Research Summary

The Electrowinning of Copper

from a Cupric Chloride Solution
H.K. Lin, X.J. WU and P.o. Rao
In this work, the Eh -pCl diagram of the Cu-
Cl-HzD system was established, and the ki-
netics of copper dissolution in cupric chlo-
ride solution were studied with an emphasis
on possible difficulties that may occur dur-
ing copper electrowinning. The results were
used to guide an investigation of copper elec-
trowinning from cupric chloride solution.
O. BD

=. 0 .60
o
l
Q. 0 . 40
o F 6 .olutlon
Ca."oly,e
A-
_A-


0...____0
_0-
0
-
o 1 2 3 ..
NaC, ConcentraUon In F d Solution ,
1.20

;
o
..

1. 00 :
l
0 . 80 A.
Figure 1. The effect of NaCI concentration in
feeq solution on the potentials of the feed
solution and the catholyte. The feed solution
contained 15 g/dm
3
Cu
2
+ and 10 mg/dm3 bone
glue. Flow rate: 0.015 dm"/min.; electrowin-
ning temperature: 35C; N2 sparging: 1.0 dm
3
/
min.; current density: 300 Alm2 ..
10



<
- 25
o
o
i-
50
o
-,

-100
' .' 0
\
OCurranl alliCia"cy
A Voltage
. ..
0
, \
3
\ 0
A\
\ 0

2
0,
. 0
. 0
..
Figure 2. The effect of NaCI concentration in
feed solution on the cathodic current effi-
ciency and cell voltage. The feed solution
contained 15 g/dm" Cu
2
+ and 10 mg/dm
3
bone
glue. Flow rate: 0.015 dm"/min.; electrowin-
ning temperature: 35C; N
2
sparging: 1.0dm3/
min.; current density: 300 Alm2.
60
INTRODUCTION
Chloride hydrometallurgy has been employed for many years in the processing of
precious and platinum-group metals, but it is only within the last decade that it has
been applied on a large scale in the production of base metals. Applications to
commercial-scale nickel refining have been successful and have matured, but the
successful application of chloride hydrometallurgy to copper extractive metallurgy is
yet to be seen. Duval's CuCl/ chalcopyrite leach 1.2 process went into operation in 1976,
but the copper powders produced by electrowinning from cuprous chloride solution
had to be refined; consequently, the process was suspended.
The electrodeposition of copper from cuprous chloride solutions has been the main
concern of researchers. In cuprous chloride solutions, copper ions discharged at the
cathode are monovalent rather than divalent, and the reaction occurring at the anode
is the oxidation of the cuprous ion rather than the liberation of chlorine. As a result, the
energy requirement can be decreased by a factor of two to four compared to elec-
trowinning from a sulfate solution. But electrodeposition from cuprous chloride
solutions often produces impure copper products.
2
These chloride electrolytes are
more conductive than sulfate electrolytes, and the overpotential evolution at the
anode is 0.2 V compared with 0.8 V for O
2
, resulting in Significant energy savings.
3
Thus, electrowinning from cupric chloride solutions may save energy.
Very little work has been reported on electrowinning copper from cupric chloride
solutions, but problems caused by cupric ions are often involved in electrowinning
from cuprous chloride solutions. Frat found that in the presence of sodium chloride
and a high concentration of cupric chloride, the electrolyte essentially leached the
copper plate to form cuprous chloride before deposition took place. In some instances,
the current efficiencies for copper electrowinning were as low as zero. Kosill0
5
also
studied this problem and found that the cathodic current efficiency was only 45%. He
thought that microgalvanic corrosion reduced the current efficiency. Mitter et al.
6
pointed out that the presence of cupric ions in the electrolyte is the predominant factor
in reducing the current efficiency when copper is electrowon from cuprous chloride.
Later, Cathr0
7
reported the same conclusion and noted that the rate of copper re-
solution in the presence of cupric chloride is more rapid than the deposition of copper.
WinterS found that even small amounts of Cu
2
+ in the cuprous chloride catholyte cause
a significant drop in current efficiencies.
Electrochemical reversibility can be seen from the exchange current density' (10 = 2,400
AI m
2
) for the reaction Cu+ + e- Cuo in pure chloride solution. This exchange current
density is ten times higher than that of the reaction Cu
2
+ + 2e- Cuo in pure sulfate
solution. Due to these intrinsic attributes of the copper chloride solution system,
copper electrowinning from chloride media easily produces powdered deposits.
Thus, the earlier attempts to apply such technology (e.g., Duval, Falconbridge
10
and
Dieburg
ll
) all produced powdered products. The Cuprex metal extraction process
12
is
a more successful technology for copper electrowinning from cupric chloride solution
with the production of powder or granular copper. [For an update on the Cuprex metal
extraction process, see the article by Dalton et al. in this issue-ed.J More research
13

14
has
been done on producing dense cathodic copper from cuprous chloride solutions by
sparging inert gas and adding proper organic additives.
Because the dissolution of copper can seriously obstruct the electrodeposition of
copper from cupric chloride solution, an investigation of fundamentals (described in
the sidebar) was undertaken to study this behavior and to find a guide for avoiding its
detrimental influence on copper electrowinning.
ELECTROWINNING OPTIONS
Based on the information presented in the sidebar, there are two competitive
processes for copper electrowinning: complexation dissolution (Equation 20) or
further reduction to metallic copper (Equation 21).
Cu
2
+ Cl- + e- = CuCl.
d
, + nCl- = CuCln-(n-]) (20)
Cu
2
+ + Cl- + e- = CuCl.
d
, + e- = Cuo + Cl- (21)
Thus, two obvious problems must be confronted in electrowinning copper from
cupric chloride solution. The problem of CuCl precipitation will be encountered when
JaM August 1991
a low concentration of chloride ion in the electrolyte is adopted, and the dissolution of
copper cathode will be aggravated if a high chloride ion concentration is selected.
There are two methods to achieve high current efficiency in copper electrowinning
from cupric chloride solution. In the first method, copper can be electrowon in the
conditions in which coherent CuCI can be formed on the cathode and the dissolution
of CuCI can be prohibited (i.e., copper electrowinning under low concentrations of
chloride and cupric ions). But this scheme may have the drawbacks of high energy
consumption and contamination of copper cathode by insoluble CuC!.
In the second method, a complexing agent (e.g., NaCl) is added to dissolve CuCl and
the cuprous ion drained with depleted electrolyte becomes only a small fraction of total
copper in the feed solution via an increase of copper concentration drop between feed
solution and depleted electrolyte. This scheme may be used to obtain acceptable
current efficiency, pure copper cathode and a lower unit energy requirement.
To improve the cathode current efficiencies and reduce the energy requirement for
the electrowinning of dense copper cathode from cupric chloride solution, the follow-
ing tests were undertaken, using the apparatus shown in Figure A of the sidebar.
ELECTROLYSIS
The composition of the initial solution was equivalent to the expected composition
of anolyte and filled the cell at the beginning of the test. The feed solution had the same
basic composition as the corresponding initial solution, but had a different copper
content. The feed solution was pumped to the cell continuously during the test, and its
flow rate was controlled so that the copper content of the anolyte equalled that of the
corresponding initial solution. The process temperature was controlled electronically.
The solution potential was measured using a silver-silver chloride electrode as a
reference electrode and a platinum electrode as a working electrode. The three-
electrode method was used to measure the potential of the cathode. A calomel
electrode saturated with KCl served as a reference electrode, the copper cathode
served as a working electrode and a dimensionally stable anode served as an auxiliary
electrode. A Lurgi capillary was used to reduce the ohmic potential drop of electrolyte.
All values of potential were converted to those versus standard hydrogen electrode.
Most of the total copper content in solution was analyzed by atomic absorption
spectroscopy. Cu(I) was determined in the presence of Cu(II) by oxidation with an
excess of KIO
y
Cu(II) being masked with an oxalate. The unconsumed 103- was de-
termined iodometrically, and the total copper was then determined by iodometric
titration. Chloride ion content was analyzed by the argentometric method.
DETERMINING OPTIMUM ELECTROWINNING CONDITIONS
Selecting a Diaphragm Material
Experiments were conducted under a 15 ml/min. flow rate of feed solution con-
taining 15 g/dm3 Cu
2
+ and 10 mg/dm3 bone glue, at pH 2.7 0.1 and 35C. Nine
materials were selected as diaphragms; porosity, wettability and thickness were found
to be the critical factors. Negative current efficiencies were observed in some of the
tests, indicating that the reverse process of copper electrowinning-dissolution of
copper-was very intensive. Porous polypropylene material was found to be suitable
as the diaphragm of the electrowinning cell and was used in the later experiments.
The Effect of [CI-]
As the concentration of chloride ion increases, the potentials of both the feed solution
and the catholyte increase significantly (Figure 1). The dissolution reaction of metallic
copper by cupric chloride is inevitably accelerated, and the net reaction rate, which is
decided by the rate difference between electrodeposition and electrochemical dissolu-
tion, may turn the copper electrowinning into copper dissolution (Figure 2). On the
other hand, the cell voltage is sharply reduced as the chloride ion concentration
increases. Thus, the application of a high concentration of chloride ion in the electro-
lytes will result in the disadvantage of a low current efficiency and the merit of a low
cell voltage. The current efficiency and the cell voltage should be compromised with
an optimized chloride ion concentration.
The Effect of [Cu
2
+]
The potentials of both the feed solution and the cathode increase as a function of the
increase of concentration of cupric ion in feed solution (Figure 3). As the copper
concentration increases, the catholyte potential drops sharply at lower copper contents
due to the disproportionation reaction Cu
2
+ + Cu = 2Cu+; as copper content continues
to increase, the potential rises slightly along with the increase of cupric ion concentra-
tion. This effect occurs because Cu+ is limited by the solubility product of CuC!.
The cathodic current efficiency can be kept near 100% with the catholyte containing
less than 20 g/ dm
3
copper. However, sponge copper is produced when the
concentration in the catholyte is $5 g/ dm
3
The cathodic current efficiency decreases
remarkably with copper concentration above 20 g/ dm
3
(Figure 4). The corresponding
variations of the cell voltage and the energy requirement are also shown in Figure 5.
It is clear that a copper ion concentration of 10-20 g/ dm
3
in the catholyte is desirable.
1991 August. JOM
0.35
0.30

" /0
0.25
,,---------,,-
0.20 6.---- ......
0.15
0.10


o Feed solution
.6 Cetholyle
Cathode
0.70

0.50
0."0
0.30
0.05 0.20
o 10 20 30 040 50 eo
Cu Concentration In F d Solution, g/dm
3
Figure 3. The effect of copper concentration in
the feed solution on the potentials of the
cathode, the catholyte and the feed solution.
The feed solution contained 10 mg/dm
3
bone
glue. Flow rate: 0.015 dm3/min.; electrowin-
ning temperature: 35C; N
2
sparging: 1.0 dm
3
1
min.; current density: 300 Aldm
3
.
1.0
0
'----'--."'0--'---'.0---'-----'.0
Cu Concentration in Anolyh, g/dm
J
Figure 4. The effect of copper concentration in
the feed solution on the cell voltage, the
energy requirement and the cathodic current
efficiency. The feed solution contained 10
mg/dm
3
bone glue. Electrowinning tempera-
ture: 35C. N2 sparging: 1.0 dm3/min.; current
density: 300 Alm2.
100 0 5.0
0-
80 ".0
!
;u 60 3.0

3 40 --------4 2.0 i
-
"; 20
o
1.0 20
NaCI Concentration in Feed Solution, molfdm
3
,0
Figure 5. The effect of NaCI concentration in
the feed solution on the cathodic current effi-
ciency and the energy requirement. The feed
solution contained 10 mg/dm
3
bone glue and
90 mg/dm Cu
2
+, while the anolyte contained 5
g/dm
3
Cu
2
+. N2 sparging: 1.0dm3/min.; current
density: 300 Alm2; electrowinning tempera-
ture: 25C.
61
62
FUNDAMENTALS OF COPPER DISSOLUTION
The thermodynamics and kinetics of the process of
copper dissolution were investigated. Particularattention
was paid to the internal consistency of the data in
thermodynamic considerations. The difficulty in select-
ing data was in the divergence of the available stability
constants for cupric and cuprous chloride complexes.
Kineticresearch was conducted in a 104 mm x 15 mm
x 110 mm electrolytic cell . The copper plate, with an
effective size ofO.546mmx 73 mm x87 mm, was housed
in the cathode compartment (Figure A) . Nitrogen gas
free of oxygen was introduced directly below the copper
plate at a flow rate of 1.0 dm
3
/min., both to agitate the
solution and to isolate it from air. The electrolyte solu-
tions were continuously pumped into the cathode
compartment and drained from theanodecompartment.
The two compartments were separated by a polypro-
pylene diaphragm. The flow rate of electrolyte through
the cathode compartment was kept large enough so
that the change in solution composition due to the
reaction was negligible. The ionic strength of solutions
for each group of tests was kept identical; thus, activity
coefficients of related constituents could be considered
approximately identical. Current efficiency was assumed
to be 100% and the insufficiency of copper deposition
was attributed to copper dissolution.
Thermodynamics
The thermodynamics of the CuCI-Hp system have
been discussed by some scholars; but their E,,-Iog Clo-
or E" -pCI diagrams either lacked the CuCI precipitate
dominant area, or failed to consider the equilibrium
distribution between two different valence species of
copper in calculating the fraction of each species of
copper.
I
5-17
The standard free energies of formation of species
existing in copper chloride electrolyte are summarized
in Table 1. The selected cumulative stability constants
Figure A. A cut-away view of the electrolysis
cell used in the experiments. (1) Cathode. (2)
Anode. (3) Anode compartment. (4) Electro-
lyte. (5) Cell. (6) Sparging tube. (7) Feed inlet.
(8) Anolyte and CI
2
outlet.
Table 1. Standard Free Energies of
Formation of Copper Species In the
Cu-CI-H
2
0 System
Species
Cu' (aq.)
Cu
2
(aq.)
CI- (aq.)
CuO (cryst.)
Cuq- (aq.)
Cuq/- (aq.)
CuCI/- (aq.)
CuO- (aq.)
CuCJ, (aq.)
AGO
(kllmo!)
---
50.20
64.96
-131.14
-117.9
-248.03
-377.9
-506.9
-66.81
-196.95
Calculated from the stability roru.tants of copper
chloride romple es in T.ble 2.
Ref.
18
18
18
18
Table 2. Cumulative Stability Constants of Cuprous and
Cupric Chloride Complexes at 25C
Values of Constants
Metal Ion Log Kso Logp,
---
Cu
This Study -fJ.76
Others 1.72
-fJ.76
-5
Cu
z

This Study 0.11
Others 0.1139
0.1
0.46
2.15
of cuprous and cupric chloride complexes and those for
comparison are listed in Table 2. The equations used to
calculate the equilibrium concentration distribution of
copper species and to construct the Eh-Iog 30- diagram
of this system are presented in Tables 3 and 4. The E,,-
log 30- diagram and copper species distribution are
given in Figure B and Table 5, respectively.
Most copper hydro metallurgy is carried out in sulfate
solutions in which cuprous ion is unstable and controlled
by the following disproportionation reaction:
19
Cu
2
+ Cu = 2Cu' (1)
where the equilibrium constant is
K = = lD-" 1lS (2)
The concentration of cuprous ion would not be more
than 37 x 1 0" M ilthe total concentration of copper ions,
[CulT' was 0.157 M. However, Ihe situation in the
chloride solutions of the identical total copper concen-
tration is different.
As indicated in Rgure B, the CuCI precipitate will start
to appear when the activity of free chloride ion exceeds
1.4 x 1 ()-1 M and the activity of free cupric ion exceeds
0.1 M. The disproportionation reaction loses its control
on the concentration of cuprous species only as the
concentration of chloride ion surpasses the ratio of the
solubility product of cuprous chloride (1 .72 x 10-1) to the
equilibrium constant of the disproportionation reaction:
1.72 x 10-
7
11()-606 = 0.198 M
The dominant area of CuCI precipitate extends from
the free chloride activity of 1.4 x I()-1M toO.2 M. Taking
into account the activity coefficient of the chloride ion.
the upper concentration limit of free chloride ions is
about 0.4 M. The practical electrowinning process may
not be in equilibrium, and the concentration of cuprous
ion in the area next to the surface of the cathode can be
much higher than in the bulk catholytes. Therefore,
even in solutions having 1 M total chloride ions. [CI-},
(0.625 M of free chloride ion concentration), CuCI
precipitation was observed, resulting in a sharp de-
crease in current efficiencies. Table 5 shows that the
value of the activity product of free chloride and cuprous
ions (7.68 x 1 Q-9) is about two orders of magnitude
smaller than the solubility product of CuCI (1.72 x 10-
7
)
in the solutions of 0.157 M total copper and 3 M NaCl,
which gives the cuprous species the stability to exist in
solutions.
The proportion of total cuprous species in the total
copper species is almost 100% in the solutions of 1-5 M
total chloride ion and 0.157 M total copper ooncentra-
tion. as indicated in Table 5. Moreover, the higher the
concentration of chloride ion is, the lower is the fraction
of cupric species in this system. The predominant
chlorocuprates (I) are CuCI,:I-, CuClt and The
fractions of all cupric species are exceedingly insignifi-
Log 13, Log 13
3
Log p. Ref.
6.30 6.08 5.70 19, 20
5.610 5.263 17
5.5 5.7 21
4.88 5.98 22
6.04 5.98 5.62 23
-0.64 24
-0.5444 17
--D.6 21
--D.27 -2.48 -2.30 22
2. 5 3.55 4.28 23
cant. The total concentration of all cupric species was
less than the analySiS limit of 6 x 1 ()-6 M in a solution of
10 gldm
3
Cu and 3 M NaCI agitated with copper filings
for 24 hours.
Rgufe B more strikingly shows the stability of cu-
prous species in the chloride solutions. The equilibrium
potential between metallic copper and the solution
becomes more negative along with the increase of
chloride ion concentration, which suggests that ca-
thodic reduction of cupric and cuprous ions from the
solution would be more difficult. Conversely, anodic
dissolution of metallic copper would be much easier.
The boundaries of the predominant areas olthe species
CuCI.-io-2! and CuCI.--f"
I
) rise steeply, which suggests
that the potential of feed cupric chloride solutions would
ascend sharply with increaSing concentrations of chlo-
ride ion and the corrosion of copper cathode would
become more severe. These effects were confirmed in
the laboratory tests of copper electrowinning described
in the main text.
Kinetics and Mechanisms
The dissolution rate of copper (V 100' measured in glm2
per minute) with respect to acidity, chlofide ion, cupric
ion and cuprous ion concentrations (M) are shown in
Equations 3-9: these equations have linear regression
coefficients greater than 0.95. In these tests, current
density was kept at 300 AlrnZ, bone glue was added to
a concentration of 10 mgldm
J
, and N
2
sparging (used to
eliminate or reduce diffusion resistance) took place at
1.0 dml/min.
log V$<A = 0.896 + 0.00142 log [H') (3)
(pH 2.8 to pH 0.48)
log V ... = 0.943 + 0.110 log [H' ) (4)
(pH 0.48 to pH -0.39)
log V ... = 0.420 + 1.84 log [CI-I, (5)
([CI-}, 0.472 M to 1.472 M. in the form
of NaCI and CuCI
2
)
log V ... =-1.39 + 1.92109 [CI-)T (6)
([CI-I, 0.572 M to 1.572 M, in the form
of HCI and CuCI
2
)
log V ... = 1.21 + 0.599 log [Cu2'}, (7)
([Cu
2
'h 0.0614 M to 0.562 M)
log V ... = 0.808-0.00332109 [Cu'), (8)
([Cu'), 0.0787 M to 0.315 M)
log V $<A = 0.676-{).270 log [Cu'), (9)
([Cu' ), 0.315 M to 0.708 M)
The reaction order of copper dissolution with respec1
to [H-] is zero (pH 2.8 to pH 0.48) as shown in Equation
3. The pH was adjusted with H
2
SO., and the ionic strength
was held constant with the addition of . How-
ever, acidity has a small effect on the kinetics of copper
JOM August 1991
dissolution (reaction order: 0.11 ) at pH below 0.48. The
potential of the feed solution rose sharply with increas-
ing acidity in the range of acidity at pH 0.48. Perhaps the
feed potential is related to the stability of cuprous
chloride complexes, such as HCuCl, and H
2
CuCI
3
.
Obviously, the formation of these complexes wil l show
a positive effect of acidity on copper dissolution.
The reaction order with respect to the ccncentration
of chlori de ion is two, as represented in Equations 5 and
6. A similar result was obtained by Hurlen2S when the
total chlorideccncentration was less than 1 M. TolleyZl
found the effect 01 chloride ccncentration on the reac-
tion kinetics to be first order; perhaps the data in that
case were obtained in the ccndition in which reaction
kinetics were ccntrolled by transler of reactants. Kozin
et al.
26
reported that the order of the reaction was
ccntrolled by the diffusion of chloride ion from the bulk
solution to the surface of the ccpper electrode under
certain ccnditions. The reaction order with respect to the
ccncentration 01 chloride ion above 1.47 M gradually lell
below two in this study, which suggests that the reaction
mechanism is more complicated.
With respect to cupric ion ccncentration in the range
010.0614 M to 0.562 M, the reaction order was found to
be about 0.5 (Equation 7). This is ccnsistent with the
result obtained by Tolley.Zl
The reaction order was found to be zero with respect
to cuprous ion ccncentrations of 0.0787 M to 0.315 M
(Equation 8), but this order decreases to -{).27 at
cuprous ion concentrations above 0.315 M. This indi-
cates that the reverse reaction 01 ccpper dissolution
slows the net rate ollorward reaction under higher Cu-
ccncentration.
The order 01 zero with respect to (H') indicates H-
might not participate in the reaction in the solutions with
pH> 0.48. The order of zero with respect to [Cu' ] indi-
cates that the rate of reverse reaction caused by Cu'
cculd be negligible. Thus, the overall copper dissoluti on
process of Cu Cu(l) (aq.) should be irreversible.
However, there may be reversible intermediate steps.
Table 3. Equations for Calculating the
Distribution of Copper Species (Known
[CU]T and [CI-]T)
[Cu' J2/[Cu" ] = lCJ-6'"
[CuCk ]/ ([Cu-][CI-]' ) = 1.995 x 1()6
[CuO;'-]/([Cu' ][O-P) = 1.202 x 1()6
= 5.012 x 10'
[CuO-] I ([Cu" j[CI-J) = 1.288
[Cuq] / ([Cu
2
' )[Cl-)2) = 0.2991
fCu ' ] + [CuCl,-] + [CuCll -] + +
fCu" ] + [CuC!-] + [CuCl,] = [CulT
lCI-) + 2[CUC!i l + 3[CuC1l-) +
+ [CuO' ) + 2[CuO,] = [CI-]T
Table 4_ React ions Involved in the
Eh Iog aCl- Diagram of the
Cu CI H
2
0 System"
Cu" + 2e- = Cu
CuCI(s) + e- = Cu + 0 '
Cu" + 0 - + e- = CuC!(s)
CuCl(s) + CI- = Cuq-
+ e- = Cu + 20-
+ Cl- = CuCI/ -
CuCI/ - + e' = Cu + 30-
Cu" + C)- = CuCl '
Cu" + 20- + e- =
CuO' + 0 - + e- =
CuOl - + C)- =
CuCV- + e- = Cu + 4CI-
CuC)' + 0 - = CuC!.,
+ e- = CuO;-
+ C)- + e- = CuC!,'-
+ 2CI- + e- =
All soluble Cu species have an activity of 0.1 M.
1991 August JOM
Table 5_ Equilibrium Concentration Dis tribution of DiHerent Copper Species with
DiHere nt Chloride Concentrations
Species Concentration (M)
Total [C)-] 1.0 3.0 5.0
Free [0 -) 0.625 2.507 4.457
Cuprous Ion
[Cu' ) 1.366 x 10-
7
3.063 x 10-" 4.567 x 10-
10
[Cuq -) 0.1065 0.0384 0.0181
[CuCI/-] 0.0401 0.0580 0.0486
0.01040 0.0606 0.0903
[CUU})T 0.157 0.157 0.157
Cupric Ions
[Cu" ) 2.142 x 1 Q-<! 1.077 x l O-il 2.395 x 1
[CuO' ] 1.724 x 10-8 3.47 x l O-il 1.375 x 10-
12
[CuC!.,) 1.917 x 10-'1 1.551 X 10-
11
1.090 X 10-
12
[Cu(lI)I
T
4.058 x 1 Q-<! 6.106 x l O-il 2.705 x 10-
12
The total concentration of copper species in the solution is 0.157 M.
Winter' pointed out that the anodic reaction of Cu(l)
oomplexes at an inert electrode was a fast, reversible
reaction, and, of course, the cathodic reaction 01 Cu(lI)
oomplexes was also reversible. Altukhov etal. 21 pointed
out that the anodic reaction of ccpper dissolution was
ccntrolled by desorption of adsorbed CuCI (CuCl
odS
).
Kozin et al .28 more clearly pointed out that the overall
reaction of ccpper dissolution was controlled by the
dissolution kinetics of CuCI ... due to CuCl
odS
passivation.
In addition, it is well known that cuprous chloride can
form a seri es of coordinated oomplexes in ccncentrated
chloride solutions such as CuCI
2
-, CuClt, CuCI,J- and
so on.29 For the above mentioned reasons, the reaction
of oopper dissolution oxidized by cupric chloride is
proposed as lollows:
0.5Cu + 0.5Cu
2
- + CI- last CuCl1d! (10)
CuCl1d> + CI- (1 1)
+ CI- last CuClt (12)
CuClt + CI- 'asICuClt (13)
Reaction 11 is a rate-determining step: hence, the
ccpper dissolution rate can be expressed as
V sa = k
,1l
6[CI-) (14)
where [CI-) is the ccncentration of free chloride ion, e is
the ccverage of active sites on the cathode surface by
CuCl
ads
, and k, 1I is the rate ccnstant of the forward
reaction of Reaction 11.
The following rate equation can be obtained under a
steady state.
k,,,,(1--{l) 't.![Cu
2
'11" \CI-J - k,m>6 =
k
11l
6[CI-J (15)
where k,,,, and kIm> are the rate ccnstants of the forward
and reverse reactions of Equation 10, respectively, and
[Cu
2
-) is the ccncentration 01 cupric ions.
Combining Equations 14 and 15 under a ccndition of
e 1 yields
(16)
k",kIOl [Cu" )"2 [CI-)2
k,m> + kl. [CI-]
Because Equation 10 is a fast, reversible reaction, and
Reaction 11 is slower and irreversible, k,m> >> k'll ICI-I
Hence, the second term in the denominator of Equation
16 can be omitted at lower chloride concentrations, and
Equation 16 can be simplified as
Vrd = \ .k
,01
[Cu" P [CI- )2 = kl,,!<,o[Cu" )V2[CI-]2 (17)
I,.
where K
,O
is the equilibrium ccnstant 01 Equation 10.
It is thus clear that the reacti on orders with respect to
cupri c ion and chloride ion concentrations are 0.5 and
two, respectively.
As indicated in Equation 17, the reaction order with
-,
Figure B. The Eh-Iog aa- diagram for the Cu(I)1
Cu(II)-CI--HP system.
respect to Cu' concentration is zero, which isccnsistent
with our test results having a Cu' ccncentration below
0.315 M. But as the cuprous ion ccncentration ap-
proaches saturation level. the reverse reaction of Equa-
tion 11 cannot be ignored, and the negative order of
reaction with respect to Cu' ooncentration becomes more
significant (Equation 9). Thus, the supposed reaction
mechanism can explain the phenomena observed in
the experiments.
Equation 17 indicates that corrosive dissolution of
copper cathode by cupric chloride is very serious in the
solution containing high concentrations 01 chloride and
cupric ions.
Some investigators
93l
studied the discharging of
ccpper electrodeposition from chtori de solutions, but
few ccn sidered ccpper dissolution in the study of copper
electrowinning in the Chloride soluti on. In fact, elec-
trodeposition and dissolution of ccpper in chloride solu-
tion, especially in cupric chloride solution, are two
indivisible processes.
Karabinis and Duby30 studied the deposition of ccp-
per Irom chloride electrolyte with chronopotentiometry
and found that it was a single-electron discharging
process following two chemical reactions:
CuClt = CU' + 3C!- (18)
(19)
However, Pestrikov et al.
31
found Ihat the electro-
chemically active species upon cathodic reduction was
CuCI instead of Cu' . The evidence of the presence of
CuCf and the observation that current efficiency ex-
ceeds 100% under the ccnditions of forming CuCI
precipitate on the surface of ccpper cathode may in-
dicate that CuCI ... is indeed an electrochemically active
species for cathodic reduction. It was also observed that
the cuprous chlori de produced by the first discharge
step was not reduced in time and was washed off with
depleted electrolyte under the conditions 01 high levels
of cuprous and chloride ions .
63
"
Noel Conc e nlt ' lion ;0 " fle d Solu\lon, mo lld..r
Figure 6. The effect of NaCI concentration in
the feed solution on the potentials of the
cathode and catholyte. The feed solution con-
tained 90 mgJdm3 Cu
2
+ and 10 mgJdm
3
bone
glue; the anolyte contained 5 gJdm
3
Cu
2
+. N2
sparging: 1.0 dm3/min.; current density: 300
Alm2; electrowinning temperature: 25C.
100
-0
~ :=:r-o_
0 - 0
i 80
4.0
;
~
..
w
80 3 .0

C
~ ,
40 2.0
<J
. ~
0
-6--6 L. 6 -
~
fL
1.0
~
20 ~

<J
.
w
0 0
0 10 20 30
Cu Concentration in Anolyt. , gJdm
l
Figure 7. The effect of copper concentration in
the anolyte on the cathodic current efficiency
and the energy requirement. The feed solution
contained 90 mgJdm
3
Cu
2
+, 3.0 mol/dm
3
NaCI
and 10 mg/dm
3
bone glue. Electrowinning
temperature: 25C; N
2
sparging: 1.0dm3/min.;
current density: 300 Alm2.
ACKNOWLEDGEMENTS
The autJwrs express their appreciation to
Nerco Minerals Company for their financial
support and permission to publish this paper.
ABOUT THE AUTHORS ____ _
H.K. Lin received his Ph.D. in metallurgy from
the University of Uiah in 1985. He is currently
an assistant professor at the University of
Alaska at Fairbanks. Dr. Lin is also a member
ofTMS.
X.J. Wu received his M.S. in metallurgy from
Central South University of Technology. China,
in 1981 . He is currently a visiting scholar at the
University of Alaska at Fairbanks. Mr. Wu is
also a member of TMS.
P.O. Rao received his Ph.D. in mineral
preparation from Pennsylvania State Univer-
sity in 1961 . He is currently a professor at the
University of Alaska at Fairbanks. Dr. Rao is
also a member of TMS.
If you want more Information on this subject,
please circle reader service card number 62.
64
When the copper content is less than 20 g/ dm
3
, the complexation of cuprous and
chloride ions is weak. Hence, the total concentration of cuprous ions is controlled
mainly by the solubility product of cuprous chloride, which is only 1.72 x 10-
7
As a
result, the total cuprous ion concentration would not be more than 1.7x 10-
5
g/dm3 in
the solution. Therefore, the amount of cuprous ion drained with depleted electrolyte
(anolyte) is insignificant. The CuCI precipitate formed by the reduction reactions
adheres tightly to the cathode surface and is further electrolytically reduced to metallic
copper. However, CuCI reduction is not fast enough to reduce all CuCI in time so that
some white precipitate always remains on the surface. For this reason, cathodic current
efficiencies often exceed 100%. When the copper concentration in the electrolyte
increases further above 20 g/ dm
3
, the amount of precipitated CuCI grows so large that
it resists the electric current, falls off the cathode surface and suspends in the
electrolyte.
It is imperative to use an electrolyte with a high chloride ion content to prevent
formation of a cuprous chloride precipitate and to improve the conductivity of
electrolytes. But an electrolyte with a high concentration of chloride ion would reduce
the current efficiency because of the formation and drainage of cuprous complexes. It
seems that conventional electrowinning technology, with a large circulation of electro-
lytes, is not suitable for copper electrowinning from cupric chloride solutions.
ELECTROWINNING UNDER OPTIMIZED CONDITIONS
Electrowinning was conducted with a high-copper feed solution and a low-copper
anolyte. NaCI was added to the feed solution. The maximum copper contentofthe feed
solution may be limited by copper extraction and stripping processes. The minimum
copper content of the anolyte may be restricted by the physical specifications of copper
cathode. The related technological parameters remain to be investigated.
Selecting Optimum [CI-]
As shown in Figure 5, when the sodium chloride content in the electrolyte increases,
the unit energy consumption for copper electrowinning progressively descends, and
the cathodic current efficiency descends in the NaCl concentration below 1 M but
ascends somewhat above 1 M NaCl, which is distinctly different from Figure 2. A
concentration of NaCl below 1 M is not strong enough to dissolve all CuCl produced
by reduction in the electrolyte, and the amount of suspended CuCl exiting with spent
electrolyte increases with increasing NaCl concentration. A concentration of NaCl
above 1 M was a different situation; here, the loss of electricity with the cuprous ions
exiting with the spent electrolyte could be limited by controlling the copper concentra-
tion drop. The polarization of the cathode (its potential changes in a negative direction)
ensured the electrodeposition of copper; thus, high current efficiencies were obtained
(Figure 6). Therefore, the electrolyte containing 3 M NaCl was chosen.
Optimizing Copper Content in the Spent Electrolyte
Cathodic current efficiency decreases somewhat, and energy requirements increase,
as the copper content in spent electrolytes increases. Accordingly, the minimum
copper content in the spent electrolyte should be selected (Figure 7). However, as NaCl
is added into electrolytes, the concentrations of free cupric and cuprous ions are
gradually reduced and the supply of electrochemically active CuCI becomes insuffi-
cient for cathodic discharge to obtain dense and smooth deposited products. A dense
copper cathode can be obtained from a 5 g/dm3 Cu chloride solution containing 1 M
NaCl, but only sponge copper is obtained from the same solution containing 3 M NaCl.
With a 3 M NaCl concentration, the spent anolyte should contain 10-15 g/ dm
3
Cu to
produce a dense copper cathode at high current efficiencies.
The Effect of Animal Glue
Mackinnon and Brannen
14
categorized the effect of various addition agents on
copper electrowinning from cuprous chloride solution. Animal glue (e.g., bone glue)
has been extensively applied in the practice of copperelectrorefining. After a preliminary
test, bone glue was selected as the additive in this study. It is worth noting that the
cathodic potential drops as the amount of bone glue increases, which indicates the
increasing polarization of the cathodes (Table I). Thus, the addition of bone glue has
the function of leveling and smoothing the surface of copper cathodes. Based on the
results of metallographic examinations, a dose of 10 mg/ dm
3
bone glue was selected.
The Effect of Current Density
Without sparging or stirring,32 the electrodeposition of copper from chloride solu-
tion produced only a rough and nodular deposit at a current denSity above 100 A/m
2
.
With nitrogen sparging at 1.0 dm
3
/ min., a very smooth and dense copper cathode
can be produced from cupric chloride solution containing 10 g/ dm
3
Cu, 3 M NaCI and
10 mg/ dm
3
bone glue at current densities up to 500 A/m2 and a temperature of 25C.
If a higher energy consumption and rougher cathode surface were permitted, a dense
cathode product could be produced from the identical feed solution at up to 800 A/m2.
Current densities above 1,000 A/m
2
result in sponge copper. The increase of current
JOM August 1991
Table I. The Effect of Bone Glue on Copper Electrowinning*
Amount of Bone Glue (mg/dm3)
Parameter 0 10 20 40
Potential of Cathode (m V) 44 39 34 23
Current Efficiency (%) 94.00 93.58 93.36 93.28
Appearance of Cathode Smooth Very Very Very
Surface Smooth Smooth Smooth
Ions in Catholytes
[Cu
2
+] (g/dm
3
) 4.26 3.85 3.92 4.12
[Cu+] (g/dm
3
) 6.79 6.96 7.62 8.78
[Cu
2
+]/[Cu+j 0.63 0.53 0.54 0.47
The feed solution contained 90 g/ dm' Cu" and 3 M NaCl; the catholyte contained a total of 10 g/ dm' Cu and 3 M NaCl;
other conditions-300 A/m'; 25C; N, sparging: 1.0 dm'/min.
Table II. The Effect of Current Density on Copper Electrowinning
Current Cone. of Ions in Catholyte Current Energy Surface
Density
[Cu+], [Cu
2
+], [Cu
2
+]1 Efficiency Voltage Consumption Appearance of
(Alm
2
) (g/dm3) (g/dm3) [Cu+] (%) (V) (kWhlkgCu) Cathodes
---
300 6.96 3.85 0.553 93.58 1.80 1.62 Smooth
400 6.46 4.85 0.762 93.80 1.92 1.67 Smooth
500 5.83 4.58 0.786 93.91 2.15 1.93 Smooth
600 5.31 4.78 0.885 94.00 2.25 2.02 Smooth
700 4.81 4.58 0.952 95.66 2.38 2.10 Dense
800 5.34 5.15 0.964 95.60 2.47 2.18 Dense
900 5.88 4.74 0.813 88.04 2.57 2.46 Some Sponge
1,000 7.49 2.94 0.393 77.45 2.67 3.04 Sponge
density favors the electrodeposition of copper; the current efficiency and ratios of
concentrations of cupric to cuprous ions in the catholyte all go up with increasing
current densities (Table II, Figure 8). It is believed that the decrease of the current
efficiency above 900 AI m
2
is due to dropping of the sponge copper, which reacts with
cupricionstoformcuprousions.Thisisevidencedbythedecreaseof[Cu
Z
+] I [Cu+] (Table
II). Energy consumption increases with increasing current densities. Thus, current
density selection is a compromise between capital cost and energy consumption.
References
1. F.M. Schweitzer and R. W. Livingston, "DuvaY s CLEAR Hydrometallurgical Process," Chloride Electrometallurgy, ed. P.D. Parker
(Warrendale, PA: TMS, 1982), pp. 203-220.
2. D.M. Muir and G. Senanayake, "Refining of CLEAR Copper Powders by the Parker Process," Proceedings on Extractive Metal-
lurgy (Victoria, Australia: AusIMM, 1984) pp. 353-359.
3. J.P. Pemsler, D. Dempsey andJ.K. Litchfield, Proc. Electrochem. Soc., 86-13 (Pennington, NJ: the Electrochemical Society, 1986),
pp.207-216.
4. D.J. Fray, "Electrolysis of Cupric and Cuprous Chloride Solutions," Mineral Processing & Extractive Metallurgy: Transactions-
Section C, 96 (March 1987), pp. 49-53.
5. A.Y. Kosillo, "Electrowinning Copper from a Cupric Chloride Solution," Kompleksn. Ispol'z. Miner. (]2) (]983), pp. 68--<;9.
6. G.c. Mitter et al., "Electrowinning Copper from Cuprous Chloride," J. Sci. Ind. Rev., 20D (]961), pp. 114-116.
7. KJ. Cathro, "Electrowinning Copper from Chloride Solutions," Trends in Electrochemistry, ed.J.O.M. Bockris et a!. (New York:
Plenum Press, 1977), pp. 355-372.
8. D.G. Winter, J.W. Covington and D.M. Muir, "Studies Related to the Electrowinning of Copper from Chloride Solutions," op.
cit. 1, pp. 167-188.
9. L. Albert and R. Winand, "Copper Electrowinning in Chloride Aqueous Solutions," op. cit. 1, pp. 189-202.
10. E. Andersen et aI., "Production of Base Metals from Complex Suiphide Concentrates by the Ferric Chloride Route in a Small
Continuous Pilot Plant," J. du Four Electrique, (8) (1981), pp. 32-40. ..
11. U. Filor, "Regenerations-undKupfer-Riickgewinnungssystemfiir Atzmedien," Metalloberf/ache, 41 (1 ]) (] 987), pp. 511>-520.
12. R.F. Dalton et aI., "Cuprex-New Chloride-Based Hydrometallurgy to Recover Copper from Sulfide Ores," Mining Engi-
neering (January 1988), pp. 24-28.
13. L. Albert and REP. Wind, "Characterization of the Behavior, in Chloride Solution, of Copper and of the Most Important
Impurities Contained in a Sulphide Concentrate, in Order to Recover the Copper," Chloride Hydrometallurgy, (Brussels, Belgium:
Benelux Metallurgie, 1977), pp. 319-335.
14. D.J. Mackinnon andJ.M. Brannen, "Factors Affecting the Structure of Copper Deposits Electrowon from Aqueous Chloride
Electrolyte," J. Appl. Electrochem., 15 (5) (1985), pp. 649-658.
15. A. Yazawa and N. Eguchi, Hydrometallurgy Process and Waste Water Treatment (Tokyo: Kyoritsu, 1975), pp. 32-41.
16. D.M. Muir and G. Senanayake, "Refining of CLEAR Copper Powders by the Parker Process," op. cit 2, pp. 353-359.
17. J.P. Wilson and W.W. Fisher, "Cupric Chloride Leaching of Chalcopyrite," JOM, 33 (February 198]), pp. 52-57.
18. W.M. Latimer, Oxidation Potentials, 2nd ed. (Englewood Cliffs, NJ: Prentice-Hall, 1952), pp. 183-188.
19. E. Hogfelt, Stability Constants of Metal-Ion Complexes, Part A: In-organic Ligands (Oxford, U.K.: Pergamon Press, 1982), pp. lO-
ll.
20. R.c. Weast, CRC Handbook of Chemistry and Physics, 68th ed. (Boca Raton, FL: CRC Press, 1987-1988), B. 207.
21. J.A. Dean, Lange's Handbook of Chemistry, 11th ed. (New York, NY: McGraw-Hill, 1973), p. (5)-46.
22. P. Duby, INCRA Monograph N, The Metallurgy of Copper: The Thermodynamic Properties of Aqueous Inorganic Copper Systems (New
York: International Copper Research Association, 1977), p. 22-35.
23. W.K Tolley, RH. Huang andJD. Miller, "Reaction Kinetics Involved in Cupric Chloride Leaching of Metallic Copper Spheres
in a Stirred Reactor," op. cit. 13, pp. 9&-133.
24. L.G. Sillen, Stability Constants of Metal-Ion Complexes, Sect. 1: In-organic Ligands, special pub. no. 17 (London: the Chemical
SOciety, 1964), pp. 285-286.
25. T. Hurlen, "Electrochemical Behavior of Copper in Acid Chloride Solution," Acta Chemica scandinavica, 15 (196]), pp. 1231,
1239.
26. L.F. Kozin, KK Lepesov and S.N. Nagibin, "The Investigation of Copper Ionization in LiCl Solution by the Method of Rota ling
Disc Electrode with a Ring," Izveshia Akndemii Nauk Kilzahskni sSR, seriia Khimichesknia (6) (1980), pp. 21>-33.
27. V.K Altukhov et aI., "The Mechanism of Anodic Oxidation of Copper in Chloride Solutions," Elektrokhimiya, 15 (2) (]979), p.
286.
28. L.F. Kozin, S.N. Nagibin and KK. Lepesov, "Kinetics and Mechanism of Anodic Oxidation of Copper in Chloride Solutions,"
Ukrainskivi Khimicheskivi Zhumal, 48 (11) (1982), pp. 1194-1197.
29. R.J. Meyer and Erich Pietsch, "Kupfer," Gmelins Hanbuck Der Anorganischen Chemie, System-nummer 60, Teil B, Lieferung 3
(Weinheim, Germany, Verlag Chemie, 1965), p. 1420, pp. 1401>-1411.
30. V.D. Karabinis and P. Duby, "Chronopotentiometric Studies of Copper Deposition from Chloride Electrolytes," op. cit. 1, pp.
203-220.
31. V.F. Pestrikov, Yu.P. Khranilov and L.A. Merzlyakova, "On Mechanism of the Cathodic Reaction of Chloride Copper (I)
Complexes," Electrokhimiya, 13 (1979), pp. 1380-1383.
32. S.D. Gokhale, "Electrolysis of Cuprous Chloride," J. Sci. Ind. Rev., lOB (]951), pp. 31&-321.
1991 August. JOM
I
a '0. 1 mm
c
Figure 8. Micrographs showing the effect of
current density on the morphology of deposits
electrowon from a catholyte containing about
10 g/dm
3
Cu, 10 mg/dm
3
bone glue and 3 M
NaCI with 1.0 dm3/min. N2 sparging at 25C.
Current density: (a) 400Alm2; (b) 500Alm
2
; (c)
800 Alm2; and (d) 1,000 Alm2.
65