See discussions, stats, and author profiles for this publication at: https://www.researchgate.

net/publication/234111190

The Influence of Impurity Ions on The Electrowinning of Copper from Waste

PCBs Leaching Solutions

Conference Paper · October 2012

DOI: 10.13140/RG.2.1.2701.5200

CITATIONS READS

5 1,751

4 authors:

Arman Ehsani Ersin Yener Yazıcı

Adana Alparslan Türkeş Science and Technology University Karadeniz Technical University
32 PUBLICATIONS   64 CITATIONS    119 PUBLICATIONS   1,856 CITATIONS   

SEE PROFILE SEE PROFILE

Haci Deveci Fatih Erdemir

Karadeniz Technical University Karadeniz Technical University
194 PUBLICATIONS   4,748 CITATIONS    46 PUBLICATIONS   690 CITATIONS   

SEE PROFILE SEE PROFILE

Some of the authors of this publication are also working on these related projects:

Development of a Novel Process for Solution Purification, Removal of Metals and Recovery of Cyanide from Gold-Laden Pregnant Leach Solutions View project

Utilization of Natural Resources View project

All content following this page was uploaded by Haci Deveci on 30 May 2014.

The user has requested enhancement of the downloaded file.

B27
The Influence of Impurity Ions on The Electrowinning of Copper from Waste PCBs
Leaching Solutions
Arman Ehsani, Ersin Y. Yazıcı, Hacı Deveci
Div. of Mineral & Coal Processing, Dept. of Mining Eng., Karadeniz Technical Univ., Trabzon, 61080,
Turkey

Fatih Erdemir
Dept. of Metallurgical & Materials Eng., Karadeniz Technical Univ., Trabzon, 61080, Turkey

ABSTRACT: In this paper, the electrowinning of copper from a synthetic copper sulfate solution and the
pregnant leach solution (PLS) derived from the leaching of e-waste was investigated. The effects of
impurity ions (Co2+, Fe3+ and Cl-) and additives (thiourea and gelatine) on the corrosion of lead anode,
deposit quality and morphology were studied. The current efficiency (CE) was determined to be 12%
lower in the electrowinning of copper from the PLS (84% vs 96% CE) than from the synthetic solution
presumably due to the presence of impurities in the former. However, an extensive corrosion of the lead
anode was observed in the synthetic solution compared with the PLS. The presence of Co2+ in the
synthetic electrolyte solution was found to decrease the anode potentials (by ~0.1 V) and substantially
mitigate the corrosion of anode with a smooth deposit of copper in the cathode. The effects of Fe3+ and
Cl- as the other impurities and the additives (thiourea and gelatine) on the corrosion of lead anode and
specially on the surface morphology of copper deposit were also demonstrated. The findings suggest that
the impurities (Co2+ in particular) present in the PLS has a beneficial effect on the corrosion of anode and
lead contamination of the electrolyte. Nothwithstanding this, the copper cathode produced from the PLS
was poor in quality (<99.8%). It can be inferred that the purification of the PLS prior to electrowinning
could be required to improve the current efficieny and the deposit quality.

INTRODUCTION

In view of the rapid depletion of natural resources and ever increasing environmental concern for the
management of wastes, secondary resources such as the waste of electrical and electronic equipments
(WEEE, or e-waste) has become ever important for the sustainable development of copper industry. The
waste printed circuit boards (PCBs) contain 10–25% copper depending on the source and type of the
circuit board (Alam, 2007). Compared with a typical ore (i.e. 0.5% Cu), PCBs are significant secondary
source of copper (Yazıcı, and Deveci, 2009).
Pyrometallurgical processing has been a traditional technology for recovery of metals (Cu and
precious metals) from WEEE. However, in recent years, hydrometallurgical processes for the treatment of
WEEE have received significant attention owing to their relatively low capital cost, reduced
environmental impact (e.g. no hazardous gases/dusts), potential for high metal recoveries and suitability
for small scale applications (Deveci et al, 2010; Tuncuk et al., 2012). Hydrometallurgical treatment of
WEEE appears to focus mainly on the development of a leaching process with only few studies on
downstream processes for the recovery of metals from pregnant leach solutions (PLSs). In this regard, a
two-stage process based on oxidative sulphuric acid leaching of base metals (Cu in particular) followed
by leaching of precious metals are often suggested for the treatment of WEEE (Deveci et al., 2010;
Tuncuk et al, 2012). Electrowinning can be suitably used for the recovery of copper from PLSs (Panda
and Das, 2001; Davenport, 2011).
In the electrowinning of copper the pure copper metal at the cathode, oxygen gas at the anode and
regenerated sulfuric acid in the electrolyte solution are produced. In the electrowinning of copper the
cathode (1), anode (2) and overall reactions are:

443
 Cu2+ + 2e- → Cu0 (E0 = + 0.34 V).................................................................................(1)
H2O → 1/2 O2 + 2H+ + 2e- (E0 = -1.23 V)......................................................................(2)
Cu2+ + H2O → Cu0 + 1/2O2 + 2H+ ................................................................................(3)

WEEE are heterogenous in composition with the presence of many impurities (e.g. Co2+, Cr2+, Fe3+,
Cl- etc, ), which may end up in the pregnant leach solutions. These impurities at certain levels can affect
the current efficiency and deposit morphology in the electrowinning process. In the present work, the
effects of impurity ions (Co2+, Fe3+ and Cl-) and additives (thiourea and gelatine) on the corrosion of lead
anode, deposit quality and morphology, and current efficiency in the electrowinning of copper from a
synthetic copper sulfate solution and the pregnant leach solution (PLS) derived from the leaching of waste
PCBs were examined.

MATERIAL AND METHOD

The electrolytic cells used in this study were 250 and 400 ml pyrex beakers for Pb and Ti (mixed metal
oxide coated) anodes, respectively. Pb and Ti anodes were used in the tests. The cathodes used were
cylindrical copper rods (15 cm in length and 8 cm in diameter) for the Pb-anode cell and copper sheets
(18 cm in length and 2 cm in width with a thickness of 2 mm) (for the Ti anode cell). Anode and cathode
were connected to a DC source. The cells were agitated using a magnetic stirrer at a constant speed of 200
rpm.
The electrolyte solution was prepared from sulphuric acid (98% H2SO4, Merck), reagent grade copper
sulphate (CuSO4.5H2O, Merck), copper chloride dehydrate (CuCl2.2H2O, Merck), sodium chloride
(NaCl, Kimetsan), ferric sulfate (Fe2(SO4)3.xH2O, Merck), cobalt (II) sulfate heptahydrate (CoSO4.7H2O,
Merck) and deionized-distilled water.
The electrowinning experiments were carried out using synthetic electrolytes and PLSs containing 27-
30 g/L Cu2+ and 1.2 mol/L H2SO4 for 20 hours at room temperature (20±2°C) and at a current density of
150 A/m2 . PLSs were derived from oxidative acid leaching (1.2 mol/L H2SO4, 4.8 mol/L H2O2) of PCBs
at 15% w/v solids density and 80°C for 3 h. Effects of impurities including Fe3+ (2.5 g/L), Co2+ (35
mg/L), Cl- (15 and 100 mg/L) and additives (4 mg/L gelatine and 3 mg/L thiourea) on the electrolysis of
copper were studied. These impurity levels were selected based on the results of earlier typical leaching
tests. During the electrolysis, the cells were sampled at predetermined intervals to monitor the
electrodeposition of copper. After the termination of an experiment, the cathode was removed and
completely washed with distilled water and acetone prior to drying. The dried copper cathode was then
immersed into nitric acid solution (HNO3, 1:1 in volume) to dissolve the copper deposit for analysis of
impurities. The Pb anodes were also washed with distilled water and then immersed in a solution of 200
g/L potassium bitartrate (KC4H5O6), 50 g/L potassium iodide (KI), and 100 g/L potassium hydroxide
(KOH) in order to clean the anode surface prior to their re-use in the experiments (Cifuentes, 2005).
The concentration of copper was determined by the iodometric titration due to the high concentration
of copper (i.e. 27-30 g/L Cu2+) in the electrolyte (Christian, 2007; Dölen, 1988). The excess of potassium
iodide was added to the sample solution of Cu2+ and liberated iodine was titrated with a standard
thiosulphate solution using starch as indicator. An atomic absorption spectrophotometer (AAS, Perkin
Elmer AAnalyst 400) was also used to analyse low levels of copper and impurity metals. The
macroscopic surface analyses of the cathodes were carried out using a Leica DM microscope equipped
with the Leica DFC high resolution camera.

444
RESULTS AND DISCUSSIONS

Electrolysis of copper from PLS

The pregnant leach solution (PLS) derived from the leaching of printed circuit boards (PCB) can contain
a variety of impurity metals and their effect on the electrolysis of copper could be very complicated. To
illustrate, Co2+can reduce the rate of the corrosion of the anodes (Nikoloski and Nicol, 2008) whereas
Fe3+ has an adverse effect on the current efficiency (Mckevitt et al., 2009). Compared with the
electrolysis of copper from a synthetic sulphate solution, the current efficiency in the electrolysis of PLS
was low by 12% (Fig. 1) presumably due to the presence of impurities such as Fe3+. During the
electrolysis of copper from the synthetic solution, an extensive corrosion of Pb anode was observed to
occur. On the other hand, the corrosion of Pb anode was minimal in the electrolysis of PLS.
Notwithstanding this, the copper cathode produced from the PLS was relatively poor in quality (<99.8%).
The use of Ti anode further improved (99.9%) the cathode quality.

100

PLS (Pb- Anode)

95
Current Efficiency (%)

Synthetic solution
90

85

80

75

Figure 1. The current efficiency in the pregnant leach solution (PLS) and the synthetic copper sulphate
solution (30 g/L Cu2+ and 1.2 mol/L H2SO4)

Effect of cobalt

The main impurities in electrowon cathode copper are Pb from anode corrosion product entrapment and
Fe ions from the electrolyte used (Huang et al, 2010; Davenport, 2011). The calculated current efficiency
in the presence of Co2+ was high (99.9% c.f. 96% in the absence of Co2+) (Fig. 2). The presence of Co2+
(35 mg/L) in the synthetic electrolyte solution was found to decrease the anode potentials (by ~0.1 V) and
remarkably mitigate the corrosion of Pb anode with a smooth deposit of copper in the cathode (Fig. 3). It
can be inferred from these findings that the reduced corrosion of Pb anode and Pb contamination
observed in the electrolysis of PLS could be due to the presence of cobalt (34 mg/L) as impurity in PLS.

445
 100

99 Co(II) 35 mg/L

Current Efficiency (%)

No Co(II)
98

97

96

95

94

Figure 2. Effect of Co2+ on current efficiency during the electrolysis of copper from a synthetic solution
(30 g/L Cu2+ and 1.2 mol/L H2SO4)

The effect of cobalt could be attributed to the promotion of O2 evolution at the anode rather than Pb
oxidation resulting in a reduced corrosion of anode. This, in turn, minimises Pb contamination of the
copper deposit and extends anode life (Prengaman and Seigmund, 1999). In other words, the cobalt
lowers the over potential of the evolution of oxygen and, hence, the potential of the cell (i.e. reduced
energy consumption). However, a basic understanding of the mechanism of the action of cobalt ion
remains a point of debate (Nikoloski and Nicol, 2008). The change in anode potential with respect to the
presence of Co2+ could be explained on the basis of reactions taking place at the anode. In the absence of
Co2+, oxygen is evolved from the electrolysis of water taking place on PbO2 surface, which exhibits a
high overpotential (Huang et al, 2010). In the presence of Co2+, oxidation to Co3+ allows the facile
oxidation of H2O in accordance with the equations below:

Co2+ → Co3+ + e- (E0 = -1.84 V)…………………………………………………(6)

4Co3+ + 2H2O → 4Co 2+ + 4H+ + O2……………………………………………(7)
Effect of iron

One of the main impurities in PLS derived from PCB is iron. Fig. 3 confirms that the presence of iron
(Fe3+) in electrolyte solution decreases the current efficiency. The adverse effect of Fe3+ was most
discernible at the highest concentration tested (2.5 g/L Fe3+). The current efficiency dropped significantly
from 95% to 88% when Fe3+ concentration increased from 1 g/L to 2.5 g/L (Fig. 4). The detrimental
effect of Fe3+ on the current efficiency can be attributed to the side reactions involving the reduction of
Fe3+ to Fe2+ at the cathode and its generation at the anode (Mckevitt et al., 2009). Furthermore, the
addition of Fe3+ adversely influenced the morphology of copper deposit presumably due to the etching
effect of Fe3+ on the deposit (Fig. 3). These findings suggest that iron present in PLS may well contribute
to low current efficiency observed.

446
 5 mm 5 mm

(a) (b)

1 mm 5 mm

(c) (d)
Figure 3. The morphology of copper deposits produced in the presence of Cl- (a), Co2+ (b,c), Fe3+(d).

98

96 Fe(III) 2,5 g/L

Fe(III) 1 g/L
Current Efficiency (%)

94 No Fe(III)

92

90

88

86

84

Figure 4. Effect of Fe3+ on current efficiency during the electrolysis of copper from a synthetic solution
(30 g/L Cu2+ and 1.2 mol/L H2SO4)

447
Effect of chloride:

In general, chloride ion is naturally present in the most electrolytes (e.g. PLS). At very low concentrations
it promotes dense, fine grained, low impurity copper deposits at the cathode (Davenport, 2011). However,
at sufficiently high levels chloride could have a detrimental effect on the electrolysis of copper leading to
the production of Cl2 that corrodes the cell components including anode and cathode.
The test results showed that the addition of Cl- (100 mg/L) into the synthetic solution (30 g/L Cu2+, 1.2
mol/L H2SO4) resulted in non uniform and crystalline deposits (Fig. 3, Table 1). Moreover, a reduction in
the current efficiency by 6% was observed.

Effect of additives

Organic additives are commonly used as leveling and brightening agents in copper electrorefining and
electrowinning (Muresan, 2000). In this study, the effect of gelatine (4 mg/L) and thiourea (3 mg/L) as
organic additives on the morphology of copper deposit and current efficiency was also investigated using
the synthetic sulphate solution. The addition of additives was observed to improve the morphology of
copper deposit, which was bright and smooth in quality (Table 1). Furthermore, no corrosion of Pb anode
was also noted in the presence of additives.

Table 1. The effect of the additives and the PLS impurities on the parameters of electrowinning
Thiourea
Co2+ Cl – Fe3+ Fe3+
Additives and gelatin PLS
(synthetic) (synthetic) (synthetic) (synthetic)
(synthetic)
Current
99 94 95 88 99 84
efficiency (%)
Morphology
Bright, Rough, Rough, Rough, Bright, Bright,
(macroscopic
smooth coarse coarse coarse smooth smooth
observation)
Amount of So many
4 (gelatine)
additives 35 100 1000 2500 different
3(thiourea)
(mg/L) impurities.
Anode type Pb Pb Pb Pb Pb Pb-Ti

CONCLUSION

In this study, the electrowinning of copper from a synthetic copper sulfate solution and the pregnant leach
solution (PLS) derived from the leaching of PCBs was demonstrated. The results have shown that the
impurity ions including Co2+, Fe3+ and Cl-- and additives (thiourea and gelatine) affect the corrosion of Pb
anode, deposit quality/morphologyand current efficiency. The addition of Co2+ reduces the corrosion of
Pb anode and, hence, improves the cathode quality by reducing lead contamination. On the other hand,
the presence of ferric iron (Fe3+) in electrolyte solution results in a drop in the current efficiency ,
particularly at high levels. Chloride ion (100 mg/L) was observed to adversely affect the current
efficiency and the quality of copper deposit leading to a non uniform and crystalline deposit. The
additives i.e. thiourea and gelatine remarkably improve the morphology of copper deposit and mitigate
the corrosion of lead anode. Current efficieny and deposit quality may be further improved by the
purification of PLS prior to electrowinning.

448
ACKNOWLEGEMENTS

This work was done as a part of research project (project No:109M111) sponsored by Scientific and
Technological Research Council of Turkey (TÜBİTAK). TÜBİTAK is gratefully acknowledged for
providing the opportunity and the funding for this work. The authors also would like to express their
sincere thanks to Mr. Oktay Akat (Akat Engineering Co.) for kindly providing Ti (mixed metal oxide
coated) anode.

REFERENCES

Alam, M.S., Tanaka, M., 2007. Electrolyte purification in energy-saving monovalent copper
electrowinning processes, Hydrometallurgy, Vol. 87, pp 36– 44.
Christian, G., D., 2007. Analytical Chemistry sixth edition, John Wiley and sons. USA.
Cifuentes, L., Astete, E., Criso, J.Simpson, Cifuentesand, G. Pilleux, M., 2005. Corrosion and protection
of lead anodes in acidic copper sulphate solutions; Corrosion Engineering , Science and Technology,
Vol. 40, No. 4, pp 321-327.
Davenport, W.G., Schlesinger, M. E., Matthew, J. K., Kathryn, C. S., 2011. Extractive metallurgy of
copper, fifth edition, Elsevier, London, U.K.
Deveci, H., Yazıcı, E.Y., Aydın, U., Yazıcı, R., Akcil, A., 2010. Extraction of copper from scrap TV
boards by sulphuric acid leaching under oxidising conditions, Going green care innovation,Vienna,
Austria.
Dölen, E. 1988. Analytical chemistry: volumetric methods. Marmara University, Pharmacy Faculty ,
Istanbul (in Turkish).
Huang, H., Zhou, J.Y., Guo,Z.C., 2010. Effect of added cobalt ion on copper electrowinning from sulfate
bath using doped polyaniline and Pb-Ag anodes. Transactions of nonferrous society of China, Vol. 20,
pp. 55-59.
McKevitt, B., Dreisinger, D., 2009. A comparison of various ion exchange resins for the removal of ferric
ions from copper electrowinning electrolyte solutions. Hydrometallurgy, Vol. 98, pp.116-121.
Muresan, L., Varvara, S., Maurin, G., Dorneanu, S., 2000. The effect of some organic additives upon
copper
electrowinning from sulphate electrolytes, Hydrometallurgy, Vol. 54, pp. 161–169.
Nikoloski, A.N., Nicol, M.J. 2008. Effect of cobalt ions on the performance of lead anodes used for the
electrowinning of copper. A literature review. Mineral processing and extractive metallurgy. Vol. 29,
pp. 143-172.
Panda, B., Das, S.C., 2001. Electrowinning of copper from sulfate electrolyte in presence of sulfurous
acid. Hydrometallurgy Vol. 59, pp. 55-67.
Prengaman, R.D., Seigmund, A. Improved copper electrowinning operations using wrought Pb-Ca-Sn
anodes, 1999. Copper 99- Cobre 99 International symposium, Arizona, USA.
Tuncuk, A., Stazi, V., Akcil, A., Yazici, E.Y., Deveci, H., 2012. Aqueous metal recovery techniques from
e-scrap: Hydrometallurgy in recycling, Minerals Engineering, Vol. 25 pp. 28–37
Yazıcı, E.Y., Deveci, H., 2009. Recovery of metals from E-wastes. The Journal of the Chamber of
Mining Engineers of Turkey, Vol. 48, pp. 3–18 (in Turkish).

449
View publication stats