte ejected by bursting gas bubbles. This is
detrimental to workers and forces significant expenditures on ventilation.
Finally, uneven cathode deposits can grow to the point of shorting cells and a significant amount of labor is involved in tending
the cells to avoid them.
purification) contain a few tens of grams per liter of zinc (as zinc sulfate) and similar amounts of acid. Within the cells roughly half
of the zinc is removed and the sulfuric acid concentration increases to, perhaps, 200 g l1.
Other metals produced by routes entailing electrowinning from aqueous solution include cobalt, nickel, cadmium, chromium,
gold, silver, and manganese.
Electrorefining of Copper
The common route for turning copper sulfide ores into metal is high temperature oxidation of sulfides to produce an impure
liquid copper that is cast into slab-like anodes. Principal impurities are iron and precious metals (gold and silver). The anodes are
electrolytically refined in cells sketched in Figure 8. There is a resemblance to the cell of Figure 7. Both are constructed of acid
resistant concrete and contain cathodes (connected in parallel) interleaved with anodes (also connected in parallel). The principal
difference lies in what occurs at the anodes: oxygen evolution at the electrowinning anodes, dissolution of copper – the reverse of
reaction [1], at the electrorefining anodes.
Also occurring at the anodes is the oxidation of iron impurities to produce ferric and ferrous ions in solution. The anodes are
dissolved to the point at which they start to fall apart. The residuum is removed from the cell and re-melted/cast into fresh anodes
and fresh anodes are placed in the cell. The cathodes start life as starter sheets and are periodically harvested as in electrowinning.
Alternatively stainless steel cathode blanks are used as described above under Copper Electrowinning. A glance at Table 1 shows
that there is little tendency for the iron in the electrolyte to co-deposit with the copper; copper deposition is thermodynamically
much more favorable. Precious metal impurities in the anode are not oxidized, at the anode potentials employed, but fall to the
bottom of the cell as an ‘anode slime’ which is occasionally harvested from the cells and sent for recovery of precious metals.
Adjacent cells are connected in series and several hundred cells would be contained in a typical electrorefining tankhouse.
Typical operating conditions for copper electrorefining cells are (Habashi, 1998): 100–200 A m2 at a cell voltage of 0.3 Vwith an
electrolyte of 40 g l1 of copper and 150–200 g l1 of sulfuric acid.
Figure 8 Sketch of a copper electrorefining cell from Evans and DeJonghe (2002). Interspersed copper anodes and cathodes are suspended in an
electrolyte.
Introduction and the Significance of Electrometallurgy 11
The Table 1 of standard electrode potentials shows increasing difficulty of electrowinning of metals from aqueous solutions.
Referring to Figure 2, the point EM moves to the right as we move down the table. Copper is easily electrowon, cobalt with a little
difficulty, zinc with considerable difficulty. At aluminum, electrodeposition from aqueous solution becomes impossible; hydrogen
is the only thing generated at the cathode (by reaction [12]). The solution to this difficulty is to electrodeposit the metal from a
solution containing no hydrogen ions and this is employed in the primary technology for producing aluminum, the ‘Bayer–Hall
process.’
Figure 9 Sketch of a Hall–Héroult cell for the production of aluminum from Evans and DeJonghe (2002). Carbon anodes are suspended in a
molten salt electrolyte above a pool of liquid aluminum contained in a carbon lined cell. Current flows from the cathode bus to the anodes of the
next cell.
12 Introduction and the Significance of Electrometallurgy
between the anodes and the aluminum (the anode–cathode distance or ‘ACD’). This ACD is approximately 4 cm and its reduction,
say to 2 cm, would save considerable electrical energy. Unfortunately such a reduction is precluded by the necessity of avoiding
shorting aluminum to the anodes. An ACD of 4 cm provides a margin of safety for the uneven surface of the anode (from uneven
carbon consumption) and for deformation of the bath–metal interface under magnetohydrodynamic forces. Additionally, the
thermal energy generated in the ACD is then sufficient to compensate for heat losses as well as the thermal energy required for the
reactions.
Reduction of the ACD requires the positions of the bottoms of the anodes to be well defined and also the bath–metal interface.
The former might be achieved using an anode of an inert anode material. This anode would generate oxygen, rather than CO2,
which could be an additional environmental advantage. Limited success has been achieved, in laboratory and pilot-scale cells, with
ceramic, metallic, and cermet anodes (Xiao et al., 1996).
The bath–aluminum interface can be stabilized by making the aluminum a thin film on a wetted surface, the film draining to a
sump to be siphoned off. One of the few electronic conductors that is wetted by aluminum, but insoluble in it, is titanium
diboride. This material or TiB2–carbon composites have met with some success in laboratory and pilot-scale cells (Tabereaux et al.,
1998).
Emerging Technologies
Improvements in electrometallurgy fall into three categories: improved materials, novel electrochemistry, and advances in engi-
neering. Section ‘The Hall–Héroult Cell for Producing Aluminum’ treated the improvements in the Hall–Héroult cell which could
result from inert anodes and cathodes wetted by aluminum. Another material that may find widespread use in electrowinning
metals from aqueous solution is DSAs. This ‘dimensionally stable anode’ consists of an expanded titanium mesh with a pro-
prietary coating that catalyzes oxygen evolution. The mesh is designed so that oxygen bubbles evolve from the back of the mesh
(rather than the side facing the cathode) minimizing their interference with the current. Lower cell voltages are reported with DSA
and the contamination of the cathode with lead from anodes is avoided.
One example of novel electrochemistry is the use of low temperature, aprotic solvents for electrowinning and electrorefining of
aluminum. Reddy and colleagues (Wu et al., 2000, 2001; Kamavaram and Reddy, 2002) have used ionic liquids as electrolytes. An
impure aluminum anode was electrorefined using a 1-butyl-3-methylimidazolium chloride and anhydrous AlCl3 electrolyte with a
copper cathode. The same electrolyte was used to electrowin aluminum from AlCl3 using a graphite anode.
Another novel electrochemistry of note if that of Fray and colleagues (Fray, 2000; Chen et al., 2000) for the production of
titanium and other metals that cannot be electrowon from aqueous solution. This is an alternative to the cumbersome and
expensive Kroll process (Newton, 1959) used, with little change, since WWII for producing this metal. Their approach is an
electrochemical deoxidation of pellets of TiO2 in a molten salt electrolyte.
Finally there is scope for improved engineering of the cells depicted in Figures 7 and 8. These cells result in huge and expensive
tankhouses because of the need for the large electrode area imposed by current density limitations. However, the slab-like
electrodes in these figures have a very low surface area per unit volume. The necessary surface area can be accommodated in much
smaller equipment if the slabs are replaced with beds of particles. In electrodeposition the particles must be kept moving and work
has been done on fluidized and spouted bed electrodes for metal deposition (Masterson and Evans, 1982; Salas-Morales et al.,
1997a,b; Evans and Jiricny, 2011).
Improvements of this kind and the evolutionary improvement of existing technology will ensure that electrometallurgy will
play a significant role in metals production in years to come.
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Further Reading
Biswas, A.K., Davenport, W.G., 1980. Extractive Metallurgy of Copper, second ed. Oxford, UK: Pergamon Press.
Doyle, M., Arora, P., 2001. Report on the electrolytic industries for the year 2000. J. Electrochem. Soc. 148, K1–K41.
Evans, J.W., 1995. Electricity in the production of metals; from aluminum to zinc. Metallurgical and Materials Transactions B 26, 189–208.
Grjotheim, K., Kvande, H., 1986. Understanding the Hall-Héroult Process for Production of Aluminium. Düsseldorf, Germany: Aluminium-Verlag Gmbh.
Grjotheim, K., Welch, B.J., 1980. Aluminium Smelter Technology. Düsseldorf, Germany: Aluminium-Verlag Gmbh.
Hine, F., 1985. Electrode Processes and Electrochemical Engineering. New York, NY: Plenum Press.
Pawlek, R.P., 2015. Primary Aluminum Industry in the Year 2014, Light Metal Age, pp. 9−21.
Pletcher, D., 1984. Industrial Electrochemistry. London: Chapman and Hall.
Roušar, I., Micka, K., Kimla, A., 1986. Electrochemical Engineering. Prague, Czechoslovakia: Academia.