Chemical Engineering and Processing 46 (2007) 757763

The effect of additives on anode passivation in electrorening of copper

M. Ojaghi Ilkhchi a, , H. Yoozbashizadeh b , M. Sadegh Safarzadeh c,d
Faculty of Materials Engineering, Sahand University of Technology, P.O. Box 51335-1996, Tabriz, Iran Department of Materials Science and Engineering, Sharif University of Technology, P.O. Box 11365-9466, Tehran, Iran c Department of Materials and Metallurgical Engineering, Iran University of Science and Technology, Narmak, Tehran, Iran d Iranian Zinc Mines Development Company, IZMDC, Zanjan, Iran
b a

Received 17 June 2006; received in revised form 10 September 2006; accepted 4 October 2006 Available online 10 October 2006

Abstract In copper electrorening process, some additives are added to the electrolyte to improve the morphology of cathode deposits as well as the quality of products. In the present investigation, the effects of thiourea, glue and chloride ions (as additives) on the passivation of industrial copper anodes under high current densities have been reported. Experiments were conducted at 65 C; using a synthetic electrolyte containing 40 g/l Cu2+ and 160 g/l H2 SO4 . Results obtained from chronopotentiometry experiments showed that increasing the concentration of chloride ion leads to increase in passivation time. The results also indicated that from a certain level on, namely 2 ppm, the increase in thiourea and glue concentrations decreased the passivation time. Thiourea and glue in low concentrations, i.e. 2 ppm, retarded passivation, compared to an electrolyte without additives. 2006 Elsevier B.V. All rights reserved.
Keywords: Copper electrorening; Anode passivation; Thiourea; Glue; Chloride ion; Chronopotentiometry

1. Introduction Copper electrorening in acidic copper sulfate electrolytes has been widely used to produce high purity copper. According to Faradays law, there are two approaches to enhance the productivity of electrorening process; i.e. increasing the current density and surface area of the electrodes both result in more productivity. Increasing the surface area of the electrodes per se necessitates the enlargement of the cell dimensions and hence electrolyte volumes. However, increasing current density, without increasing electrolyte volume, results in higher production capacities, but has some disadvantages such as lower purity and undesired morphology of cathode and detrimental phenomenon of anode passivation. Dissolution of anodes decreases or even stops due to passivation phenomenon and subsequently; it results in high energy consumption as well as increments in residue scrap and voltage levels. The precipitation of a non-conducting copper sulfate layer on the anode surface, due to supersaturation of the electrolyte has been considered as a reason for passiva-

Corresponding author. Tel.: +98 412 3444334; fax: +98 412 3444333. E-mail address: m ojaghi@sut.ac.ir (M.O. Ilkhchi).

tion [1]. Passivation of anodes is affected by the compositions of the anode and electrolyte as well as temperature and electrolyte circulation rate. However, impurities in copper anodes, which are usually noticeable amounts of Se, Te, Bi, As, Sb, S, Ni and precious metals such as Ag and Au, affect the anode passivation. Anode passivation has received increasing attention and the factors inuencing it have been extensively studied. The studies [24] show that electrolyte composition and temperature play an important role in passivation phenomenon. Anode passivation has shown to be aggravated by increasing the factors such as copper concentration, the sulfuric acid concentration and current density, as well as decreasing the temperature. These factors increase the probability of copper sulfate precipitation. Also it is found that the time of passivation decreases with an increase in Sb3+ , As3+ , Bi3+ and dissolved O2 in the electrolyte [5]. This behavior is observed to increase the slime formation. Abe et al. [1] concluded that passivation time decreased with increasing nickel as nickel sulfate. Several recent studies have focused on the effect of additives on passivation in laboratory scale. Jin et al. [6] showed that the addition of amino acid chelating agents could inhibit passivation. In particular ethylenediaminetetraacetic acid (EDTA), diethylenediaminepentaacetic acid (DTPA), and triethylenedi-

0255-2701/$ see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.cep.2006.10.005

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M.O. Ilkhchi et al. / Chemical Engineering and Processing 46 (2007) 757763 Table 1 Chemical composition of commercial copper anode used in experiments Element Cu Na Cl Si Al Hf Ca K P Mg wt.% 98.64 0.283 0.193 0.180 0.179 0.105 0.0831 0.0625 0.0648 0.051 Element Zn Ag Se Fe As Ni Pb Sb Th Ti wt.% 0.0317 0.0316 0.0292 0.0144 0.0135 0.0084 0.0074 0.0070 0.0039 0.0028

aminehexaacetic acid (TTHA) show some benet and all of them exhibit an optimum concentration for extending passivation times. Jin and Ghali [7] studied the effects of several aromatic nitro compounds. The most benecial reagents to inhibit passivation were 3,5-dinitrosalicylic acid and 3,5dinitrobenzoic acid. Jin and Ghali [8] investigated the effect of glue, thiourea, avitone, percol and chloride ions on the passivation of copper anodes. Hiskey and Cheng [9] illustrated that time to passivation is a function of thiourea. For small additions, i.e. 15 ppm, thiourea improved the passivation behavior, whereas for large additions, namely greater than 15 ppm, passivation times decreased. Moats and Hiskey [10] examined the role of glue, thiourea and chloride ions on passivation of copper anodes. Sarcheshmeh Copper Complex in Iran uses the electrorening process to produce the high purity copper cathodes. Chemical composition of Sarcheshmeh anodes is different from the anodes that have been studied previously. Some additives as grain rening agents are added in order to improve the morphology of cathode deposits in the electrorening of copper. Thiourea, glue and chloride ion are also used in most reneries. Using these additives will result in smooth and noduleless deposits. On the other hand, these additives affect the tendency of anodes to the passivation. In this investigation, these additives were evaluated at various concentration using industrial anodes from Sarcheshmeh Copper Complex. Some experiments were carried out to detect the effects of additives and their interaction on the passivation of anodes, which are described below. In this work, chronopotentiometry, which is an electrochemical method, was employed to plot chronopotentiogram curves for investigating passivation effect. 2. Experimental

Working electrodes were cast in the form of cylindrical rods and machined carefully into 1.1 cm diameter and 1 cm height rods. Soldering a copper wire to the base of each cylinder provided electrical contact. All sides of the electrodes were insulated with nail polish excluding 1 cm2 of circular face for the working electrodes and 10 cm2 of the same area for the counter electrodes. Chemical composition of the commercial copper anode utilized in this investigation is presented in Table 1. 2.2. Instrumentation Chronopotentiometry was utilized to observe the effect of electrolyte additives on the passivation response during anodic dissolution. A constant current density of 3820 A m2 was applied in the experiments using a 273 A Potentiostat/Galvanostat EG&G equipment controlled by 352 Corrosion Analysis software. Based on previous works by other researchers [11], a 3820 A m2 current density was selected. 3. Results

2.1. Materials and methods 3.1. Additive free electrolyte A synthetic electrolyte was utilized for all electrochemical tests. The electrolyte was prepared by using sulfuric acid (MERCK, Analytical grade); commercial hydrated copper sulfate and distilled water. The commercial additives (glue and thiourea) were supplied by the Sarcheshmeh Copper Complex, Iran. Chloride ions added in the form of hydrochloric acid (MERCK, Analytical grade). An electrolyte composition of 40 g/l Cu (0.63 M) and 160 g/l H2 SO4 (1.63 M), as a standard electrolyte, was used at a temperature of 65 C. Glue and thiourea that are well-known to decompose in the electrolyte were added just prior to heating the electrolyte. The working, counter and reference electrodes were considered as a cylinder shape from an industrial anode with a length of 4 cm, made of high purity copper rod and a standard calomel electrode (SCE 0.24 V versus SHE), respectively. The working and counter electrodes were prepared by polishing with silicon carbide sandpaper and washing with de-mineralized water. Then they transferred to the electrolytic cell containing 100 cm3 of synthetic electrolyte, held at 65 C and allowed to reach steadiness with the system by being held in the electrolyte at open circuit potential for 5 min. Fig. 1 illustrates the chronopotentiogram of tested anode in the standard electrolyte. This chronopotentiogram shows a potential jump from the 960th second on that contributes to passivation of the anode. As can be seen from the curve, potential

Fig. 1. Chronopotentiogram of industrial anode in the standard electrolyte.

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Fig. 2. Chronopotentiogram of industrial anode in the electrolyte containing 1 ppm thiourea.

Fig. 4. Chronopotentiogram of industrial anode in the electrolyte containing 5 ppm thiourea.

oscillations went on to the end of the test and anode remained in passive state. 3.2. Effect of thiourea Figs. 26 illustrate the chronopotentiogram curves of tested anode in the electrolyte containing 1, 2, 5, 15 and 30 ppm thiourea, respectively. According to the results, increasing thiourea concentration up to 2 ppm, leads to increase in passivation time; however, by increasing thiourea concentration to 5 ppm level, the passivation time decreases. As can be seen, adding 1 ppm thiourea to the electrolyte increases the passivation time of anode. Fig. 7 shows the passivation time of the anode in terms of thiourea concentration. Thiourea appears to have a positive effect at low concentrations and vice versa an adverse effect at high concentrations. No depassivation effect was observed during the tests. Chronopotentiograms also showed that potential of the active dissolution region decreased, which claims that the dissolution becomes easier in the presence of thiourea, i.e. it has a depolarizing effect on the anode.

Fig. 5. Chronopotentiogram of industrial anode in the electrolyte containing 15 ppm thiourea.

3.3. Effect of glue Figs. 812 illustrate the chronopotentiograms of tested anode in the electrolyte containing 1, 2, 5, 15 and 30 ppm glue, respectively. According to the results, increasing glue concentration up to 2 ppm, leads to increase in passivation time; however, by

Fig. 3. Chronopotentiogram of industrial anode in the electrolyte containing 2 ppm thiourea.

Fig. 6. Chronopotentiogram of industrial anode in the electrolyte containing 30 ppm thiourea.

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Fig. 7. Passivation time of anode against thiourea concentration. Fig. 10. Chronopotentiogram of industrial anode in the electrolyte containing 5 ppm glue.

Fig. 8. Chronopotentiogram of industrial anode in the electrolyte containing 1 ppm glue. Fig. 11. Chronopotentiogram of industrial anode in the electrolyte containing 15 ppm glue.

increasing glue concentration to 5 ppm level, the passivation time decreases, which is completely consistent to the results attained from the effect of increasing thiourea concentration on the passivation time. As can be seen, adding 1 ppm glue to the electrolyte, increased the passivation time of the anode. However, that time decreases by increasing glue concentration. Fig. 13 shows the passivation time of anode in terms of glue

concentration. Glue appears to have a positive effect at low concentrations and an adverse effect at high concentrations. Again, no depassivation effect was observed during the tests. The glue simplies the dissolution of anode, concerning the fact that the potential of active dissolution region is small compared to its

Fig. 9. Chronopotentiogram of industrial anode in the electrolyte containing 2 ppm glue.

Fig. 12. Chronopotentiogram of industrial anode in the electrolyte containing 30 ppm glue.

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Fig. 13. Passivation time of anode against glue concentration.

quantity without the presence of additive and consequently it might be concluded that the glue has a depolarizing effect on the anode as well. 3.4. Effect of chloride ions Chloride is almost the only non-organic electrolyte additive which is used in copper electrorening. Normally added amount of chloride ion in reneries varies between 20 and 70 ppm. The chronopotentiograms of industrial anodes in electrolyte containing 20, 40, 60, 80 and 100 ppm chloride ion have been illustrated in Figs. 1418, respectively. Fig. 19 shows the passivation time of the anode in terms of chloride ion concentration. As can be recognized, the addition of chloride ion to electrolyte increases the passivation time of anodes and this period is extended with increasing the chloride ion. The potential of the active dissolution region in the presence of chloride ion is more negative than the situation in which chloride ion is not present, which states the depolarization effect of chloride ion on the anode. That is to say, the presence of chloride ion simplies the dissolution of the anodes.

Fig. 15. Chronopotentiogram of industrial anodes in electrolyte containing 40 ppm chloride ion.

Fig. 16. Chronopotentiogram of industrial anodes in electrolyte containing 60 ppm chloride ion.

3.5. Effects of simultaneous addition of three different additives The chronopotentiogram of industrial anodes in the electrolyte containing 40 ppm chloride ion, 1 ppm thiourea and

Fig. 14. Chronopotentiogram of industrial anodes in electrolyte containing 20 ppm chloride ion.

Fig. 17. Chronopotentiogram of industrial anodes in electrolyte containing 80 ppm chloride ion.

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each additive individually, it can be concluded that the addition of the chloride ion weakens the effect of thiourea and glue. This might be caused by the formation of a complex compound due to the reaction of thiourea and glue with chloride ion. Also the potential of the active dissolution region is more negative in comparison with standard electrolyte, and this demonstrates a simplication in dissolution in the presence of additives. 4. Discussion According to ndings of Mattson and Bockris [12] the dissolution of copper takes place by passing through two monoelectron transfers (Eqs. (1) and (2)), the latter being slow and kinetically, determines the dissolution rate: Cu Cu+ + e Cu+ Cu2+ + e (1) (2)

Fig. 18. Chronopotentiogram of industrial anodes in electrolyte containing 100 ppm chloride ion.

Consequently, concentration of Cu+ ion increases near the anode surface and disproportionation of these ions (Eq. (3)) produces copper powder and Cu2+ ions: 2Cu(sol) + Cu(sol) 2+ + Cu0 (3)

Fig. 19. Passivation time of anode in term of chloride ion concentration.

1 ppm glue is displayed in Fig. 20. It is evident that the industrial copper anode in the electrolyte containing three additives simultaneously, passivated after 1140 s, which shows that there is a delay in the passivation in the presence of all kinds of additives. By comparing this timeframe with the passivation time in the electrolytes containing equal contents of

Fig. 20. Chronopotentiogram of industrial anodes in electrolyte containing 40 ppm chloride ion, 1 ppm thiourea and 1 ppm glue.

As a result, copper powder can inter the slime and increase the copper losses; furthermore, it increases the volume of the anode slime and troubles the diffusion of the copper ions. Copper powder can moreover reduce the silver ions to metallic silver that makes a diffusion barrier for the copper ions. In the acidic electrolyte, thiourea can be oxidized as the formamidine disulde (FDS) form and thiourea and FDS both can form complexes with Cu+ ions. In the case of thiourea, this complex is in the form of [Cu(Tu)4 ]+ , i.e. each Cu+ ion complexes with four molecules of thiourea. This complex has a high stability constant, which demonstrates that it is very stable. Due to the formation of such complexes, the concentration of Cu+ ions decreases and their detrimental effects on the anode passivation is then neutralized. Furthermore, thiourea and its decomposition products can adsorb on the anode, similar to sulfur, and act as a barrier against the diffusion of copper ions. In low concentrations, the complexing effect of thiourea becomes prior to adsorption but with increasing the concentration, decomposition products also will increase and consequently, adsorption effect will appear in advance. As a result, the adsorbed compounds on the anode will cover its active surface area and block the anode dissolution and help to its passivation, That is to say, the passivation time of the anodes decreases. Glue is an animal protein, which is composed of amino acids. The positive effect of glue on the passivation of anode in low concentrations is probably owing to the complexation of Cu+ ions with amino acids. Glue can also be adsorbed on the anode. With respect to decreased passivation time in high concentrations of glue, probably the adsorption effect increases with an increment in the concentration and prevails over the complexing effect.

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The positive effect of adding chloride ion on the passivation of industrial anodes can also be explained. Noguchi et al. [5,13] showed that passivation time decreased with increasing dissolved O2 ; Then again, Bombach et al. [14] demonstrated that Cu+ ions decreased by increasing dissolved O2 . According to these two observations, it would be concluded that increasing the cuprous content might be benecial to passivation. Hence one can say chloride ions are benecial for prevention of passivation effect through stabilization of cuprous ions. However, as mentioned above, the increasing of Cu+ ions near the anode surface is detrimental. Most likely chloride ions decrease the concentration of the Cu+ ions with the formation of CuCl2 that is a soluble complex ion. 5. Conclusions Based on the investigation conducted on the effect of additives on anode passivation in electrorening of copper, the following items may be concluded: In the standard electrolyte containing 160 g/l sulfuric acid and 40 g/l copper, the Sarcheshmeh industrial copper anodes passivated at the current density of 3820 A m2 after elapsing 960 s at 65 C. Adding 12 ppm of thiourea to the electrolyte increased the passivation time of the anode; whereas adding more amounts of thiourea decreased that time. Presence of 12 ppm of glue in the standard electrolyte delays the anode passivation, whereas increasing the glue concentration accelerates it. Chloride ion delays the passivation of industrial copper anode. However, it must be noticed that the presence of chloride ion is deleterious and will result in severe corrosion of the apparatus, subsequently, it is not useful to add a great deal of chloride ion to delay passivation, from an economical point of view. The effect of thiourea and glue is related to complex formation with Cu+ ions in low concentrations and the adsorption phenomenon is the reason for their adverse effect in high concentrations.

Acknowledgments The authors wish to thank Dr. M. Ghorbani, Mr. J. Ahmadian and Mr. A. Khalili for their kind support. References
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