Hydrometallurgy 82 (2006) 150 153 www.elsevier.

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Activation mechanism of Sb2O3 during removal of cobalt from zinc sulphate solution
R. Xu , K. Ma, Z. Guo
Faculty of Materials and Metallurgical Engineering, Kunming University of Science and Technology, Kunming 650093, PR China Available online 6 May 2006

Abstract The EpH diagram for the CoSbH2O system indicates that antimony and cobalt combine to form an inter-metallic compound that enhances the thermodynamic driving force of removal of cobalt from zinc electrolyte solution by cementation with zinc powder. The results of scanning electron microscopy and X-ray diffraction show that antimony exists in the same form as nickel and cobalt which suggests that antimony and cobalt combine to form an inter-metallic compound CoSb. However, zinc exists in the form of basic zinc sulphate, zinc oxide and zinc. The activation mechanism of Sb2O3 is investigated in this paper. 2006 Elsevier B.V. All rights reserved.
Keywords: Mechanism; Sb2O3 activator; Zinc sulphate electrolyte; Cobalt cementation

1. Introduction Zinc is one of the important non-ferrous metals. Owing to its low melting point and fluidity in the molten state, and easy die-casting of its alloys, zinc is increasingly used in the manufacture of shape-complicated components. In addition, zinc has good corrosion resistance and is used in galvanizing. Alloys of zinc with some non-ferrous metals are useful anti-friction materials. The efficient purification of zinc sulphate electrolyte is an essential requirement for the successful electrowinning of zinc. In order to intensify the electrowinning process, higher current density is adopted, and the electrolyte must be highly purified to make the level of impurities in the electrolytes as low as possible and to ensure the desired quality of cathode zinc.
Corresponding author. Tel.: +86 871 8352598. E-mail addresses: rdxukm@126.com, ruidongxu@sina.com (R. Xu). 0304-386X/$ - see front matter 2006 Elsevier B.V. All rights reserved. doi:10.1016/j.hydromet.2006.03.009

The methods of removing cobalt present in hydrometallurgical zinc plants can be classified into two categories: one is precipitation of cobalt with special reagents (e.g. xanthate), and another is removal of cobalt by cementation with zinc powder or alloy into which an activator (e.g. arsenate or antimonate) are added. Since the methods of removing cobalt by xanthate or by arsenate have many shortcomings (Cheng, 1992; Xu, 1988; He, 1991; Lawson and Nhan, 1981; Wang, 1995), most plants use antimonate to remove cobalt. Some related research has been reported (Chang, 1991; Xu, 1987), but the role of Sb2O3 during the removal of cobalt from zinc sulphate solution has not been reported. In this paper, the activation mechanism of Sb2O3 during removal of cobalt from zinc sulphate solution is examined. 2. Experimental The test solution was zinc sulphate solution after removal of copper and cadmium from a leadzinc plant. The zinc powder was coarse atomized zinc dust

R. Xu et al. / Hydrometallurgy 82 (2006) 150153 Table 1 Composition of zinc sulphate solution after removal of copper and cadmium (mg/L) Element Zn Cu Co Cd Sb Fe Ni As

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Content (g/L) 137 4.24 4.93 9.40 0.035 3.50 1.60 0.008

Table 2, the EpH diagram of the CoSbH2O system can be constructed as shown in Fig. 1. It can be seen from Fig. 1 that antimony and cobalt combine to form an inter-metallic compound during removal of cobalt by cementation with zinc powder, and this enhances the thermodynamic driving force of removal of cobalt. 3.2. Activation mechanism of Sb2O3 In the zinc sulphate solution, the water-soluble species of Sb3+ are HSbO2 and SbO2 . When zinc powder is present, antimony in HSbO2 and SbO2 is cemented and combines with precipitated cobalt to form inter-metallic compound CoSb. The reactions are as follows: Co2 SbO 4H Zn 3e 2 CoSb Zn2 2H2 O Co2 HSbO2 3H 5=2Zn CoSb 2H2 O 5=2Zn2 1

produced by this leadzinc plant and the fine electric furnace zinc dust produced by another plant. The activator is Sb2O3. The composition of the zinc sulphate solution after removal of copper and cadmium is shown in Table 1. 3 L of the test solution was added into a 5 L beaker. The experimental conditions were: temperature 85 5 C, pH 5.0, coarse zinc dust 1 g/L, fine zinc dust 2 g/L, Sb2O3 2 mg/L, stirring speed 200 rpm, purification duration 90 min. The purified solution was filtered and the filter residue washed, heated and dried. Scanning electron microscope (SEM) and X-ray diffractometer (XRD) was used to analyze the dried residue to determine the existing forms of cobalt and antimony. 3. Results and discussion 3.1. Thermodynamic analysis of Sb2O3 as cobaltremoving activator According to related thermodynamic data (Yang and Yang, 1991; Pourbaix, 1966; Barner and Scheuerman, 1978), the reactions and equations of the equilibrium lines in the EpH diagram of CoSb H2O system are presented in Table 2. On the basis of
Table 2 Reactions and equations of equilibrium lines in the EpH diagram of CoSbH2O system Reactions 1. 2SbO + 2H+ = Sb2O3 + H2O 3 2. 2Sb2O5 + 4H+ + 4e = Sb2O3 + 2H2O 3.2SbO + 6H + + 4e = Sb 2 O 3 + 3 3H2O 4. Co(OH)2 + 2H+ = Co2+ + 2H2O 5. SbO + 2H2O + 3e = Sb + 4OH 2 6. 2Co(OH)2 + Sb2O3 + 10H+ + 10e =2CoSb + 7H2O 7. Co2+ + 2e = Co 8. 2Co2+ + Sb2O3 + 6H+ + 10e = 2CoSb + 3H2O 9. CoSb + 3H+ + 3e = Co + SbH3(g) Equations pH = 4.16 + log a(SbO) 3 E = 0.649 0.059pH E = 0.0772 0.0887pH + 0.0295log a(SbO) 3 pH = 6.4 0.5.log a(Co2+) E = 0.443 + 0.0197log a(SbO) 2 0.0788pH E = 0.265 0.059pH E = 0.28 + 0.0295pHlog a(Co2+) E = 0.101 0.059pH + 0.013log a(Co2+) E = 0.7760.059pH + 0.059log P(SbH3)

The EpH diagram of CoSbH2O system shows that the electrochemical potential of CoSb is 200 mV higher than that of Co2+/Co, so the thermodynamic driving force for removal of cobalt by cementation with zinc powder is increased and favours the reaction. The dried residue after removal of cobalt was analyzed by scanning electron microscope (SEM), and the results in Fig. 2 show that cobalt and

Fig. 1. EpH diagram of CoSbH2O system at 25 C (a = 1).

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Fig. 2. (a) K electron distribution patterns of element Ni in the residue after removal of cobalt (400 ). (b) K electron distribution patterns of element Zn in the residue after removal of cobalt (400 ). (c) K electron distribution patterns of element Co in the residue (400 ). (d) K electron distribution patterns of element Sb in the residue after removal of cobalt (400 ).

antimony combine to form an inter-metallic compound while zinc exists as basic zinc sulphate, zinc oxide and metal zinc. The K electron distribution patterns of Ni, Zn, Co and Sb show that the existing forms of Sb and Co are the same, which suggests they combine to form a compound. In summary, the activation mechanism of Sb2O3 is that SbO2 or HSbO2 is reduced by zinc, the Sb produced combines with Co to form an inter-metallic compound CoSb. Since the domain of stability of CoSb is larger and its standard reduction potential is higher than that of Co, the removal of cobalt by cementation with zinc dust is increased remarkably. 3.3. Resolution of mechanism of cobalt Generally, Sb2O3 and a small amount of copper ions are added as the activator during the two-stage purification and cobalt-removal of zinc sulphate solution. The Sb2O3 and copper ions added are cemented by zinc powder and become the cathodes of micro-cells. The formation of SbZn and CuZn micro-cells facilitates the continuous dissolution of zinc dust and the continuous precipitation of cobalt,

so the cobalt is removed and the solution is purified. Since the deposition overpotential of Co on the Cu cathode is much lower than that on the Sb cathode, Co deposits preferably on the CuZn micro-cells. When the CuZn micro-cells no longer play the role, the Co obtains electrons and deposits on the SbZn micro-cells. Eqs. (1) and (2) in Table 1 indicate that the H+ decreases with the deposition of Co and the zinc dust dissolves continuously. This makes the pH in the vicinity of the surface of zinc powder and the Zn2+ concentration both higher, so that the basic zinc sulphate forms and deposits on the surface of zinc dust. In addition, during pressure filtration, a decrease of the solution temperature will cause an increase in pH of the solution. This is because pHt = pH(298)pKw (t) /pK w(298) , in which pH (298) and pK w(298) are constant. When the temperature (t) decreases, pKw(t) increases and pH(t) increases, so that the trend for Zn2+ to form basic zinc sulphate increases. With the prolongation of time, more and more basic zinc sulphate forms, and this finally leads to the deactivation of CuZn and SbZn micro-cells. At this stage, the CoSb micro-cells can allow cobalt to re-dissolve again in an anodic process.

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4. Conclusions The EpH diagram of CoSbH2O system indicates that antimony and cobalt combine to form an inter-metallic compound during removal of cobalt by cementation with zinc dust. This enhances the thermodynamic driving force of removal of cobalt by cementation with zinc dust. The activation mechanism of Sb2O3 is that SbO2 or HSbO2 is reduced by Zn, and the Sb combines with Co to form the inter-metallic compound CoSb. Since the domain of stability of CoSb is larger and its standard reduction potential is higher than that of Co, the thermodynamic removal of cobalt by cementation with zinc dust is significantly increased. During the removal of CoSb from the zinc sulphate solution, in which the copper and cadmium are eliminated by cementation with zinc dust, the pH in the vicinity of the surface of zinc dust increases, so that Zn2+ in the solution forms basic zinc sulphate and deposits on the surface of zinc dust. This inhibits cobalt from being cemented, and the Co and Sb in the reduced products form micro-cells, which allows Co to dissolve again.

References
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