Hydrometallurgy 52 1999.

209222

Copper and nickel selective recovery by

electrowinning from electronic and galvanic
industrial solutions
P. Fornari, C. Abbruzzese

Institute of Mineral Processing, Consiglio Nazionale delle Ricerche, Via Bolognola, 7, 00138 Rome, Italy
Accepted 22 December 1998

Abstract
Laboratory investigations on the kinetics of copper and nickel electrowinning from electronic
and metal finishing industries have been carried out as depending voltage at 408C, using a
platinum mesh cathode, an anode of platinum spiral wire and a saturated calomel electrode as
reference. The selective deposition of copper and nickel is possible considering their difference in
standard potentials of about 0.6 V. The copper deposition was performed in acid conditions and
nickel deposition in basic conditions. A quantitative, selective recovery was found for both
elements. Under suitable conditions, current efficiencies are approximately 100% for both metals
and energetic consumptions are 2.422.97 and 2.413.05 kW h for copper and nickel deposition,
respectively. q 1999 Elsevier Science B.V. All rights reserved.
Keywords: Copper; Nickel; Electrowinning

1. Introduction
Copper is a metal of great importance for technical utilization. The large consumption
of copper in industry is due to his properties of electric conductivity, ductibility and
thermal conductibility. More than 50% of this metal is used in the electronic industries
and about 3040% of the copper world production is used for alloy production. Copper

Corresponding author

0304-386Xr99r$ - see front matter q 1999 Elsevier Science B.V. All rights reserved.
PII: S 0 3 0 4 - 3 8 6 X 9 9 . 0 0 0 1 9 - 5

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

electrowinning is usually the final step in the production of the metal from oxide ores
which have been treated by sulphuric acid leaching.
Nickel is a strategic metal which finds application in the electroplating industry and
in the production of different grades of stainless steel and alloy steel.
Boldt w1x described treatments of oxide ores where the nickel is recovered from
solution after ammonia leaching as a hydroxide carbonate which is then calcined to NiO.
Also, metal has been recovered by hydrogen reduction from a sulphuric acid leach.
Possibly in the future similar leach solutions could be treated by electrolysis to recover
nickel, although hydrogen reduction would seem to be the preferred method w2x.
Recently, nickel deposition at about pH 3, using pure sulphate solutions with and
without sodium sulphate and boric acid additives, a current efficiency of 7481% was
obtained at a temperature more than 608C w3,4x. The experiments reveals a sharp fall in
the current efficiency with a decrease of pH and corresponding energy consumption for
unit weight kg. of metal increased more than 3.4% due to the increase Hq concentration of the electrolyte, and consequently hydrogen evolution over metal deposition.
Many patents w57x have been described for copper and nickel separation. The aim of
this work is devoted to reduction of the environmental impact of industrial effluents
from electronic and galvanic industries and to recover valuable products. Generally the
effluents of this industry are treated by precipitation with CaOH. 2 or NaOH. A
subsequent ionic exchange process reduces the metals contents at the metal ions.
Considering their high metal content Cu, Ni, Sn, Pb etc.. they are considered toxic and
hazardous wastes. In this work an alternative approach is proposed, based on leaching
and electrowinning treatments. During leaching the industrial sludge was treated by
sulphuric acid in proper concentration and temperature. The leach solution contains
about 10 g dmy3 Cu and 10 g dmy3 Ni at 2.02.2 pH. The other elements such as Pb
and Sn were kept in the solid residue for their low solubility in sulphuric acid solution.
Copper reduction by electrowinning is performed on the leaching acid solution at about
pH 2.0 at 408C. For nickel deposition, an alternative method is proposed using
ammoniacal nickel complex at basic pH ) 10. as electrolytic bath, at 408C, utilising the
leaching nickel sulphate solution alkalinized with 30% ammonia, after copper reduction,
to eliminate hydrogen cathodic reduction and consequently to increase the current
efficiency of the process and to minimise the energy consumption.

2. Electrowinning
2.1. The cathodic reactions
Cuqqq 2eys Cu8
Niqqq 2eys Ni8

E8 s q0.34 V
E8 s y0.27 V

1.
2.

are coupled in copper electrowinning from acidic solution to the anodic reaction:
2H 2 O s O 2 q 4Hqq 4ey

E8 s q1.23 V

3.

Temperature
8C.

j A dmy2 .

Ec vs.
SCE V.

Ecell V.

V cm3 .

t s.

K d cm sy1 .

Copper electrowinning conditions and K d

Pt mesh
10 000
103.5

40

y0.30

2.20

170

14 400

0.55=10y3

Pt mesh

10 000

40

y0.40

2.40

170

7200

1.23=10y3

Pt mesh

10 000

0.701.0
approaching 0 at the end.
0.701.10
approaching 0 at the end.
1.01.15
approaching 0 at the end.

y0.50

2.60

170

7200

1.04=10y3

0.500.70
approaching 0 at the end.
0.550.75
approaching 0 at the end.
0.701.0
approaching 0 at the end.

y1.30

2.30

170

18 480

0.48=10y3

y1.35

2.50

170

7200

0.64=10y3

y1.40

2.70

170

7200

0.93=10y3

Cathode

c1
mg dmy3 .

c2
mg dmy3 .

54.10
123.5

40

Nickel electrowinning conditions and K d

Pt mesh
10 000
56.0

40

Pt mesh

10 000

45.3

40

Pt mesh

10 000

40

40

Cu and Ni contentss10 g dmy3 .

Solutions170 ml at 408C and at three constant cathodic potentials.

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

Table 1
Deposition rate constant K d during copper and nickel recovery

211

212

Table 2
Specific energy consumption by effective )98%. copper and nickel recovery
Electrowinning conditions for copper recovery
Mass
recovered mg.

Cell
voltage V.

Current
density
mA cmy2 .

Charge
C.

Time
min.

% Copper
recovery

% Current
efficiency

Specific
energy
consumption
kW h kgy1 .

y0.30

1.6824

2.20

6426

240

98.96

78.67

2.97

y0.40

1.6908

2.40

5404

120

99.46

95.86

2.22

y0.50

1.6790

2.60

0.701.0
approaching 0 at the end.
0.701.10
approaching 0 at the end.
1.01.15
approaching 0 at the end.

5552

120

98.80

93.50

2.42

Electrowinning conditions for nickel recovery

W-SCE
potential V.

Mass
recovered mg.

Cell
voltage V.

Current
density
A dmy2 .

Charge
C.

Time
min.

% Nickel
recovery

% Current
efficiency

Specific
energy
consumption
kW h kgy1 .

y1.30

1.6905

2.30

5966

308

99.44

93.44

2.41

y1.35

1.6923

2.50

6014

300

99.55

97.91

2.52

y1.40

1.6932

2.70

0.500.70
approaching 0 at the end.
0.550.75
approaching 0 at the end.
0.701.0
approaching 0 at the end.

6196

220

99.60

89.85

3.05

Cu and Ni contentss10 g dmy3 .

Solutions170 ml at 408C and at three constant cathodic potentials.

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

W-SCE
potential V.

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

213

and during the nickel electrowinning in basic solution, to the following reaction:
4OHys O 2 q 2H 2 O q 4ey

E8 s y0.40 V

4.

The order of the cathodic reduction considering the standard potential values is in the
sequence coppernickel.

3. Experimental details
3.1. Chemicals
The only chemical used was ammonia of analytical reagent grade for nickel deposition.

Fig. 1. Experimental j E curve to determine the copper cathodic decomposition potential at 408C without
stirring. Actual leaching solution 22.2 pH, contains about 10 g dmy3 Cu and 10 g dmy3 Ni. Galvanostatic
operations performed changing cell current densities proportional to current densities j . and measuring
working-reference potential W-SCE. at the equilibrium.

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

3.2. Equipment
A cylindrical glass laboratory electrolytic cell was used, 6 cm in diameter and 6.5 cm
in height with about 180 cm3 capacity. The cap of the cell was circular with guidance
holes permitting the symmetrical arrangement of the electrodes. The cell was equipped
with a thermostatic water jacket connected with thermostatic bath, magnetic stirrer under
the cell supplied for the stirring was performed with a magnetically coupled anchor, 0.7
cm in diameter and 3.5 cm in height, placed on the cell bottom and three cylindrical
electrodes: 3.5 cm in diameter and 5 cm in height of platinum mesh with a surface
which is 100 cm2 in width technical data. as cathode or working electrode W., a
centrally situated spiral 0.5 cm diameter anode or counter electrode C. of platinum wire
and saturated calomel electrode SCE. as reference situated near the cathode surface.
The cell was connected to the potentiostat-galvanostat model 555B AMEL, Italy.,
equipped with an instrument system to automatically control process parameters pro-

Fig. 2. Experimental j E curve to determine the nickel cathodic decomposition potential at 408C without
stirring. Residual solution after copper deposition alkalinized with ammonia at 10.5 pH contains about 10 g
dmy3 Ni. Galvanostatic operation performed changing cell current intensities proportional to current densities
j . and measuring the working-reference potential W-SCE. at the equilibrium.

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

215

grammable function generator mod. 568, interface mod. 560rA, integrator mod. 721,
differential electrometer mod. 631 AMEL, Italy..
3.3. Procedure
Electrowinning experiments were carried out in potentiostatic operations at constant
cathodic potential constant potential electrolysis. and constant stirring conditions
corresponding to 200 rev miny1 , studying kinetics of copper and nickel deposition at
408C at three different preset voltages. In such way the voltage between Working and
Reference electrodes was continuously monitored automatically. The corresponding
voltages V . between working and counter electrode cell voltages. measured with
differential electrometer were varied during electrolysis. Average experimental cell
voltages reported in Table 1 were utilized to calculate the energy consumption. The
current flowing through the electrolytic cell was integrated automatically. Experimental
data q . were utilized to calculate the current efficiency . and the average energy
consumption Es .. Table 2..
During the first and successive reduction of copper, previous alkalization of the
residual solution with concentrated ammonia, nickel deposition was performed. Copper
and nickel was gravimetrically determined, during kinetics as a function of time.
3.4. Chemical analysis
Copper and nickel deposits, previous dissolution, were analysed for purity with
respect to the minor elements using a Perkin Elmer ICP inductively plasma spectrophotometer.. The deposit of the both metals was also analysed by X-ray diffraction.

4. Results and discussion

The first cathodic decomposition potential 1 for copper referred to SCE at 408C, was
determined without stirring, depending on the current intensities applied to the electrolytic system by galvanostatic operations. The solution used was the actual leach
solution at 22.2 pH. Nickel cathodic decomposition potential was detected on the
residual solution after copper deposition analogous to the previous alkalization by
ammonia at 10.5 pH. The cathodic decomposition potential is about y0.1 V for copper

1
Generally the electrode potential Ecell . at which the electrolysis current begins to increase appreciably is
the decomposition potential. In this work, using galvanostatic operations, was experimentally measured at the
equilibrium W-SCE potential or cathode-reference potential as a function of the increase of applied cell current
intensities proportional to current densities.. For this we use the term cathodic decomposition potential to
describe the minimum experimental W-SCE value at which electrolysis takes place.

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

and y1.1 V for nickel vs. the SCE Figs. 1 and 2, respectively.. These are the minimum
cathodic potentials required at which electrolysis can occur. An increase in these
potential values is required to improve the rate of the process.
4.1. Copper deposition
Copper was deposited at a constant cathodic potential with respect to the reference
electrode constant potential electrolysis. from actual leach solution 22.2 pH at 408C at
the potential values of y0.30 V, y 0.35 V and y0.40 V vs. SCE, by kinetic
experiments maintaining a constant agitation corresponding to 200 rev miny1 . In Fig. 3
dependence of copper concentration variation to time decay curve. was presented in
kinetic curves. Generally copper concentration falls in time, increasing when cathodic
potential increases. The fastest kinetic rate was obtained at y0.40 V at a cell voltage

Fig. 3. Concentration decay curves of copper by electrowinning at 408C stirring 200 rev miny1 . Actual
leaching solution contains 10 g dmy3 Cu and 10 g dmy3 Ni. Potentiostatic operation performed at constant
potential electrolysis a three cathodic potential values vs. SCE. B y0.30 V, Ecell 2.20 V, v y0.40 V, Ecell
2.40 V, ' y0.50 V, Ecell 2.60 V. Initial cell current intensities I . 7001000 mA, 7001100 mA,
10001150 mA, respectively, and corresponding respective current densities of 11.716.7 mA cmy2 ,
11.718.3 mA cmy2 , 18.319.2 mA cmy2 .

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

217

approximately 2.40 V, when a copper residual concentration of 9.2 mg dmy3 and a

corresponding 99.46% copper recovery was achieved after 2 h of electrolysis. The
current efficiency under these conditions was approximately 95.86%. The kinetics at
y0.50 V, corresponding to a cell voltage of 2.6 V, were faster than the kinetics at
y0.40 V in the central part and in a continuous process. In fact after 1 h of electrolysis,
a copper residual concentration of 313 mg dmy3 , and a corresponding 81.6% copper
recovery, was obtained with a current efficiency more than 96%. The total electrolysis
time is the same for the both kinetics but at y0.50 V a small increase in current
efficiency occurs 93.5%.. At y0.30 V cathodic potential the kinetics was slow and the
current efficiency average is less than 79%. In Fig. 4 current efficiency curves,
corresponding to the decay curves of Fig. 3 are reported.

Fig. 4. Copper current efficiency by electrowinning at 408C stirring 200 rev miny1 , corresponding to
concentration decay curves as in Fig. 3. Actual leaching solution contains 10 g dmy3 Cu and 10 g dmy3 Ni.
Potentiostatic operation performed at constant potential electrolysis a three cathodic potential values vs. SCE.
B y0.30 V, Ecell 2.20 V, v y0.40 V, Ecell 2.40 V, ' y0.50 V, Ecell 2.60 V. Initial cell current intensities
I . 7001000 mA, 7001100 mA, 10001150 mA, respectively, corresponding respective current densities of
11.716.7 mA cmy2 , 11.718.3 mA cmy2 , 18.319.2 mA cmy2 .

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

4.2. Nickel deposition

Nickel deposition was performed in similar way, using the residual alkalinized
solution at 10.5 pH. Nickel was deposited at a constant cathodic potential at the potential
values of y1.30 V, y1.35 V and y1.40 V vs. SCE at 408C. In Fig. 5 presented are the
concentration decay curves of nickel vs. the electrolysis time. Nickels concentration fall
was improved when cathodic potential increases. A residual nickel concentration of 6.8
mg dmy3 and a corresponding almost quantitative nickel reduction 99.6%. was
obtained after 3 h 40 min at 408C and with a y1.40 V cathodic potential value, with a
2.70 V cell voltage average. The current efficiency has a 93.44% average. The kinetics
at y1.35 V cathodic potential, with a 2.50 V-cell voltage average was slower than the
kinetics at y0.40 V. A residual nickel concentration of 7.7 mg dmy3 and the same
recovery value 99.55%. was obtained after 4 h of electrolysis time. Current efficiency
increased to a 99.4% average. When cathodic controlled potential was kept at y1.30 V,
a nickel residual concentration of 9.5 mg dmy3 and corresponding recovery value of

Fig. 5. Concentration decay curves of Nickel by electrowinning at 408C stirring 200 rev miny1 . Residual
solution after copper deposition alkalinized with ammonia at 10.5 pH contains about 10 g dmy3 Ni.
Potentiostatic operation performed at constant potential electrolysis a three cathodic potential values vs. SCE.
B y1.30 V, Ecell 2.31 V, v y1.35 V, Ecell 2.50 V, ' y1.40 V, Ecell 2.70 V. Initial cell current intensities
I . 500700 mA, 550750 mA, 7001000 mA respectively, corresponding respective current densities of
8.3311.70 mA cmy2 , 9.1712.50 mA cmy2 , 11.7016.70 mA cmy2 .

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

219

99.7% was obtained after 5 h 8 min of electrolysis. Current efficiency was 93.44%
average. In Fig. 6 the current efficiency curves corresponding to the kinetic decay curves
of Fig. 5 were reported.
4.3. Deposition rate constant
The deposition rate constant K d cm sy1 . can be calculated using Eq. 5. Table 1.:
K d s 2.303V log c1rc2 . rSt

5.

where V is the volume of the test solution cm3 .; S is the cathode area cm2 ; c1 is the
start concentration of metal mg dmy3 .; c 2 is the final metal concentration mg dmy3 .
and t is the electrolysis time. Copper and nickel deposition rate constants are presented
in Table 1 for given experimental condition where j is the current density, Ec is the
cathodic potential vs. SCE. and Ecell is the cell voltage.

Fig. 6. Nickel current efficiency by electrowinning at 408C stirring 200 rev miny1 , corresponding to
concentration decay curves as in Fig. 5. Residual solution after copper deposition alkalinized with ammonia at
10.5 pH contains about 10 g dmy3 Ni. Potentiostatic operation performed at constant potential electrolysis a
three cathodic potential values vs. SCE. B y1.30 V, Ecell 2.31 V, v y1.35 V, Ecell 2.50 V, ' y1.40 V,
Ecell 2.70 V. Initial cell current intensities I . 500700 mA, 550750 mA, 7001000 mA, respectively,
corresponding respective current densities of 8.3311.70 mA cmy2 , 9.1712.50 mA cmy2 , 11.7016.70 mA
cmy2 .

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

Fig. 7. X-ray diffraction pattern of metallic copper and nickel deposits.

P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

221

4.4. Energy consumption

For all the experiments, specific energy consumption Es kW h kgy1 . was calculated
according to the following equation Table 2.:
Es s 100 qEcellrm

6.

where: q is the electric charge kA h.; Ecell is cell voltage V.; m is weight of deposited
metal kg., and is current efficiency %..
The average energy consumption was 2.422.97 and 2.413.05 kW h kgy1 of
metallic copper and nickel recovered, respectively. Fig. 7 shows RX pattern of metallic
copper and nickel recovered. After dissolution copper and nickel deposits were analysed
using a Perkin Elmer mod. ICP for purity with respect to the minor elements. Chemical
analysis shows the purity of the deposits and the residual solutions, analysed in a similar
way, present only traces of copper and nickel elements.

5. Conclusions
1. The cathodic decomposition potential was experimentally measured at 408C for
copper using the actual leach solution at 2.02.2 pH and for nickel in ammoniacal
solution pH 10.5., after copper reduction, at 408C by galvanostatic measurements.
These values vs. SCE were about y0.1 V and y1.1V for copper and nickel,
respectively.
2. Copper and nickel selective recovery was performed at laboratory scale at 408C in
acidic condition for copper and in basic condition for nickel, three values of constant
cathodic potential for both elements all stated with respect to the reference electrode.
3. An alternative method for nickel recovery was proposed and optimized conditions
were found in terms of voltage and current.
4. Current densities were stated and compared with the literature.
5. The current efficiency about 100%. was achieved for both elements and a
relatively low energetic consumption was obtained corresponding to 2.422.97 kW h
kgy1 of copper and 2.413.05 kW h kgy1 of nickel recovered.
6. Copper and nickel deposits were adherent to the cathode and were of acceptable
morphology, excellent quality and purity. The residual solution has a reduced environmental impact.

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Elsevier, Amsterdam, 1971, pp. 175217.
w3x V. Kumar, B.D. Pandey, D.D. Akerkar, Electrowinning of nickel in the processing of polymetallic sea
nodules, Hydrometallurgy 24 1990. 189201.

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P. Fornari, C. Abbruzzeser Hydrometallurgy 52 (1999) 209222

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