JOURNAL OF APPLIED ELECTROCHEMISTRY 15 (1985) 789-805

REVIEWS OF APPLIED ELECTROCHEMISTRY 11

Advances and future prospects in copper electrowinning

W. C H A R L E S C O O P E R
Department of Metallurgical Engineering, Queen's University, Kingston, Ontario, K7L 3N6,
Canada
Received 7 January 1985

In recent years research on the electrowinning of copper has led to a number of significant advances.
These developments include improved mass transfer and higher current density operation through
air sparging, reduced anode overvoltage in the conventional cell as a result of cobalt(II) addition
to the electrolyte or the use of alternative types of anodes, and the production of high quality
cathodes in the electrowinning of copper from solvent extraction strip liquor. The fluidized-bed
cathode offers the possibility of continuous electrowinning as well as the direct electrowinning of
copper from dilute solutions. The problem of high power consumption may find its solution in the
adoption of an alternate anode reaction or in the electrowinning of copper(I) electrolytes. Note-
worthy is the development of unique electrowinning cells in conjunction with the hydrometallurgical
treatment of copper concentrates. These cells utilize cuprous or ferrous anodic oxidation with the
resulting cupric or ferric ions being active lixiviants of sulphide copper minerals. The numerous
advances combined with the increasing tonnage of copper being produced by the electrowinning
route ensure an interesting and promising future for this process.

1. Introduction emissions. At the same time considerable

research has been devoted to developing hydro-
In recent years there has been a marked increase metallurgical processes for the treatment o f
in the production of copper by electrowinning. copper concentrates. In the great majority of
At present some 15% of the copper produced is these hydrometallurgical alternatives the copper
obtained by this route and it is estimated that is recovered by electrowinning. Thus far it
this figure will rise significantly during the 1980s. appears that no hydrometallurgical process has
The development of specific reagents, in par- yet been developed which can compete success-
ticular the hydroxyoximes, for the selective fully with the newer pyrometallurgical processes
extraction of copper from sulphuric acid leach on the basis of overall cost and energy require-
solutions has been a major step in copper extrac- ments [1]. A major cost component of the hydro-
tion technology. Solvent extraction of copper metallurgical processes is the electrowinning
followed by electrowinning has replaced, to a operation which requires 8 to 10 times more
very large degree, the older cementation process. power than electrorefining (2.0 kWh kg- 1versus
The increased activity in heap and dump leach- 0.25 kWh kg- 1 ).
ing has been aided considerably by the upgrad- The high power consumption associated with
ing of dilute leach liquors by solvent extraction. the electrowinning of copper is an important
The heap and dump leaching is not restricted to consideration in any improvements in the
low-grade oxide copper ores but is being applied process. Also of importance are means of
successfully to low-grade sulphide ores aided in increasing the operating current density and the
many cases by microbiological leaching. possibility of electrowinning copper directly
The environmental constraints which have from dilute leach solutions. Advances and the
been imposed on copper smelters in many future prospects for copper electrowinning will
countries have led to greatly improved smelting be discussed in this paper in the light of the
processes and the increased capture of SO2 above considerations.
0021 891X/85 $03.00 + .12 9 1985 Chapmanand Hall Ltd. 789
 790 W. CHARLES COOPER

2. Methods for increasing the critical current and Steel) directed circulation system does not
density permit uniform circulation over the face of the
entire cathode due to the rapid damping of the
The critical curren t density is the maximum cur- electrolyte movement. In addition, the high
rent density at which one can expect to obtain an pumping costs associated with the circulation
acceptable cathode deposit. Above this value the rates employed in the CCS system and possible
deposit becomes rough, less dense, less pure and problems associated with the orifices are suf-
g e n e r a l l y unacceptable from a commercial ficient to lead to only marginal benefits. As wilt
standpoint. be discussed later, air sparging is a much more
To be able to operate the cell house success- attractive approach to improved agitation and
fully at higher current density and to increase higher current density operation.
productivity, it is necessary to improve the mass The electrowinning of copper at higher cur-
transfer via increased agitation. A word of rent densities in ultrasonically agitated cells has
caution should be noted here as regards elec- been investigated on a laboratory scale by Davy
trolytes which contain significant amounts of Powergas Limited [3]. Eight stainless steel cylin-
ferric ion since, as will be discussed later, drical ultrasonic probes excited by magneto-
improved agitation can be counter-productive in strictive transducers operating at 13 kHz were
the case of such solutions. located along the bottom of the experimental
In recent years improved electrolyte agitation cell. The working range was 146-1000W or
has been investigated via a number of avenues 710-4842Wm -2 of electrolyte plan area. The
including forced circulation of electrolyte, ultra- electrolyte flowed at right angles to the electrode
sonic agitation, the use of tapered anodes, and face at a rate of 0.65 US galm -2 of immersed
air sparging. cathode. The spent electrolyte (temperature
Balberyszski and Andersen [2] developed a 45 ~ C) had the composition: 25 g dm -3 copper,
high current density copper electrowinning cell 150gdm 3 sulphuric acid and 2 g d m 3 iron
which incorporated the concept of an injected (total). The copper drop amounted to 10 g dm -3.
and directed flow of electrolyte to each electrode The results showed that dense, compact depo-
surface. The electrolyte was injected through a sits could be obtained at substantially higher
series of 0.64 cm diameter orifices drilled 5 cm current densities (range investigated 10.8 to
apart in a 5 cm diameter pipe located centrally in 54 m A c m 2). As expected the voltage increased
the cell and near the cell bottom. The electrolyte with current density. However, ultrasonic agi-
outlet pipes were located parallel to the inlet pipe tation which effectively eliminated the barrier
and had a diameter of 5 cm, and 1 cm diameter layer, resulted in a decrease in the cell voltage.
outlet openings 10 cm apart and 5 cm from the A serious disadvantage with ultrasonic agi-
centre of each cathode. The critical circulation tation was the serious lead contamination of the
rate (defined as the circulation rate below which cathode deposit which was noted when 6% anti-
a satisfactory deposit could not be obtained at monial lead anodes were used (170-350ppm
any current density) was related linearly to the lead in cathodes at a current density of
current density. Copper was electrowon from 43 mAcro-2). Thus the ultrasonic agitation dis-
both synthetic and actual solutions at current lodges the oxide layer on the anode resulting in
densities of 38 to 43 mA cm -2 at circulation rates high lead levels in the cathodes and rapid wear
of 1.1 to 2.2 US galmin -~ m -2. An actual solu- of the anodes. Although no tests were conducted
tion was a solution produced in a leach solvent on other anode materials, it was considered that
extraction circuit and had the following com- lead-calcium anodes and noble metal-type
position: Cu: 49.4 g dm-3, Fe (total): 1.6 g din-3, anodes should be stable under ultrasonic agi-
CI: 0.04gdm -3, H2804: 50.0gdm -3. The solu- tation.
tion contained no organic additives or surface Although ultrasonic agitation provides the
demisting agent. possibility of electrowinning copper at higher
Balberyszski and Andersen's cell which was current densities with reduced power costs and
also known as the CCS (Continental Copper capital costs, there are a number of factors
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 791

which must be considered including cost and Ettel and Gendron's data show in the case of
maintenance of ultrasonic agitation transducers the tapered anode a quite uniform cathode over-
and modifications to conventional cells. Noise voltage with distance and a current density
might present a problem. Regular antimonial which increases linearly from 25 to 35 mA cm -2.
lead anodes could not be used. Also if high This behaviour is a marked improvement over
current densities such as 80 to 90 mA cm -2 were that in the regular electrowinning cell where the
employed, problems related to acid mist and mass transfer coefficient increases by a factor of
electrode shorts could be serious. Also it should three in the upper region of the cell.
be noted that ultrasonic agitation, like forced The use of air sparging for improved mass
electrolyte circulation, does not result in uni- transfer in copper electrowinning is a develop-
form mass transport over large cathode surfaces. ment of great interest as regards improved tank-
In examining the problem of current distribu- house performance. Although gas agitation in
tion over the face of the cathode in copper elec- metal electrowinning has been known for some
trowinning, Ettel and Gendron [4] noted that in time and has been applied to a limited extent, it
the conventional cell the evolution of oxygen at was not until the pioneering work of Harvey and
the anode provides superior agitation and hence co-workers at Kennecott [5-9] that definitive
higher mass transfer rates only in the upper part studies on this technique were carried out with a
of the cell. To overcome this problem and to view to its application on an industrial scale.
realize a more uniform current density over the Harvey et al. examined in considerable detail the
surface of the entire cathode, Ettel designed the means of bubble generation (i.e. the cell hard-
tapered anode (Fig. 1). This anode which per- ware) and its optimization in commercial-sized
mits a higher current density operation cells, the inter-electrode spacing, current density,
(30mAcm 2), is being used commercially in and electrolyte composition. These variables
INCO's copper electrowinning tankhouse at were related to the nature and purity of the
Copper Cliff, Ontario. cathode deposit, current efficiency, and power
consumption. One of the principal objectives of
this work was to demonstrate the viability of
CATHODE OVERPOTENTIAL, mV air-agitation electrowinning in copper electro-
40 60 80 lytes produced from heap leaching, vat leaching,
100
E
O
~ ,
and solvent extraction. As Harvey and Hsueh [9]
0 [] point out, air agitation has the three capabilities
...0
(D of improving cathode quality, making possible a
-0 80 higher rate of production and allowing closer
0
t-
spacing of electrodes.
8
o The data in Table 1 give an indication of the
E
o 60 results that can be achieved using air sparging in
E the cases of a vat leach liquor and a simulated
v I
solvent extraction strip liquor. It will be noted
z that the current density in both experiments is
o
well above that employed in conventional
oe~ copper electrowinning. Even at this elevated

o
200
I J

300
I

400
. . . . . . . . . . .

NET CATHODECURRENTDENSITY, A r6 2
Fig. 1. Current distribution using tapered anode. The net
current density excellent quality cathodes were
obtained with surprisingly low lead and sulphur
contents.
In demonstrating the superiority of air sparg-
ing over forced electrolyte circulation and con-
ventional electrowinning Ettel et al. [10]
developed a method for determining the mass
current density was obtained by weighing sections of the
deposit. (Average current density 30 mA cm 2, temperature transfer coefficient for Ag § which in turn can be
60 ~ C, 60 g dm -3 Cu, 150 g dm -3 H 2SO4) [4]. related to that for Cu 2+. (Under the experi-
792 W. CHARLES COOPER

Table l. Air-agitation copper electrowinning data [7, 9]

Experiment EW3A EW5A

Electrolyte vat leach solution *
Average c.d., m A c m -2 64.0 63.4
Cu, g dm -3 (initial) 20.4 29.9
H2SO 4 g d m -3 (initial) 49 180
Temperature, ~ C 60 60
Anode cathode spacing, cm 3.12 2.67
Current efficiency, % 84.6 98.3
Power consumption, kWhkg I Cu 4.0 1.96
Analysis of cathodes
Pb, ppm 0.26 0.62
S, ppm <2 < 2.5

* Simulated solvent extraction strip liquor-actually stripper section electrolyte containing as

major impurities nickel at 0 . 1 g d m -3 and iron at 0.15gdm -3. The addition agent was
removed by treatment with activated charcoal and the electrolyte saturated with 40% LIX
64N in kerosene.

mental conditions employed Ettel et al. [10] Cathode reactions:

calculated kc,2+ = 0.75kAg+ .) The cathode mass Cu 2+ + 2e ~ Cu (1)
transfer coefficient was measured in terms of Fe 3+ + e , Fe 2+ (2)
kAg+ in a copper electrowinning cell under con-
ditions of electrolyte forced flow and air sparg- Anode reactions:
ing. The results show concrete evidence of a H20 ~ 2H + + 1/202 + 2e (3)
much greater and a uniform mass transfer coef- Fe + , Fe 3+ + e (4)
ficient in the case of the air sparged cell (Fig. 2).
As expected air sparging greatly reduces the The reduction of ferric ions at the cathode
thickness of the boundary layer. This behaviour causes a decrease in the current efficiency so that
contrasts sharply with the much thicker and i2L
nonuniform boundary layer in the conventional Current efficiency ( C E ) = it~it = 1 - - - (5)
io
cell without sparging (Fig. 3).
In the electrowinning of copper from an acid where it = current density, Reaction 1, ic =
leach solution containing Fe 3+ ions, the follow- cathode current density, i2L = limiting diffusion
ing reactions are to be noted: current density, Reaction 2 and

100 i i i i i

E V Electrolyte jetted
z ' -~ 80 4amp dn~2 171 Air sparged
oo O
25~
12.3 amp dm 2
25 g !.-tCu
100 g l'~H2 S04

ua 20
>5
o I I I I I I
0 100 200 300 400 500 Fig. 2. Vertical distribution OfkAg+ in elec-
trolyte jetted and air sparged copper elec-
kAg+X 10 5, cm s -t trowinning cell [10].
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 793

100 less pronounced at higher current density. Thus

according to Andersen e t al. [12] it is possible to
E 80 B ~%1 A increase the current efficiency in the recovery of
-o copper from an acid leach solution by decreasing
z...
0 o
~..D k
~Noairsparging the temperature, increasing the inert salt con-
centration, decreasing the ferric ion concentra-
Air spargmgfmin ~; tion, increasing the applied current density and

ul
~ decreasing the agitation.
In the use of periodic current reversal (PCR)
to achieve higher current densities in copper
electrowinning one is confronted with the prob-
> ~ 20 lem of a substantial back e.m.f, to the rectifier
upon switching the direction of the current. It
has been suggested that this problem can be
o I I 1
0 0.1 0.2 0.3 overcome by short circuiting the cells after the
current has been interrupted [13]. This has the
THICKNESS OF gN, Ag+, mm
effect of producing an intense current in the
Fig. 3. Diffusion layer profiles showing beneficial effect of air reverse direction. A more serious problem is the
sparging [11].
effect of current reversal on anode wear and
contamination of the cathode deposit. No pub-
CE = 1 FDve3+CFe3+ (6) lished data are available on the behaviour of'the
noble metal-type anodes in PCR but indications
are that PCR could be detrimental to these
where DFo3+ = diffusion coefficient of Fe 3+ ion; anodes as well.
F = Faraday constant.
From the above equation we can see that the 3. Reduction in the cell voltage
current efficiency is affected adversely by
increased agitation and higher ferric ion con- The power requirement in electrowinning can be
centration. The effect of the ferric ion concentra- decreased by effecting a reduction in the cell
tion on the current efficiency in copper electro- voltage. The cell voltage can be reduced by
winning at different current densities is shown in decreasing the oxygen overvoltage in the con-
Fig. 4. It will be noted that the effect becomes ventional cell or by means of a change in the
100 anode reaction.
In the conventional cell recent studies have

\,,Q shown that the addition of cobalt(II) to the

electrolyte can lower the oxygen overvoltage on
c- 60 ~.,~., the Pb-Sb anodes with an even greater reduc-
tion in the overvoltage (500-600 mV) being real-
r- L,O " ized by the substitution of dimensionally stable
(lJ

01
l_J anodes (DSA) for the lead alloy anodes (Fig. 5).
,4--
,-I--
L.EI
20 The particular anodes referred to in Fig. 5 are
titanium anodes with an oxygen low potential
(OLP) coating of selected non-stoichiometric
i._

k..J
compounds of certain platinum metals, notably
-20 iridium and platinum [15].
I '
In recent years considerable work has been
0.1 0.2 0.3 carried out on the development of new and
C~,3 in mo[ I -~ improved anodes for metal electrowinning [16].
Fig. 4. Cathodic current efficiency as a function o f con-
The problems associated with the stability of the
centration of Fe 3+ ions and current density [12]. coating on titanium anodes has led to the study
794 W. CHARLES COOPER

cell voltage [ V ] lead alloy anodes

2.2- Pb-Sb II
2.1 ~ Pb-Sba I
2.0
1.9
1.8 ~ ~ Ti anodes with
0 2 - l o w - potentml- coating
1.7
type I
1.6 type 11
1.5-
1,4-
1.3-
1,2-
1.1
current density
1.0
o 16o 260 a6o' 460 56o 660 760 860' 56o 16oo [A n32 ]

Fig. 5. Current density-voltage curves for copper electrowinning using different types of anodes [14]. Electrolyte: 50 g dm -3
Cu, 50 g dm-3 H2 SO4, temperature 40 ~ C; Cathode: copper clad graphite.

and adoption of oxides other than RuO2 such as rolled product has a fine uniform grain struc-
the OLP coatings mentioned above and to ture, superior to that of the cast alloy.
anodes having an oxide subcoating [17]. Of Gendron et al. [20] found that the addition of
interest is the activated lead electrode (ALE) Co 2+ ions to the electrolyte to give a cobalt
in which RuO2-coated titanium sponge is concentration > 1 0 m g d m -3 lowered the volt-
embedded into the lead substrate by pressing or age at the P b - S b anode and reduced the cor-
rolling [18]. In commercial copper electrowin- rosion rate of the anode significantly.
ning tests this electrode has provided a voltage In the presence of cobalt the anode reaction
reduction of 300 mV. In the case of lead alloys, becomes
a promising advance appears to be the wrought Co 2+ , Co 3+ + e (7)
lead-calcium-tin alloy [19] which is in use
in solvent extraction-copper electrowinning followed by the oxidation of H 2 0 by Co 3+
operations. The strong dross and crack-free 4Co 3+ -I- 2 H 2 0 ) 4 C o 2+ -t- 4 H + + 02 (8)

2.5
i
r-

0 1000
'~Ei 2.o

I~" 1.5
ul
N

~ooo
X 1.0
0
..Q
Q,.
,,~ 0.5
I--
O
I--

o I I I Fig. 6. Corrosion rate o f P b Sb anode

0.o01 o.01 0.1 1.o 10 as a function of cobalt level in elec-
trolyte. Figures in parenthesis denote
COBALT IN ELECTROLYTE, g 1-1 duration of test in hours [20].
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 795

Thus in the presence of small amounts of Co 2+ that for the conventional electrowinning
the polarization of the P b - S b anode in H2SO 4 process.
solution is reduced, the cobalt facilitating the Pace and Stauter [23] succeeded in electrowin-
evolution of oxygen. The favourable effect of the ning copper directly from synthetic pregnant
cobalt addition to the electrolyte on the cor- leach liquors utilizing the SO2 sparging of the
rosion rate of lead is shown in Fig. 6. The addi- electrolyte in the presence of a graphite anode.
tion of as little as 50 to 100 p p m of cobalt to the They were able to demonstrate that copper
electrolyte appears to be sufficient to give copper cathodes can be produced at higher current
cathodes containing less than 10 p p m lead when efficiencies than those encountered in conven-
using 6% antimonial lead anodes [21]. tional electrowinning practice for electrolytes in
K o c h [22] noted that in the presence of which the copper is plated down from 10 to
2 0 0 m g d m -3 Co z+ as cobaltous sulphate in 1 M 2 g d m -3 in the presence of 1 0 g d m 3 iron.
H2 SO4 very much less PbO2 was formed on the The rather slow kinetics of the sulphur dioxide
surface of lead anodes and that in some cases oxidation especially at higher current densities
the metallic appearance of the surface was results in an unfavourable anode overvoltage
unchanged when O2 was evolved. K o c h demon- and makes for an anode potential which is less
strated that cobalt has no effect on the initial advantageous than that indicated by thermo-
sulphation of lead and only becomes effective dynamic considerations alone.
when the potential reaches a value where the The opportunity afforded by the anodic
oxidation of Co 2+ to Co 3+ can occur. reaction:
A significant reduction in the cell voltage in
copper electrowinning can be realized if the Fe 2+ , Fe 3+ + e, (13)
conventional anode reaction is replaced by a E ~ = 0.77 V versus SHE, as an alternative to the
reaction such as conventional reaction:
Fe 2+ , Fe 3+ + e (9)
or H20 ' 1/202 + 2H + + 2e, (14)

2H20 + SO2 , SO42 + 4H + + 2e (10) E ~ = 1.23 V versus SHE, in realizing a reduced

A comparison of the SO2 oxidation and the cell voltage was investigated by Cooke e t al. [24].
conventional oxygen evolution reaction reveals Anode polarization curves were obtained to
the following thermodynamic data: assess the effect of anode sparging with air and
nitrogen as well as mechanical oscillation of the
N e t cell r e a c t i o n - S02 process: anode to improve the transfer of ferrous ions.
C u S O 4 + H 2 S O 3 -]- H 2 0 ~ C u -Jr- H z S O 4 The regeneration of the ferrous ions is very
important since the reduction of Fe 3+ at the
AH ~ = -77.28kJmol lCu (11)
cathode, as has been shown by Andersen et al.
AG O = -31.76kJmol -lCu [12], greatly reduces the current efficiency in
the electrowinning process. Cooke et al. [24]
N e t cell r e a c t i o n - conventional process:
explored the problem of ferric ion reduction
CuSO4 + H 2 0 = Cu + 1/2 O2 + H 2 8 0 4
using as reducing agents sulphur dioxide,
AH ~ = 221.46kJmol -l Cu (12) cuprous sulphide, sugar, and coal. However,
they failed to come up with a satisfactory
AG O = 172.21kJmol -l Cu
regeneration procedure.
The enthalpy difference between the two In recent work Mishra and Cooper [25] have
reactions amounts to 298.74kJmo1-1 of Cu in demonstrated that the ferrous ion is a more
favour of the SO2 reaction. This value works out effective anode depolarizer in copper electrowin-
to be 1.30 Wh kg -1 Cu less for the SO2 reaction. ning than is sulphur dioxide. The data presented
F r o m the free energies of reaction, it can be in Fig. 7 show that reductions in anode potential
shown that the SO2 reaction takes place at a while sparging 10, 20, and 100% SO2 at a current
theoretical potential which is 1.05V less than density of 2 0 m A c m -2 are in the order of 100,
796 W. CHARLES COOPER

1.5

W
r'~
0
rl"
t-- 1 . 2 5
_ ,_
U
W
_1
W

o
Od 1.0 "-S-02
'NAIR(VOL~ / /l~l < __
"r

I
0.75
;77-- /
~ = ,o / =
/ Z ~
/ y _
--a=)5 Z / //0 J
u) ;: , _/.//-/"
0 ==5o "/ / / .'=
> 9 =,oo / / o" / ,~/
~ 0,5 - o : o , u , , , / / / / . , < -
<
I'-- ,"
._J
0 a" <=P-"" /
w
C)
0,25 -

Fig. 7. Anode polarization curves

using sulphur dioxide and air for
0
Z
<
5 / /o/O sparging [25]. Experimental con-
J 0 ditions: Cu 10gdm -3, H2SO4
o _.~/~/I
I, 5 2 2.5
I
3
I
3,5 4
50gdm -3, temperature 50~
sparging rate 60 cm3rain- 1, graph-
ite anode (Speer Carbon of
Canada Ltd, 890-S).
~.n ANODIC CURRENT DENSITY (mA em ~')

700, and 1000mV respectively whereas in the total iron after 3 h of gas sparging. The results
presence of 10 g dm 3 of ferrous ion and sparg- indicate that SO2 first acts as an oxidant when its
ing air at the same rate the reduction amounts to concentration is between 0 and 5% of SO: in air
1200 inV. and above 5% as a reducing agent for ferric ions.
In the ferrous oxidation process it is essential The rate of reduction of ferric ions increases
to regenerate the ferrous ions from the ferric with the increase in the SO2 concentration in the
ions produced at the anode. This reduction can air. These findings agree with the conclusions of
be accomplished by SO: sparging which also Tiwari et al. [26] that the oxidation of ferrous
serves to improve mass transfer in the electro- ions or the reduction of ferric ions depends upon
lytic cell. the ratio of SO2 to oxygen in the gas phase.
Dissolved sulphur dioxide can act as a strong As discussed later in this paper Mishra and
reducing agent for ferric ions as well as an oxi- Cooper used a mixture of 15% SO2 in air as the
dant for ferrous ions in the presence of oxygen as sparging gas to electrowin copper directly from
shown by the following equations: actual sulphuric acid leach solutions.
2Fe 3+ + SO2 + 2H:O = 2Fe 2+
4. The electrowinning of copper following
+ H:SO4 + 2H + (15) leaching and solvent extraction
2Fe 2+ + SO2 + O2 = 2Fe 3+ + SO]- (16)
The production of copper by the leaching of
Fig. 8 shows the effect of SO2 concentration in lower grade copper ores (both oxide and sul-
the sparging gas on the ratio of ferric iron to phide), solvent extraction and electrowinning is
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 797

7o/ I I 1 I I I I reported good quality copper deposits in elec-

trowinning at 65 mA cm -2 using air sparging in
an electrolyte saturated with 40% LIX 64N in
kerosene.
The most definitive studies on the effect of
entrained organic on the nature of the copper
deposit have been conducted by MacKinnon et
al. [28-30]. These investigators studied the effect
of LIX 65N (the active component of the
~ 30- ~ organic extractant LIX 64N) in combination
with the chloride ion and the additives glue and
3 []\ thiourea on the morphology of electrowon
[] j
~ 20--
copper. In an investigation of the effect of LIX
65N and chloride ion concentration on copper
~ I0-- electrodeposition at a current density of
43 mA cm 2 [28], it was found that a low LIX
I I I I I 1 I 65N concentration (8 ppm) appears to improve
5 6 9 12 15 18 21 24
the copper deposit. However, entrained LIX
S U L P H U R DIOXIDE IN A I R ( V O L . % )
65N at levels of 50 and 100 ppm has a deleterious
Fig. 8. Effectof sulphur dioxide concentration on the ferric
ion concentration [25]. Experimental conditions: Cu 10g effect on the copper deposits, causing them to be
dm -3, H2SO 4 50gdm 3, total Fe 7gdm -3, temperature extremely pulverulent and nodular. This harm-
50~C, gas mixture sparging rate 500cm3min ~, electrolyte ful effect can be offset to some extent by the
volume 250 cm3, sparging duration 3 h.
addition of 100 ppm of chloride ion.
a process which is accounting for an increasing The combined effects of glue and LIX 65N at
percentage of total copper production. Conse- LIX 65N concentrations greater than 8 p p m
quently it is important to consider the extent to were found to result in pulverulent non-
which the solvent extraction operation affects crystalline deposits [30]. In agreement with
the electrowinning procedure. previous work [29] it was noted that the adverse
The advantages of solvent extraction prior to effect of LIX 65N could be compensated by the
electrowinning reside principally in the upgrad- presence of sufficient chloride ion. In the case of
ing of leach solutions of low copper concentra- the glue and LIX 65N study, the chloride ion
tion which result from heap and dump leaching concentration required was ~>40 ppm.
and in the purification of the leach solutions In the presence of glue 30 ppm, chloride ion (0
particularly as regards iron. to 40 ppm) and LIX 65N (8 ppm), variation in
The problems that arise in the electrowinning the current density from 21.5 to 4 3 m A c m -2
of copper from the solvent extraction loaded produced no significant effect on the preferred
strip liquor appear to be related principally to orientations or surface morphologies of the
the carry-over with the strip liquor of any of the copper electrodeposits [30]. The electrolyte con-
organic phase. The presence of entrained tained 20 g dm -3 Cu and 150 g dm -3 H2SO 4 and
organic is indicated by the dark brown colour- was maintained at 35 ~ C.
ation of the copper deposit known as organic N o distinctly different results were obtained in
burn. the studies involving thiourea, LIX 65N and
In studies on the electrowinning of copper chloride ion although no experiments were con-
from loaded strip liquor Hopkins et al. [27] ducted in which both glue and thiourea were
observed that kerosene itself had no effect on the present in the same electrolyte.
electrodeposit but organic burn appeared under
their experimental conditions when the con- 5. The direct electrowinning of copper from
centration of the organic phase (20 to 40% LIX dilute leach solutions
64N in kerosene) in the electrolyte exceeded
200 ppm. It is noteworthy that Harvey et al. [7] The direct electrowinning of copper from more
798 W. CHARLES COOPER

concentrated leach solutions such as are Table 2. Operating conditions for a prototype direct electro-
winning unit for use with waste dump leach liquors [31]
obtained following vat leaching has been prac-
ticed for many years. However, even here if the
leaching produces solutions containing dele- Leach liquor composition
Copper 0.6gdm 3
terious impurities such as ferric iron and dis- Iron (III) 0.6 g d m -3
persed colloidal silica, it may be advantageous to pH approx. 2
subject the leach liquor to solvent extraction
Cell Conditions
prior to electrowinning. Such a procedure is Feed rate 20 US g a l m i n -t
employed by the Kennecott Copper Corpor- Potential 4.7 V
ation in the treatment of the chrysocolla ores at Current density 21.5 m A cm -2
Ray Mines, Arizona. Cell performance
The direct electrowinning of copper from Copper recovery > 85%
dilute leach solutions would, if successful, elimi- Energy consumption 7.0 k W h k g - 1 Cu
Copper loading 16.6 kg Cu m -2 cathode
nate the solvent extraction step in the overall
Cathode turnaround time 3 - 4 days
process.
Several approaches to the direct electrowin-
ning of copper from dilute leach solutions have
been investigated but so far no process has been
developed and used on a commercial scale. sive to the point where the process economics
An interesting process which was piloted suc- become unattractive.
cessfully by Kennecott [31] involves the deposi- Skarbo and Harvey [5] have demonstrated
tion of copper onto a packed coke bed cathode that air-agitation electrowinning can be used to
from a solution containing less than 2 g d m -3 recover copper directly from dilute leach solu-
copper. The deposited copper forms a strongly tions containing less than 5 g d m -3 copper. The
use of sparged sulphur dioxide for anode
bonded c o p p e r - c o k e material which following
removal from the cells would be melted, fire depolarization at a graphite electrode offers the
refined, and cast as a final copper product. potential of electrowinning copper directly from
The process chemistry embraces the following dilute leach liquors at a significantly reduced
cathodic and anodic reactions. power consumption. In fact Pace and Stauter
[23] obtained good quality cathodes with a cur-
Cathode reactions
rent efficiency of 95% in electrowinning copper
Cu 2+ + 2e , Cu (17)
from 10gdm -3 down to 2 g d m 3 in SO2 sparged
Fe 3+ + e ~ Fe 2+ (18) synthetic leach liquors. The operating cell volt-
age at a current density of 2 1 . 5 m A c m -2 was
2H + + 2e ~ H 2 (19) 2.5 V for an initial solution containing copper,
iron(II), and H2SO 4 each at 10gdm -3. This
Anode reactions value is well above the open-circuit voltage
Fe 2+ , Fe 3+ + e (20) of 0 . 3 - 0 . 4 V and indicates substantial over-
voltages.
H20 , 1/2 0 2 -[- 2H + + 2e (21)
The direct electrowinning of copper from
From these reactions it can be seen that the leach solutions from oxide copper ores has been
current efficiency in terms of copper production carried out by Mishra and Cooper [25] using
is reduced substantially. ferrous ion oxidation together with SO2 sparg-
The operating conditions for a prototype elec- ing. Following dissolution of the ore, the filtered
trowinning system based on this process as leach solutions were sparged with a mixture of
applied to waste dump leach solutions are given air and SO2 (15%) until most of the iron was
in Table 2. reduced to the ferrous state. The current density
Although this process permits the direct elec- was selected so as to produce bright, dense
trochemical recovery of copper from extremely copper deposits. Electrowinning data on one of
dilute solutions, its power consumption is exces- the copper ores are presented in Table 3.
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 799

Table 3. Electrowinning copper from sulphuric acid copper leach solution from oxide copper ore, Noranda Inc., Mines Gaspk
Division, Murdochville, Quebec [25]

Copper drop CD CE Sulphuric acid Ferrous ion Ferric ion

(g dm -3) ( mA cm -2) (%) (final conch.) (final concn.) (final conch.)
(gdm -3) (gdm 3) (gdm-3)

6.4 5.8 20 87 20 5.20 0.80

5.8-2.7 16.7 86 43 4.98 1.02
2.7-2.1 10 85 53 5.00 1.00
2.1-1.6 8 75 61 5.12 0.88
1.6-0.87 7.5 65 65 5.12 0.88
0.87 0.45 5 45 70 5.23 0.77

Power requirement 0.94 k W h k g - ~ copper at 20 m A cm-2.

Sparging 15% SO2 in air at 200 cm 3 rain ~ between the electrodes.
Sulphuric acid initial concentration 11 g d m 3.

While this study was aimed primarily at the the basis of the cross-sectional area of the fluid-
direct electrowinning of copper from leach solu- ized-bed cell is, of course, very much larger.
tions, it should be possible to apply the ferrous Operation at a current density of 300 m A c m -z
oxidation-SO2 sparging technique to the sol- of cell cross-sectional area has been proposed
vent extraction-electrowinning process to [331.
reduce the energy requirements of copper The excellent agitation in the cathode bed
production. greatly reduces the thickness of the Nernst
The use of a fluidized-bed cathode appears to boundary layer and increases the limiting dif-
offer a viable means of electrowinning copper
directly from very dilute leach solutions, e.g.
< 2 g d m -3 Cu [32, 33].
In the fluidized-bed electowinning cell par-
ticles of copper are fluidized by the upward flow
of electrolyte through the bed. The bed is
CATHODE~ /~ANODE
rendered cathodic by the presence of a feeder
electrode which can be a copper or titanium rod.
In the plane parallel cell configuration (Fig. 9)
the anode is placed in the electrolyte in the upper
part of the cell. Alternatively the anode and
cathode can be placed in adjoining compart-
ments and separated by a diaphragm or porous
partition as in the side-by-side configuration
(Fig. 10). This latter configuration seems to be
the option to be considered in any scale-up for
BED ~IBII~,\\\\\\~II
/ POLRAOTUES

commercial purposes.
The large surface area presented by the
cathodic copper particles means that in elec-
trowinning the actual current density per unit
surface area of the particles may be in the order
IN
0.2 mA cm -2 which is one hundredth of the cur-
rent density used in conventional electrowin- Fig. 9. Fluidized-bed electrowinning cell having a plane par-
ning. The nominal current density calculated on allel configuration [34].
800 W. CHARLES COOPER

=m treated

Anol,

Process stream to be treated Fig. 10. Fluidized-bed electrowinning cell

having a side-by-side configuration [35].

fusion current density. The net result is that in drop in the cell and raising the cell voltage and
fluidized-bed electrowinning copper can be in turn the power consumption.
plated down to a concentration of 0.01 g dm -3 The power consumption data which have
before the onset of polarization as shown by a been reported for electrolytes of low copper and
sharp rise in the cell voltage [33]. H2 SO4 concentrations are not favourable. Thus
Monhemius and Costa [34] in a statistical Wilkinson and Haines [32] reported power con-
modelling study of the interaction of the import- sumption values which are 1.5 to as much as 5
ant variables in the fluidized-bed electrowinning times higher than the figure for conventional
of copper from dilute solutions, have drawn copper electrowinning (2 kWh kg -1 Cu) in the
attention to two serious problems. The first is fluidized-bed electrowinning of copper from
the problem of ferric iron which, as has been sulphuric acid solutions having a pH of 2 to 3.
discussed earlier, can have a strong negative Had the electrolytes contained ferric iron the
effect on the current efficiency and hence on the power consumption would have been even
power consumption. This problem would be higher.
ameliorated to some extent in the side-by-side The recent data of Dubrovsky et al. [36] are of
cell configuration in which the anode and particular interest even though these inves-
cathode are separated by a suitable membrane. tigators did not study the fluidized-bed electro-
The second problem concerns the low conduc- winning of copper from dilute solutions. They
tivity of the dilute leach solutions in which the did examine the effect of the anode and the
H2SO4 concentration may be at a level of anode reaction on the cell voltage and were able
1 0 g d m -3 as opposed to 100 to 150gdm -3 in to attain improved power consumption values
conventional copper electrowinning. This low (Tables 4 and 5). The use of noble metal-type
conductivity has the effect of increasing the I R anodes or DSA anodes was effective in reducing
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 801

Table 4. Fluidized-bed copper electrowinning [36]; summary of experimental results

Cylindrical Side-by-side rectangular fluidized-bed cell

cell
Small anode Graphite packed bed anode

Oxygen Oxygen Cuprous Cuprous- FeSO 4 SO 2

evolution evolution oxidation anode oxidation oxidation
plus with
cathode FES04

Temperature (~ C) 50 50 50 50 50 35
Electrolyte 3.0 2.53 4.25 4.25 5.1 6.1
resistivity (f~ cm)
Cell voltage (V) 6.2 6.5 4.20 4.60 3.95 4.6
(at 0.45 Acm -2)
Energy consumption 5.24 5.48 3.54 1.94 3.33 3.88
at 100% efficiency
(kWh kg- ~Cu)
Current efficiency (%) 89
Energy consumption 5.94
(kWh kg t Cu)

the power consumption to a level which was less the fluidized-bed electrowinning of copper from
than 50% above the conventional figure. Experi- dilute leach solutions containing ferric iron is an
ments were also conducted using SO2, cuprous, impediment which must be resolved if serious
and ferrous oxidation in place of oxygen consideration is to be given to this approach to
evolution. direct electrolytic reduction without the inter-
The high power consumption associated with mediate solvent extraction step.

Table 5. Fluidized-bed copper electrowinning [36]; summary of experimental results

Side-by-side rectangular fluidized-bed cell

DSA double mesh anode Diaphragm Screen-

against covered
SO 2 Oxygen Oxygen DSA mesh. lead
oxidation evolution evolution Oxygen anode.
50gdm 3 150gdm-3 evolution Oxygen
H 2SO 4 H2 S04 50gdm 3 evolution
H 2S O 4

Temperature (~ C) 50 50 50 20 30
Electrolyte 4.5 4.6 2.5 4.7 3.0
resistivity (f~ cm)
Cell voltage (V) 3.25 3.6 2.90 2.85 3.41 at 1Acm -2
Energy consumption 2.75 3.08 2.44 2.38 2.88
at 100% efficiency
(kWh kg 1Cu)
Current efficiency (%) 98 70
Energy consumption 2.51 4.09
(kW h kg 1Cu)
802 W. CHARLES COOPER

6. Electrowinning from copper(l) electrolytes Anode reaction

Cu + , Cu 2+ + e (23)
A significant reduction in power consumption in
copper electrowinning can be realized if the Cathode reaction
copper in the electrolyte is present in the cuprous Cu + + e , Cu (24)
form. In recent years a number of noteworthy According to Muir and Parker [42], typical
advances have been made in electrowinning electrolyte composition, conditions and energy
from both cuprous chloride and sulphate requirements for electrowinning copper from a
solutions. Cu2SO 4 acidified solution containing aceto-
In the electrowinning of cuprous chloride nitrile are as follows:
solutions at around 30~ (CuC1 0.7M, NaCI
4M, HCl 0.5M), Winand and co-workers [37, CH3CN 80-240 g din-3
H2SO4 100- 200 g dm- 3
38] were able to obtain power consumptions of Cu + 30-60gdm 3 (RCN:Cu § :~ 4: I)
between 0.45 and 0.60 kWh kg i Cu at current Current density 10- 20 mA crn- 2
densities ranging from 20 to 30mAcro -2. If Temperature 25- 50~C
oxidation of the catholyte was avoided through Cell voltage 0.3-0.8 V
the use of a diaphragm in the cell, the current Anode dense graphite
efficiency was quite high at 93%. The copper High quality, dense electrodeposits can be
deposits were dendritic in nature with crystals obtained at current efficiencies in the order of
protruding from the surface. These somewhat 95% or better provided Cu 2+ ions are prevented
rough though coherent deposits present prob- from entering the cathode compartment. The
lems as regards occlusion of the electrolyte. The typical energy requirement is quite favourable at
crystals can be broken and recovered con- 0.14 to 0 . 3 6 k W h k g -1 Cu and is the same order
tinuously on a conveyor belt as is done in the of magnitude as the energy requirement in
Duval CLEAR process [39]. The CLEAR process copper electrorefining.
is an interesting commercial application of This process has not as yet been developed
cuprous chloride electrowinning. beyond the laboratory stage. As Muir and
Through the use of inert gas sparging Winter Parker [42] have indicated many fundamental
et al. [40] were able to obtain smooth deposits in data are required for this mixed solvent system.
electrowinning copper from a 4M NaCI-1 M Also processes related to the recovery of copper
HC1 cuprous chloride solution at a current den- fi'om ores, concentrates, and other copper-
sity of 3 0 m A c m -2. bearing materials using organic nitriles to
The electrowinning of copper from cuprous stabilize Cu2SO4 solutions have yet to be sub-
sulphate electrolytes has been shown by Muir jected to a complete techno-economic analysis.
and co-workers [41, 42] to be especially attrac- In the electrowinning of copper from cuprous
tive if it is carried out in solutions containing chloride electrolytes some excellent data have
organic nitriles such as acetonitrile. The process been presented regarding the physicochemical
appears to be applicable to the upgrading of and electrochemical properties o f such electro-
copper-bearing materials such as scrap copper lytes [40, 43, 44]. However, it remains for these
and cement copper which are not amenable to results to be applied in the development of an
being cast directly as anodes. These materials industrial process yielding marketable cathodes.
provide the cuprous ions for electrowinning via In his review of the status of the electrolytic
reaction with the Cu 2+ ions which are generated recovery of metals from aqueous chloride media,
anodically in the electrowinning cell. MacKinnon [45] draws attention to shortcom-
ings in the present technology.
Cu 2+ + Cu , 2 Cu + (22)
7. Future prospects in copper electrowinning
Electrowinning in the diaphragm cell contain-
ing C H 3 C N - H 2 0 - H 2 SO4 proceeds according to There is little doubt that electrowinning will
the reactions: continue to be employed as the final reduction
ADVANCES AND FUTURE PROSPECTS IN COPPER ELECTROWINNING 803

step in the production of substantial tonnages of at the anode is found in the Electroslurry process
copper. Support for this statement can be found [1]. Here not only is the anode voltage reduced
in the increasing treatment of lower grade significantly, but also the ferric ions which are
copper ores and waste rock by heap and dump generated are used for the in situ leaching of
leaching followed by solvent extraction and elec- covellite and chalcocite.
trowinning. In addition, the continuing research The direct electrowinning of copper from
on hydrometaUurgical alternatives to the pyro- dilute solutions with the elimination of the sol-
metallurgical processing of copper concentrates vent extraction step is possible down to levels of
is bound to produce processes which will around 2 g dm -3 copper using ferrous oxidation
provide unique advantages. The electrowinning and SO2 sparging. The difficulty arises when one
of copper in two such processes namely, the desires to plate down to ppm concentrations.
Duval CLEAR process and the Electroslurry The answer may well be found by taking advan-
process should be noted. tage of the cell systems which have been
The high power consumption in conventional designed for the electrolytic recovery of metals
copper electrowinning is a problem which may from waste solutions [46]. Interesting examples
find its eventual solution in the electrowinning of are the Eco-Cell [47] in which metal powders are
copper from cuprous electrolytes. In the case of produced at a rotating cylinder cathode and the
cuprous electrowinning there can be the double impact rod reactor (Fig. 11) in which the metal
advantage of a one-electron reduction and a deposited onto stainless steel rods is removed by
modified anode reaction which involves the oxi- the oscillation of the rods [35]. Also noteworthy
dation of cuprous ions in place of oxygen is the Chemelec cell in which mass transport is
evolution. facilitated by a fluidized-bed of inert glass beads
In the conventional electrowinning process it in which expanded mesh electrodes are
would appear that the reduction of the oxygen immersed [48].
overvoltage via the use of DSA anodes is at The fluidized-bed electrowinning cell, besides
present too expensive and that the addition of providing the possibility of treating very dilute
cobalt(II) to the electrolyte may be the simplest solutions, affords the opportunity of continuous
expedient. Cobalt has the additional advantage electrowinning. This application may be especi-
of reducing the corrosion rate of the antimonial ally advantageous when applied to more con-
lead anodes and permitting the production of centrated solutions. Compared to conventional
copper cathodes of low lead content. A number copper electrowinning fluidized-bed electrowin-
of alternative anodes are available which allow
the production of quality cathodes without lead
contamination [16]. Continuing advances in
anode materials and further increases in energy
costs will undoubtedly lead to the wider accept-
ance in copper electrowinning of anodes having
a low oxygen overpotential.
The reduction in the cell voltage and the
power requirement in copper electrowinning
through the use of ferrous ion as anode de-
polarizer in place of oxygen evolution requires
additional study to define the optimum
procedure by which the regeneration of ferrous
ions might be achieved. In the application of
ferrous ion oxidation in wfiich an SO2/air mix-
ture is employed for sparging, the problem of
SO2 entering the tankhouse environment from Fig. 11. Impact rod electrolytic cell GOECOMET[35]. 1.
the sparging gas must be resolved. An important Electrolyticcell,2. electrodes,3. drivingsystem,4. reservoir,
5. metal collector, 6. liquid level,and 7. currentconnecting
development in the use of ferrous iron oxidation plugs.
804 W. CHARLES COOPER

ning, a c c o r d i n g to a p r e l i m i n a r y e c o n o m i c nische Universitfit Berlin, I n s t i t u t fiir M e t a l -

analysis, has s u b s t a n t i a l l y lower c a p i t a l costs. lurgie for his c o n t r i b u t i o n to this work.
H o w e v e r , this a d v a n t a g e is n e g a t e d b y the
higher o p e r a t i n g costs w h e n the p o w e r con- References
sumption in fluidized-bed e l e c t r o w i n n i n g [1] C.H. Pitt and M. E. Wadsworth, US Department
of Energy, DOE Contract No. DE-AS07-
exceeds t h a t in the c o n v e n t i o n a l o p e r a t i o n b y 78CS40132, Final Report, December 1980.
m o r e t h a n 50% [36]. C o n s e q u e n t l y , to t a k e full (Available from National Technical Information
a d v a n t a g e o f the fluidized-bed process it is Service, US Department of Commerce, 5285 Port
Royal Road, Springfield, VA 22161).
necessary n o t o n l y to design a cell t h a t will [2] T. Balberyszski and A. K. Andersen, Proc. Aust.
permit continuous electrowinning on a commer- Inst. Min. Met. 244 (Dec. 1972) 11.
cial scale, b u t also a system t h a t has a p o w e r [3] G. Eggett, W. R. Hopkins, T. W. Garlick and M. J.
Ashley, paper presented at Annual AIME Meet-
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p r e s e n t e l e c t r o w i n n i n g process. D u b r o v s k y e t al. [4] V.A. Ettel and A. S. Gendron, Chem. Ind. (1975)
[36] have s h o w n t h a t the l a t t e r r e q u i r e m e n t is 376.
[5] R.R. Skarbo and W. W. Harvey, Trans. Inst. Min.
presently close to being met. Metal. Sect. C 83 (1974) C213.
In the case o f cell design a n d c o n t i n u o u s m e t a l [6] W.W. Harvey, A. H. Miguel, P. Larson and I. S.
electrowinning, K a m m e l a n d c o - w o r k e r s [35, 49] Servi, ibid. 84 (1975) C11.
[7] W.W. Harvey, M. R. Randlett and K. I. Banger-
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o p t i o n s which are w o r t h f u r t h e r investigation. I t [8] Idem, Chem. Ind. (1975) 379.
m u s t be e m p h a s i z e d t h a t simplicity o f design [9] W.W. Harvey and L. Hsueh, CIM Bulletin 69(768)
(1976) 109.
a n d o p e r a t i o n are two very i m p o r t a n t criteria [10] V.A. Ettel, B. V. Tilak and A. S. Gendron, J. Elee-
for a c o m m e r c i a l cell. M a n y o f the electrochemi- troehem. Soe. 121 (1974) 867.
cal r e a c t o r s which have been d e v e l o p e d especi- [11] V.A. Ettel, A. S. Gendron and B. V. Tilak, Metall.
Trans. B 6B (1975) 31.
ally in the field o f m e t a l r e c o v e r y f r o m very [12] T.N. Andersen, C. N. Wright and K. J. Richards,
dilute s o l u t i o n streams are far t o o s o p h i s t i c a t e d "International Symposium on Hydrometal-
for t r o u b l e - f r e e p e r f o r m a n c e in an i n d u s t r i a l lurgy", edited by D. J. I. Evans and R. S. Shoe-
maker (AIME, New York, 1973) pp. 171-202.
environment. [13] H.A. Liekens and P. D. Charles, World Mining 40
A i r s p a r g i n g has been s h o w n to i m p r o v e m a s s (April, 1973) 38.
transfer a n d to p r o v i d e for m o r e u n i f o r m elec- [14] K.R. Koziol and E. F. Wenk, AIME, TMS (1980)
Paper No. A80-41.
t r o w i n n i n g c o n d i t i o n s across the entire c a t h o d e [15] K.R. Koziol, "Technical Information", (CON-
surface. This p r o c e d u r e is definitely s u p e r i o r to RADTY GmbH and Co., MetalMektroden KG,
forced electrolyte c i r c u l a t i o n as a m e a n s o f (1982).
[16] Proceedings of Sessions, Anodes for Electrowinning,
higher c u r r e n t density o p e r a t i o n . T h e technique AIME Annual Meeting, Los Angeles, CA,
has a future in u p g r a d i n g c o n v e n t i o n a l c o p p e r February 1984, edited by D. J. Robinson and
electrowinning, b u t due a c c o u n t m u s t be t a k e n S. E. James (AIME, New York, 1984).
[17] I.H. Warren, in Proceedings of Sessions, Anodes for
o f the effect o f increased a g i t a t i o n on c u r r e n t Electrowinning, AIME Annual Meeting, Los
efficiency in the presence o f ferric ions, o n the Angeles, CA, February 1984, edited by D. J.
e n h a n c e d c o r r o s i o n o f the c a t h o d e at the air- Robinson and S. E. James, (AIME, New York,
1984) pp. 69-78.
s o l u t i o n interface, a n d o n the stability o f the [18] J.K. Walker and J. I. Bishara, ibid. pp. 79-86.
a n o d e in l o n g e r t e r m electrowinning. [19] R.D. Prengaman, ibid. pp. 59 67.
[20] A.S. Gendron, V. A. Ettel and S. Abe, Cdn. Met.
Quart. 14 (1975) 59.
Acknowledgements [21] G. Eggett and D. Naden, Hydrometall. 1 (1975) 123.
[22] D . F . A . Koch, Electroehimiea Aeta 1 (1959) 32.
F i n a n c i a l assistance f r o m the N a t u r a l Sciences [23] G.F. Pace and J. C. Stauter, CIM Bulletin 67(741)
(1974) 85.
and Engineering Research Council of Canada [24] A.V. Cooke, J. P. Chilton and D. J. Fray, "Extrac-
a n d the G e r m a n A c a d e m i c E x c h a n g e Service tion Metallurgy 1981" (The Institution of Mining
( D A A D ) is gratefully a c k n o w l e d g e d . T h e and Metallurgy, London, 1981) pp. 430-441.
[25] K.K. Mishra and W. C. Cooper, Proceedings of
a u t h o r also wishes to t h a n k D r W . W . H a r v e y Sessions, Anodes for Electrowinning, AIME
for fruitful discussion a n d c o m m e n t a n d Annual Meeting, Los Angeles, CA, February
P r o f e s s o r D r -Ing. R o l a n d K a m m e l o f Tech- 1984, edited by D. J. Robinson and S. E. James,
(AIME, New York, 1984) pp. 13 36.
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[26] B.L. Tiwari, J. Kolbe and H. W. Hayden, Metall. Electrometallurgy, Proceedings of Symposium,
Trans. B 10B (1979) 607. AIME Annual Meeting, Dallas, Texas, February
[27] W . R . Hopkins, G. Eggett and J.B. Scuffham, 1982, edited by P. D. Parker (AIME, New York,
"International Symposium on Hydrometal- i982) pp. 221-227.
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maker, (AIME, New York, 1973) pp. 127-154. ibid. pp. 167-188.
[28] D.J. MacKinnon, V.I. Lakshmanan and J . M . [41] D . M . Muir, A. J. Parker, J. H. Sharp and W. E.
Brannen, Trans. Inst. Min. Metall. Sect. C 85 Waghorne, Hydrometall. 1 (1975) 155.
(1976) C183. [42] D . M . Muir and A. J. Parker, in Energy Consider-
[29] V.I. Lakshmanan, D.J. MacKinnon and J . M . ations in Electrolytic Processes, Papers Sym-
Brannen, J. Appl. Electrochem. 7 (1977) 127. posium, Society of Chemical Industry, London,
[30] D.J. MacKinnon, V.I. Lakshmanan and J . M . 1980, pp. 29-42.
Brannen, ibid. 8 (1978) 223. [43] L. Albert and R. Winand, in Chloride Electrometal-
[31] P.R. Ammann, G. M. Cook, C. Portal and W. E. lurgy, Proceedings of Symposium, AIME Annual
Sonstelie, "Extractive Metallurgy of Copper", Meeting, Dallas, Texas, February 1982, edited by
edited by J. C. Yannopoulos and J. C. Agarwal, P. D. Parker (AIME, New York, 1982) pp.
(AIME, New York, 1976) Vol. II, pp. 994 1008. 189-202.
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