Hydrometallurgy, 31 (1992) 243-255 243

Elsevier Science Publishers B.V., Amsterdam

Enhancement of operating current density in a

copper electrowinning cell

P. Gopala Krishna and S.C. Das

Regional Research Laboratory, Bhubaneswar - 751 013, India
(Received September 12, 1991; revised version accepted February 8, 1992)

ABSTRACT

Gopala, Krishna, P. and Das, S.C., 1993. Enhancement of operating current density in a copper elec-
trowinning cell. Hydrometallurgy, 31:243-255.

Efforts have been made to enhance the operating current density of an open channel cell to obtain
high-quality cathode copper. Since increase of copper concentration and circulation rate did not im-
prove the nature of the cathode deposit, the cell was modified to circulate the electrolyte through jets
parallel to the cathode surface. With the modified cell it was possible to achieve quality deposits at a
current density as high as 400 A m-2. The hydrodynamic conditions of the cell were studied in detail.
The results show that high limiting current densities and high mass transfer coefficient values are
possible due to increase in the linear velocity. It has also shown that there are four distinct regions of
limiting current distribution on the cathode plate. Since there is no turbulence up to ~ 3.0 cm height
from the bottom edge of the cathode plate (dead zone), the cell with a jetting system may be used as
a high current density copper electrorefining cell.

INTRODUCTION

In this laboratory, a process has been developed for the extraction of cop-
per, zinc and lead from complex sulphides through ammoniacal leaching
[ 1,2 ]. The separation of copper from zinc in leach liquor has been carried out
by extracting the copper with LIX 64N and electrowinning it from the puri-
fied solution. In order to test the SX-EW process on a laboratory scale, the
continuous electrowinning of copper in conjuction with solvent extraction
was carried out in an open channel cell using a current density of 250 A m -z.
Because of the poor hydrodynamic conditions prevailing in the cell, copper
deposited in a powder form. In order to obtain quality cathode copper at such
a high current density, it is essential that the operating cell should provide
improved hydrodynamic conditions. Several methods have been suggested in

Correspondence to: Dr. P. Gopala Krishna, Regional Research Laboratory, C.S.I.R. Bhubanes-
war, 751013 Orissa, India.

0304-386X/92/$05.00 1992 Elsevier Science Publishers B.V. All rights reserved.

244 P. GOPALA KRISHNA AND S.C. DAS

the literature [3-11 ] to improve the hydrodynamic conditions and hence to

achieve higher operating current densities. These include electrolytic circula-
tion [ 3 ], air sparging [ 4-6 ], ultrasonic agitation [ 7 ], inserting turbulence
promoters [ 8,9 ] and using improved cell designs [ 10,11 ].
Submerged jets as a means of creating agitation have been used frequently
to enhance either heat or mass transfer rates. The system has uniform acces-
sibility for mass transfer [ 12 ] and has been used as a tool for electrochemical
analysis [ 13 ]. Examination of the literature shows only scant availability of
information on submerged jets [ 14-19 ] and most of these studies [ 14-16 ]
are confined to mass transfer and heat transfer in dissolution and sublimation
studies from a submerged jet impinging on the surface perpendicularly.
Information on submerged jets in electrowinning of metals is rare [ 17-21 ].
Balberyszski and Anderson [ 18 ] made an attempt to increase the operating
current density of a copper electrowinning cell by injected and direct flow of
fresh electrolyte to each anode surface. Sonin [20 ] examined the effect of
electrolyte jetting perpendicular to the cathode surface while electroplating
copper. These studies show that electrolyte jetting plays an important role in
electrowinning cells by improving mass transport conditions even at compar-
atively low circulation rates. In the present study, attempts have been made
to increase the operating current density of our copper electrowinning cell.
The various methods adopted include (i) increase of copper concentration
in the electrolyte, (ii) increase of electrolyte circulation rate and finally (iii)
injecting electrolyte parallel to the cathode surface. The hydrodynamic con-
ditions in such a cell was also studied in detail using the limiting current den-
sity technique.

EXPERIMENTAL

Materials

For copper electrowinning in a continuous circulation cell, both C u S O 4 and

H 2 S O 4 used
were of commercial grade chemicals, whereas AR grade reagents
were used in the limiting current measurements.

Apparatus

Continuous copper electrowinning

The electrolytic cell was fabricated in the laboratory using fibre reinforced
sheets (F.R.P.). The cell had a cross section of 22 X 130 cm and a height of
20 cm, inlet and outlet each of 0.8 cm diameter were provided with the cell
for continuously circulating the electrolyte. The electrolyte was fed at the bot-
tom of the cell and was permitted to overflow at the top at a height of 15 cm
from the bottom. The electrolyte jetting system was made of Perspex tubes
and placed along the bottom of the cell. The tubes (side and central, Fig. 1 )
ENHANCEMENT OF OPERATING CURRENT DENSITY 245

1.0 0.3

1.5 O, 010

.FEEDER

~
8.5

1.5 0
i

0
6.0

0 0
2
8.5
J
1.5 I 0 0 0 0

ALL DIMENSIONS ,ARE IN cm

Fig. 1. Electrolyte jetting system.

had a series of 0.3 cm diameter orifices at 1.0 cm intervals. These orifices

were made on each side of the cathode. The cathode to cathode distance was
maintained at 6.0 cm. The electrolyte was fed to the cell through the feeder
(Fig. 1 ) by a Watson Marlow metering pump at a predetermined rate. Under
the experimental conditions, each cathode was assumed to be covered by a
uniform distribution of the electrolyte and to have the same flow velocity.
Stainless steel sheets of length 20.0 cm and width of 15.0 cm were used as
cathodes and Pb-Sb (7% Sb) of the same dimensions were used as anodes.

Measurement of limiting current

The local limiting current density and mass transfer coefficients were ob-
tained by measuring the limiting current for reduction of copper at copper
micro-electrodes. The schematic diagram of the experimental apparatus is
shown in Fig. 2a. The cell employed for such studies had dimensions
30 19 20 cm and was provided with an electrolyte distributor of 1.0 cm
diameter. The distributor was provided with an orifice of 0.3 cm diameter for
jetting the electrolyte parallel to the cathode surface. The cathode was an in-
sulator plate of Perspex sheet (cross section 15 X 8 cm ) upon which 10 micro-
electrodes of 0.2 cm diameter were fixed along its central axis (Fig. 2b ). The
electrical connections protruded from the rear of the cathode surface. The
vertical position of the micro-electrodes on the cathode surface are given in
Table 1.
Fresh electrodes were used for each limiting current measurement. The mi-
cro-electrodes were carefully polished with fine emery paper to secure uni-
formity under running tap water, scrubbed with filter paper, soaked in ace-
tone, rinsed with distilled water and finally air dried. The electrode plate was
then transferred into the cell and connected to the limiting current measure-
ment circuit. A copper electrode, in the same copper sulfate electrolyte as
246 P. GOPALA KRISHNA AND S.C. DAS

o
o
I[ o

7loi o

0
o7
o
o
8cm
2ram

---,-

Fig. 2. S c h e m a t i c d i a g r a m o f e x p e r i m e n t a l set u p a n d c a t h o d e s u r f a c e w i t h m i c r o e l e c t r o d e s :
1 = c a t h o d e s u r f a c e w i t h c o p p e r m i c r o e l e c t r o d e s ; 2 = c o p p e r a n o d e ; 3 = salt bridge; 4 = m e t e r i n g
p u m p ; 5 = r e f e r e n c e electrode; 6 = p o t e n t i o s t a t ; 7 = X - Y r e c o r d e r ; 8 = j e t orifice; 9 = v o l t a g e s c a n
generator; 10=electrometer probe.

TABLE 1

Position o f the micro-electrode on the c a t h o d e surface

No. o f micro-electrode Vertical position f r o m the b o t t o m

o f the c a t h o d e plate ( c m )

1 0.7
2 2.0
3 3.3
4 4.6
5 6.0
6 7.2
7 8.5
8 9.9
9 11.2
10 12.5

Electrode area = 0.03412 c m 2.

used in the cell was employed as the reference electrode. The reduction of
copper ion to copper metal was used for limiting current measurement.

L i m i t i n g current measurement

Current potential curves for copper deposition were measured with PAR
ENHANCEMENT OF OPERATING CURRENT DENSITY 247

potentiostat (Model 173 ) operated in the potentiostatic mode. The scan rate
was maintained at 5 mV s-~ controlled by a voltage scan generator (Model
ABA 26 ). The i-Vplots were recorded by using an X-Yrecorder. The effects
of different variables on i-V curves were measured for 0 to - 7 0 0 mV with
respect to copper electrode in the same electrolyte.

Deposit examination

In order to compare the surface roughness of the electrodeposited copper

produced under different experimental conditions, the copper plates were ex-
amined under an optical microscope at a magnification of 10.

RESULTS AND DISCUSSION

Continuous electrowinning of copper in conjuction with solvent extraction

was carried out using an open channel cell. The electrolyte contained 30 g 1-
of copper and 150 g 1-1 of sulphuric acid and was continuously circulated at
a rate of 15 1 h-~. When electrolysis was carried out at a current density of
250 A m -e and at room temperature ( 3 0 + 2 C ) , powdery deposits were ob-
tained within an hour. This indicated that the current density probably ex-
ceeded the limiting current density, iL, defined as:
iL = nFDC/~ ( 1)
Equation ( 1 ) shows that the limiting current (iL) can be increased by: ( 1 )
increasing copper ion concentration and (2) decreasing the diffusion layer
thickness. The latter can only be achieved provided the hydrodynamic con-
ditions of the cell are improved.
In order to improve the quality of the deposit, the copper concentration in
the electrolyte was raised from 30 to 40 g 1- ~but no appreciable change in the
cathode deposit was marked.
The circulation rate was then raised from 15 to 60 1 h-~ in steps for im-
proving hydrodynamic conditions in the cell. It was observed that the same
powder deposits were formed even at a circulation rate of 60 1 h - 1. The cell
was then modified incorporating the electrolyte jetting system. Preliminary
experiments with the modified cell showed encouraging results for which a
detailed investigation was undertaken. The parameters taken into considera-
tion were: ( 1 ) current density; (2) electrolyte circulation rate; and (3) cop-
per concentration in the electrolyte.
Current density was varied in the range of 300 to 450 A m -2 at copper
concentrations of 30, 35 and 40 g 1-1. In this set of experiments, the circula-
tion rate was maintained at 25 1 h-1. Compact deposits of copper at nearly
95% current efficiency were achieved when 30 g 1- z of copper was electro-
lysed at 300 A m -2. As the current efficiency was raised, nodular growth with
248 P. GOPALA KRISHNA AND S.C. DAS

powder formation resulted in each case (Fig. 3). Copper concentration was
then raised to 35 g 1-~, where copper deposited in the compact form at each
current density studied. The cathode surface became comparatively rough,

Fig. 3. Photomicrograph of electrodeposited copper, X 10, Cu = 30 g 1-1, flow rate = 25 1 h - ~,

current density = 450 A m-2.

Fig. 4. Photomicrograph of electrodeposited copper, 10, Cu--- 35 g 1-1, flow rate = 25 1 h - ~,

current density = 450 A m - 2.
ENHANCEMENT OF OPERATING CURRENT DENSITY 249

TABLE 2

Effect of current density on current efficiency

Current density Current efficiency (%)

(Am -2)
Cu conc, 35 g l - ~ C u conc, 40 g l -

300 97.0 98.2

350 94.0 97.4
400 93.0 95.0
450 91.5 92.5

Concentration of H 2 S O 4 = 160 g 1-~; electrolytic circulation rate = 25 1 h - t ; period of electrolysis = 6

h; electrolysis temperature = 30 +_2 C.

Fig. 5. Photomicrograph of electrodeposited copper, 10, C u = 40 g 1-% flow rate = 25 1 h - %

current density= 4 5 0 A m -2.

and nodular formation appeared with higher current density (Fig. 4). At the
same time a fall in current efficiency was also noted (Table 2 ). As the copper
concentration was further raised to 40 g 1-1, comparatively better cathode
deposits (Fig. 5) than those at 35 g 1- l o f copper, were obtained at each cur-
rent density. The current efficiency in this case also showed a similar decreas-
ing tendency as in the earlier case (Table 2 ).
Hydrodynamic conditions in a cell are improved by high circulation rates
and thus, in turn, are the measure of operating current density of the cell. The
effect of circulation rate was studied in the range o f 15-301 h-1. During such
studies the copper concentration was varied from 30 to 40 g 1-1 and electro-
winning was carried out in the range of 300-400 A m - 2 . The results are sum-
250 P. GOPALA KRISHNA AND S.C. DAS

marized in Table 3. Copper deposited in the powdery form at all copper con-
centrations up to a circulation rate of 20 1 h-1, at 300 A m -z. On increasing
the circulation rate to 25 1 h-1, copper deposited in powder form from an
electrolyte containing 30 g 1-~ of Cu at a current density beyond 300 A m-2.
Beyond this copper concentration compact deposits were obtained at a cir-
culation rate of 25 1 h - 1 and above, within the current density range studied.
Smoother deposits were obtained at copper concentrations greater than 30 g
1-~ and circulation rates greater than 20 1 h-~. Some typical photomicro-
graphs of the deposits are shown in Figs. 6 and 7. The results so far achieved
show that incorporation of the jetting system into the cell could raise the op-

TABLE3

Effect of circulation rate on current efficiency

Circulation rate Cu conc Current Nature of

(1 h-~ ) (g 1-1 ) efficiency deposit
(%)
25.0 30.0 - powder
25.0 35.0 93.0 compact
25.0 40.0 95.0 compact
30.0 35.0 97.2 compact
30.0 40.0 98.5 compact

Concentration of H 2 S O 4 = 160 g 1- ~; current density = 400 A m - 2; period of electrolysis = 6 h; elec-

trolysis temperature = 30 _+2 C.

Fig. 6. P h o t o m i c r o g r a p h o f e l e c t r o d e p o s i t e d copper, 10, C u = 3 5 g 1- l , flow r a t e = 30 1 h - l ,

c u r r e n t d e n s i t y = 400 A m -2.
ENHANCEMENT OF OPERATING CURRENT DENSITY 251

Fig. 7. Photomicrograph of electrodeposited copper, X 10, Cu--40 g 1-1, flow rate--25 1 h ~,

current density = 400 A m -2.

erating current density at the copper concentrations used in this study. In

order to support these findings, the hydrodynamic conditions of a similar cell
(with a jetting system ) were studied in detail. The main objective of this study
was to examine the mass transport conditions of a conventional cell following
incorporation of a jetting system.
The variables taken into consideration for this study were: ( 1 ) position of
micro-electrode from the leading edge (bottom) of the cathode plate (L);
(2) electrolyte circulation rate, (3) horizontal distance between electrode
plate and the orifice of the jet (X) and (iv) height of the cathode plate from
the orifice of the jet (Y). The micro-electrodes were fixed at different heights
on the cathode plate to measure the mass transport distribution on the cath-
ode plate.
Limiting currents were measured at micro-electrodes located at different
heights on the cathode plate (Table 1 ). The mass transfer coefficients were
calculated using the following equation:

K= iL/nFC (2)
Figure 8 shows the plot of limiting current density (iL) versus vertical posi-
tion of the micro-electrode at different circulation rates. The results indicate
that the iL value increases with increase in circulation rate at each micro-elec-
trode. However, the iL value also changes depending on the position of the
micro-electrode on the cathode plate. The increase in the iL value with circu-
lation rates for the micro-electrode located at 10 cm height (from the bottom
252 P. GOPALA KRISHNA AND S.C, DAS

3200
A
~280C

~ 240C

z200C

160(:

~ 120C
~_ 80C Symbol X,cm Ycm Velocity/
c m . S -I
2.0 1.5 42.42
-~ 40C '~' " 84.84
0 - '~ 127.26
A ~ . 169.68

VERTICAL POSITION OF MICRO ELECTRODE, cm

Fig. 8. D e p e n d e n c e o f i L on vertical position o f micro-electrode.

TABLE 4

Effect of circulation rate on limiting current density

Circulation rate iL
(Lh -l ) (Am -2)

4.8 1090
9.6 1639
14.4 1910
19.2 2204

Concentration of copper= 30.0 g 1 - ' ; concentration of H2SO4= 150.0 g 1-~; electrolysis tempera-
ture = 30 _+2 C; height of the micro electrode from the bottom of the cathode plate = 10.0 cm.

o f the cathode plate) is summarized in Table 4. From these results, it is ob-

served that four-fold increase in circulation rate increases the iL value two-
fold. It is also observed that the iL value is high even at a circulation rate as
low as about 5 1 h - 1. To produce good quality deposits, most industrial refin-
ing and electrowinning processes must operate at < 50% of the limiting cur-
rent [ 22 ]. Considering this criterion, it can be seen by calculation that with
the modified cell it is possible to achieve quality electrodeposits with a cur-
rent density o f about 550 A m -2, even at a circulation rate o f 15 1 h - 1. It must
be mentioned that it was not possible to achieve compact deposits at a current
density o f 250 A m -2 and at a circulation rate as high as 60 1 h-~ when a
conventional cell was used. The operating current density of the present cell
system is high due to an increase in the cross-sectional velocity. The mass
transfer coefficient increased with an increase in the cross-sectional velocity
(Fig. 9 ), which ultimately enhanced the operating current density of the cell.
ENHANCEMENT OF OPERATING CURRENT DENSITY 2 53

X,cm Y, cm Electrode Symbol

No.
9C 2.0 1.5 4
2.0 1.5 9 O

80

7C

6O

E
~. 5O

4O

30

20

10

0
20 40 60 80 10 10 lZ,0 160 180
V / m s -I

Fig. 9. Dependence of mass transfer coefficient on velocity of electrolyte.

Figure 8 not only shows an increase in iL values with circulation rates and
position of the micro-electrodes but also shows four distinct regions on the
cathode plate as regard to the distribution of iL.
The regions and the distribution o f iL values in these regions are as follows:
(i) up to ~ 3.0 cm height from the bottom edge of the cathode plate, there
is negligible increase in iL;
(ii) from ~ 3.0 to 6.0 cm there is sharp increase in iL;
(iii) from ~ 6.0 to 8.0 cm the iL values remain almost constant; and
(iv) beyond ~ 8.0 cm the iL values slowly fall.
This shows that under experimental conditions the maximum turbulence
occurs between ~ 3.0 and 8.0 cm height on the cathode plate. The region be-
low a height o f ~ 3.0 cm acts almost as a dead zone. Similar results were ob-
tained by Ettel et al. [23] for the bottom part of the cathode plate in a con-
ventional cell. Harvey et al. [24 ] used air sparging for attaining high current
density in a copper electrowinning/electrorefining cell. They also observed a
similar unstirred zone (dead zone) near the bottom of the cathode plate. They
suggested the use o f an airosparged c~ll for copper electrorefining since the
anode slime still remain settled. The present data indicates that the cell with
254 P. GOPALAKRISHNAAND S.C. DAS

TABLE 5

Effect of orifice distance from the cathode plate (X) on mass transfer coefficient (K)

X(cm) K ( c m s -1)

1.5 37.74
2.0 38.40
3.0 37.70

Y= 0.0 cm; velocity = 84.84 cm s - ~; electrode No. = 4.

TABLE 6

Effect of the height of the cathode plate over the orifice (Y) on the mass transfer coefficient (K)

Y(cm) K(cms -I)

0.0 37.40
0.5 36.32
1.5 38.48

X = 2.0 cm; velocity = 84.84 cm s -~.

a jetting system m a y also be used for copper electrorefining at high current

densities.
The effect o f the distance between the cathode plate and orifice of the jet
(X) and the height of the cathode plate from the orifice (Y) were studied and
the results are given in Tables 5 and 6. The results indicate that within the
ranges studied both X and Y have no effect on the mass transfer coefficient.

CONCLUSIONS

Electrowinning of copper was carried out at 250 A m - 2 using an open chan-

nel cell. This resulted in formation o f loose deposits at the cathode. In order
to achieve compact cathode deposits, efforts were m a d e to enhance the oper-
ating current density o f the cell. Increase o f both copper concentration and
electrolyte circulation rate did not improve the deposit. The cell was then
modified for circulating electrolyte through jets parallel to the cathode sur-
face. With the modified cell it was possible to achieve quality electrodeposits
at a current density as high as ~ 400 A m -2 from an electrolyte containing
~ 35-40 g 1-~ o f Cu, circulated at ~ 25-30 1 h-1. The h y d r o d y n a m i c condi-
tions o f such a cell were studied in detail using the limiting current density
technique. The following observations were m a d e from these studies:
( 1 ) Increase in circulation rate increases both iL and K values. Increase in
circulation rate by four-fold increases the iL value by two-fold.
(2) It is possible to operate the modified cell at a current density as high as
,-~ 550 A m -3 even at a circulation rate o f 15 1 h - 1
ENHANCEMENT OF OPERATING CURRENT DENSITY 255

(3) Achievement of high values for ie and K are due to increase in the
cross-sectional velocity.

NOTATION

C Concentration of reacting copper ion in the bulk of the solution, g l- l

F Faraday constant
iL Limiting current density, A m -2
K Mass transfer coefficient, cm s- 1
n Number of electrons involved in the charge transfer reaction
X Distance between the cathode plate and orifice, cm
Y Height of the electrode plate from the orifice, cm
Diffusion layer thickness

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