Abstract
In recent years, a renewed interest in studying the electrochemical corrosion behavior of lead anodes during zinc electrowinning is probably due to the particularly high sulfuric acid concentrations in zinc electrolyte where lead alloy anodes have high cell voltage and high corrosion rate of lead. The high corrosion rate of lead alloy resulted in Pb contamination on zinc deposit. In zinc electrometallurgy, the electrolyte from a zinc-rich ore contains a significant amount of Mn2+. Mn2+ in the zinc electrolyte results in forming an oxide film on lead anodes during electrolysis. Pb-0.7% Ag anode is generally used in the zinc industry. To improve the technical performance and decrease product cost, other anodes, such as Pb-Ca or Pb-Ag-Ca or Pb-Ag-Ti or Pb-Ag-Se alloys were tested. Till now, none of them has succeeded in the substitution of Pb-Ag anodes in the zinc electrowinning. As an alloying element, silver in small quantities is considered because of the benefits that generates on the anode during electrolysis. During zinc electrolysis, lead dissolution into the zinc electrolyte can be harmful to the quality of zinc deposit. However, the lead silver alloy anode can decrease the lead content in the zinc deposit by pre-treated methods such as blasting and preconditioning.
Funding source: Natural Sciences and Engineering Research Council of Canada
Award Identifier / Grant number: RDCPJ 428402
Funding statement: The authors are grateful to Hydro-Quebec, CEZ, and the Natural Sciences and Engineering Research Council of Canada (NSERC) (Grant No. RDCPJ 428402) for their financial support.
About the author
Wei Zhang has 31 years experience in electrochemical behavior and corrosion-related research. He has in-depth knowledge of corrosion science and corrosion engineering, including technologies for corrosion mitigation, and scientific techniques for corrosion research. Also, he has a solid background in materials science and engineering, and a variety of materials processing technologies. He got his Master’s and PhD degrees from the University Laval in 2005 and 2010, respectively.
References
Ault AR, Frazer EJ. Effects of certain impurities on zinc electrowinning in high-purity synthetic solutions. J Appl Electrochem 1988; 18: 583–589.10.1007/BF01022254Search in Google Scholar
Barnes SC, Mathieson RT. Electrochemical properties of lead alloys in sulfuric acid solution. In: Collins DH, editor. Batteries. New York, Pergamon Press, 1963: 41–54.Search in Google Scholar
Bodsworth C. The extraction and refining of metals, Boca Raton, FL, USA, CRC Press, ISBN0849344336, 1994: 148–161.Search in Google Scholar
Bone SJ, Singh KP, Wynne-Jones WFK. Some potential and exchange studies of α-lead dioxide. Electrochim Acta 1961; 4: 292–297.10.1016/0013-4686(61)80023-6Search in Google Scholar
Bozhkov C, Petrova M, Rashkov S. The effect of nickel on the mechanism of the initial stages of zinc electrowinning from sulfate electrolytes. Part II. Investigations on aluminum cathodes alloyed with iron impurities. J Appl Electrochem 1990; 20: 17–22.10.1007/BF01012465Search in Google Scholar
Bratt GC, Smith WN. The effects of strontium compounds and related materials in electrolytic production of zinc. Electrochemistry 1965; 7: 939–948.10.1016/B978-1-4831-9831-6.50075-8Search in Google Scholar
Brungs A, Haddadi-Asl V, Skyllas-Kazacos M. Preparation and evaluation of electrocatalytic oxide coatings on conductive carbon-polymer composite substrate for use as dimensionally stable anodes. J Appl Electrochem 1996; 26: 1117–1123.10.1007/BF00243736Search in Google Scholar
Burbank J. Anodization of lead and lead anode alloys in sulfuric acid. J Electrochem Soc 1957; 104: 693–701.10.1149/1.2428455Search in Google Scholar
Cachet C, Wiart R. Zinc deposition and passivated hydrogen evolution in highly acidic sulfate electrolytes: depassivation by nickel impurities. J Appl Electrochem 1990; 20: 1009–1014.10.1007/BF01019581Search in Google Scholar
Charlesby A. Ionic currents in thin films of zirconium oxide. Acta Met 1953; 1: 340–347.10.1016/0001-6160(53)90110-2Search in Google Scholar
Czerwinski A, Zelazowska M, Grden M, Kuc K, Milewski JD, NowackiA, Wojcik G, Kopczyk M. Electrochemical behaviour of lead in sulfuric acid solution. J Power Sources 2000; 85: 49–55.10.1016/S0378-7753(99)00381-XSearch in Google Scholar
Dawson JL. Principles of lead corrosion in sulfuric acid. In: Kuhn AT, editor. The electrochemistry of lead. New York, USA, Academic Press, 1979.Search in Google Scholar
Eggett G, Naden D. Developments in anodes for pure copper electrowinning from solvent ex traction produced electrolytes. Hydrometallurgy 1975; 1: 123–137.10.1016/0304-386X(75)90003-1Search in Google Scholar
Forsen O, Kukkonen JJ, Aromaa J, Ylasaari S. Improved technologies for rational use of energy in the non-ferrous industry in Europe. In: European Seminar, Milan, Italy, 1992: 125–129.Search in Google Scholar
Gendron AS, Ettel VA, Abe S. Effect of cobalt added to electrolyte on corrosion rate of Pb-Sb anodes in copper electrowinning. Can Metall Quart 1975; 14: 59–61.10.1179/000844375795050436Search in Google Scholar
Gonzalez-Dominguez JA, Lew RW. Evaluating additives and impurities in Zinc electrowinning. JOM, 1995; 47: 34–37.10.1007/BF03221128Search in Google Scholar
Gui JF, Jiang LX, Zhong XC, Yu XY, Lai YQ, Li J, Liu YX. Effects of Ag and RE contents on electrochemical performance of Pb-Ag-RE alloy anode. Chinese J Nonferr Met 2015; 25: 111–118.Search in Google Scholar
Hine F, Ogata Y, Yasuda M. Consumption of lead-silver alloy anodes in sulfuric acid solution. B Electrochem 1988; 4: 61–65.Search in Google Scholar
Hrussanova A, Mirkova L, Dobrev TS. Electrochemical properties of Pb-Sb, Pb-Ca-Sn and Pb-Co3O4 anodes in copper electrowinning. J Appl Electrochem 2002; 32: 505–512.10.1023/A:1016591810240Search in Google Scholar
Hrussanova A, Mirkova L, Dobrev T, Vasilev S. Influence of temperature and current density on oxygen overpotential and corrosion rate of Pb-Co3O4, Pb-Ca-Sn, and Pb-Sb anodes for copper electrowinning: part I. Hydrometallurgy 2004; 72: 205–213.10.1016/j.hydromet.2003.07.004Search in Google Scholar
Huang H, Zhou JY, Chen BM, Guo ZC. Polyaniline anode for zinc electrowinning from sulfate electrolytes. Trans Nonferrous Met Soc China 2010; 20: s288–s292.10.1016/S1003-6326(10)60058-1Search in Google Scholar
Ivanov I. Increased current efficiency of zinc electrowinning in the presence of metal impurities by addition of organic inhibitors. Hydrometallurgy 2004; 72: 73–78.10.1016/S0304-386X(03)00129-4Search in Google Scholar
Ivanov I, Stefanov Y. Electroextraction of zinc from sulfate electrolytes containing antimony ions and hydroxyethylated-butyne-2-diol-1,4: part 3. The influence of manganese ions and a divided cell. Hydrometallurgy 2002; 64: 181–186.10.1016/S0304-386X(02)00039-7Search in Google Scholar
Ivanov I, Stefanov Y, Noncheva Z, Petrova M, Dobrev T, Mirkova L, Vermeersch R, Demaerel JP. Insoluble anodes used in hydrometallurgy: part I. Corrosion resistance of lead and lead alloy anodes. Hydrometallurgy 2000; 57: 109–124.10.1016/S0304-386X(00)00097-9Search in Google Scholar
Jaksic M, Rajkovic M, Stanojevic D. Development and application of the preconditioned alloyed lead anode for zinc electrowinning. I. Theoretical basis of the preconditioning process. Hem Ind 1987; 41: 226–232.Search in Google Scholar
Joao M, Rodrigues S, Eward H, Meyer O. Influence of impurities in the electrolyte on zinc deposition. Miner Met Mater Soc 1995; 47: 78–83.Search in Google Scholar
Kiryakov GZ, Stender VV. The study of electrochemical properties of different lead alloys in sulfuric acid solution. J Appl Chem (Russian) 1951; 24: 1263–1272.Search in Google Scholar
Lafront AM, Zhang W, Ghali E, Houlachi G. Effect of gelatin and antimony on zinc electrowinning by electrochemical noise measurements. Can Metall Quart 2009; 48: 337–346.10.1179/cmq.2009.48.4.337Search in Google Scholar
Lai YQ, Jiang LX, Lie J, Zhong SP, Lu XJ, Peng V, Liu YX. A novel porous Pb–Ag anode for energy-saving in zinc electrowinning: part II: preparation and pilot plant tests of large size anode. Hydrometallurgy 2010; 102: 73–80.10.1016/j.hydromet.2010.02.012Search in Google Scholar
Lander JJ. Silver, cobalt, and positive-grid corrosion in the lead-acid battery. J Electrochem Soc 1958; 105: 289–292.10.1149/1.2428831Search in Google Scholar
Li DG, Chen DR, Wang JD, Chen HS. Influence of temperature, H2SO4 concentration and Sn content on corrosion behaviour of PbSn alloy in sulfuric acid solution. J Power Sources 2011; 196: 8789–8801.10.1016/j.jpowsour.2011.06.082Search in Google Scholar
Lupi C, Pilone D. New lead alloy anodes and organic depolarizer utilization in zinc electrowinning. Hydrometallurgy 1997; 44: 347–358.10.1016/S0304-386X(96)00060-6Search in Google Scholar
Mackinnon DJ, Brannen JM, Kerby RC. The effect of lead on zinc deposit structures obtained from high purity synthetic and industrial acid sulfate electrolytes. J Appl Electrochem 1979; 9: 55–70.10.1007/BF00620587Search in Google Scholar
Mansfeld F, Gilman S. The effect of lead ions on the dissolution and deposition characteristic of a zinc single crystal in 6 N KOH. J Electrochem Soc 1970; 117: 588–592.10.1149/1.2407584Search in Google Scholar
Marshall AT, Haverkamp RG. Nanoparticles of IrO2 or Sb-SnO2 increases the performance of iridium oxide DSA electrodes. J Mater Sci 2012; 47: 1135–1141.10.1007/s10853-011-5958-xSearch in Google Scholar
McGinnity JJ, Nicol MJ. The role of silver in enhancing the electrochemical activity of lead and lead-silver alloy anodes. Hydrometallurgy 2014; 144–145: 133–139.10.1016/j.hydromet.2014.02.005Search in Google Scholar
Mohammadi M, Alfantazi A. The performance of Pb-Ag anode in 2 Mn(II) – containing sulphuric acid electrolyte solutions. Hydrometallurgy, 2015; 153: 134–144.10.1016/j.hydromet.2015.02.009Search in Google Scholar
Morimitsu M, Tamura H, Matsunaga M, Otogawa R. Polarization behaviour and lifetime of IrO2–Ta2O5–SnO2/Ti anodes in p-phenolsulfonic acid solutions for tin plating. J Appl Electrochem 2000; 30: 511–514.10.1023/A:1003977928651Search in Google Scholar
Msindo ZS. An investigation of the electrorefining of copper with dimensionally stable titanium anodes and conventional lead alloy anodes. Master’s thesis, Chemical Engineering, Johannesburg, South Africa: University of the Witwatersrand, 2010: 205.Search in Google Scholar
Muresan L, Maurin G, Oniciu L, Gaga D. Influence of metallic impurities on zinc electrowinning from sulfate electrolyte. Hydrometallurgy 1996; 43: 345–354.10.1016/0304-386X(96)00012-6Search in Google Scholar
Newham AH. Corrosion rates of lead based anodes for zinc electrowinning at high current densities. J Appl Electrochem 1992; 22: 116–124.10.1007/BF01023812Search in Google Scholar
Nguyen TKT. A study of the mechanism by which cobalt ions minimize corrosion of lead alloy anodes during electrowinning of base metals. Ph.D. Thesis, Australia: University of Queensland, 2007.Search in Google Scholar
Nguyen T, Atrens A. Composition and morphology of the film formed on a lead alloy under conditions typical of the electrowinning of copper. Hydrometallurgy 2009; 96: 14–26.10.1016/j.hydromet.2008.07.014Search in Google Scholar
Nijjer S, Deposition and reduction of manganese dioxide on alternative anode materials in zinc electrowinning. Doctoral thesis, Trondlheim: Norwegian University of Science and Technology, 2000: 35–46.10.1016/S0013-4686(00)00597-1Search in Google Scholar
Niu J, Conway BE, Pell WG. Comparative studies of self-discharge by potential decay and float-current measurements at c double-layer capacitors and battery electrode. J Power Sources 2004; 135: 332–343.10.1016/j.jpowsour.2004.03.068Search in Google Scholar
Osorio WR, Peixoto LC, Garcia A. The effects of Ag content and dendrite spacing on the electrochemical behaviour of Pb-Ag alloys for Pb-acid battery components. J Power Sources 2013; 238: 324–335.10.1016/j.jpowsour.2013.03.099Search in Google Scholar
Pavlov D. Mechanism of the processes of the processes during anodic oxidation of a lead electrode in sulfuric acid solutions. In: Bullock KR, Pavlov D, editors. Proceedings of the Symposium on Advances in Lead-Acid Batteries, Battery Division, Electrochemical Society, New Orleans, 1984; 1: 110–122.Search in Google Scholar
Pavlov D, Rogachev T. Mechanism of the action of Ag and As on the anodic corrosion of lead and oxygen evolution at the Pb/PbO(2−x)/H2O/O2/H2SO4 electrode system. Electrochim Acta 1986; 31: 241–249.10.1016/0013-4686(86)87115-8Search in Google Scholar
Pavlov D, Monahov B, Petrov D. Effect of Ag element on the formation of lead oxide layer. In: 6th European Lead Battery Conference, Prague, 1998; 21–25: 3–6, Abstracts.Search in Google Scholar
Petrova M, Noncheva Z, Dobrev T, Rashkov St, Kounchev N, Petrov D, Vlaev St, Mihnev V, Zarev S, Georgieva L, Buttinelli D. Investigation of the processes of obtaining plastic treatment and electrochemical behaviour of lead alloys in their capacity as anodes during the electroextraction of zinc I. Behaviour of Pb-Ag, Pb-Ca and Pb-Ag-Ca alloys. Hydrometallurgy 1996; 40: 293–318.10.1016/0304-386X(95)00009-6Search in Google Scholar
Pourbaix M. Atlas of electrochemical equilibria in aqueous solutions, New York, USA: Pergamon Press, 1974.Search in Google Scholar
Prengaman RD. Structural control of non-antinational lead alloys via alloy additions, heat treatment and cold work. In: Lead Development, 7th International Lead Conference, Madrid, 1980: 34–47.Search in Google Scholar
Prengaman RD. The metallurgy of lead alloys for electrowinning anodes. In: Robinson DJ, James SE, editors. Proceedings of the Sessions sponsored by The Electrolytic Processes Committee of the Metallurgical Society of AIME, The Metallurgical Society of AIME, Los Angeles, California, 1984; 28: 49–56.Search in Google Scholar
Prengaman RD. Improvements to active material for VRLA batteries. J Power Sources 2005; 144: 426–437.10.1016/j.jpowsour.2004.11.004Search in Google Scholar
Prengaman RD, Siegmund A. New wrought Pb-Ag-Ca anodes for zinc electrowinning to protective oxide coating rapidly, LEAD-ZINC 2000. In: Dutrizac JE, Gonzalez JA, Henke DM, James SE, Siegmund AH-J, Warrendale PA, editors. The Metallurgical Society of AIME, 2000: 589–597.10.1002/9781118805558.ch39Search in Google Scholar
Porter F. In: Faulkener LL, editor. Zinc handbook, New York: Marcel Dekker, ISBN9780824783402, 1991.10.1201/9781482276947Search in Google Scholar
Rajkovic MB, Vladisavljevic GT, Ristic NM, Jaksic MM. A preconditioning process for extended passivation of alloyed lead anodes in zinc electrowinning. Bull Electrochem 1998; 14: 107–114.Search in Google Scholar
Rerolle C, Wiart R. Kinetics of oxygen evolution on Pb and Pb-Ag anodes during zinc electrowinning. Electrochem Acta 1996; 41: 1063–1069.10.1016/0013-4686(95)00439-4Search in Google Scholar
Robinson DJ, O’Keefe TJ. On the effects of antimony and glue on zinc electrocrystallization behaviour. J Appl Electrochem 1976; 6: 1–7.10.1007/BF01058863Search in Google Scholar
Rosenqvist T. Principles of extractive metallurgy, 2nd ed. New York, USA, Tapir Academic Press, ISBN8251919223, 1992: 7–16.Search in Google Scholar
Ruetschi PJ, Cahan BD. Electrochemical properties of PbO2 and the anodic corrosion of lead and lead alloys. J Electrochem Soc 1958; 105: 369–376.10.1149/1.2428866Search in Google Scholar
Schmachtel S, Toiminen M, Kontturi K, Forsén O, Barker MH. New oxygen evolution anodes for metal electrowinning: MnO2 composites electrodes. J Appl Electrochem 2009; 39: 1835–1848.10.1007/s10800-009-9887-1Search in Google Scholar
Sorour N, Zhang W, Gabra G, Ghali E, Houlachi G. Electrochemical studies of ionic liquid additives during the zinc electrowinning process. Hydrometallurgy 2015; 157: 261–269.10.1016/j.hydromet.2015.09.003Search in Google Scholar
Srinivasan VS, Cuzmar JS, O’Keefe TJ. The effects of lead on the electrochemical and adhesion behaviour of zinc electrodeposits. Metall Trans B 1990; 21B: 81–86.10.1007/BF02658118Search in Google Scholar
Sun QJ, Guo YG. Effects of antimony on the formation process of 3PbO·PbSO4·H2O on Pb and Pb-Sb electrodes. J Electroanal Chem 2000; 493: 123–129.10.1016/S0022-0728(00)00328-4Search in Google Scholar
Takehara Z, Kanumura K. The effect of the sulfuric acid concentration on the oxidation of PbSO4 to PbO2. J Electrochem Soc 1987; 134: 1604–1610.10.1149/1.2100721Search in Google Scholar
Tikkanen MH, Hyvarinen O. Tall. Dep., Inst. Technol., Otaniemi, Finland. Ed: Hamner, Norman E. Proc. Int. Congr. Metal. Corros., 4th (1972), Meeting Date 1969, pp. 669–675. Publisher: Nat. Ass. Corrosion. Tomas, L., Chem. Prum. (Czech.) 1984; 34: 286–291.Search in Google Scholar
Tripathy BC, Das SC, Hefter GT, Singh P. Zinc electrowinning from acidic sulfate solutions part I: effects of sodium lauryl sulfate. J Appl Electrochem 1997; 27: 673–678.10.1023/A:1018431619595Search in Google Scholar
Tshimwanga N, Maweja K, Tshula K. Efficacy of polyacrylamide and protein flocculants in preventing anode depassivation induced Pb-contamination of copper electrowinning cathodes. Hydrometallurgy 2011; 105: 240–245.10.1016/j.hydromet.2010.10.011Search in Google Scholar
Tunnicliffe M, Mohammadi F, Alfantazi A. Polarization behaviour of lead-silver anodes in zinc electrowinning electrolytes. J Electrochem Soc 2012; 159: C170–C180.10.1149/2.055204jesSearch in Google Scholar
Umetsu Y, Nozoka H, Tozawa K. Anodic behaviour of Pb-Ag alloys in sulfuric acid solution. In: Proceedings of the International Symposium on Extract. Metall. Zinc, MMJ, Tokyo, Japan, 1985: 265–279.Search in Google Scholar
Valeriote EML, Heim A, Ho MS. Variables affecting the deep-cycling characteristics of expanded-grid lead/acid battery plates. J Power Sources 1991; 33: 187–212.10.1016/0378-7753(91)85059-6Search in Google Scholar
Varela FE, Codaro EN, Vilche JR. Electrochim Acta 1995; 40: 1183–1188.10.1016/0013-4686(94)00321-QSearch in Google Scholar
Vereecken J, Winand R. Influence of manganese (II) ions on the anodic oxidation of methanol. Electrochim Acta 1972; 17: 121–278.10.1016/0013-4686(72)85028-XSearch in Google Scholar
Woollacott LC, Eric RH. Electrometallurgy, mineral and metal extraction: an overview, Johannesburg: The South African Institute of Mining and Metallurgy, 1994: 371–379.Search in Google Scholar
Yang HT, Liu HR, Guo ZC, Chen BM, Zhang YC, Huang H, Li XL, Fu RC, Xu RD. Electrochemical behaviour of rolled Pb-0.8%Ag anodes. Hydrometallurgy 2013a; 140: 144–150.10.1016/j.hydromet.2013.10.003Search in Google Scholar
Yang HT, Liu HR, Zhang YC, Chen BM, Guo ZC. Electrochemical behaviour of Pb-Ag-Sb-Ca quaternary alloys anodes for zinc electrowinning. J Kuming Univ Sci Technol 2013b; 8: 7–11.Search in Google Scholar
Yang HT, Guo ZC, Chen BM, Liu HR, Zhang YC, Huang H, Li XL, Fu RC, Xu RD. Electrochemical behaviour of rolled Pb-0.8% Ag anodes in an acidic zinc sulfate electrolyte solution containing chloride ions. Hydrometallurgy 2014; 147–148: 148–156.10.1016/j.hydromet.2014.05.004Search in Google Scholar
Yu P, O’Keefe TJ. Evaluation of lead anode reactions in acid sulfate electrolytes. I. Lead alloys with cobalt additives. J Electrochem Soc 1999; 146: 1361–1369.10.1149/1.1391771Search in Google Scholar
Yu P, O’Keefe TJ. Evaluation of lead anode reactions in acid sulfate electrolytes, II. Manganese. J Electrochem Soc 2002; 149: A558–A569.10.1149/1.1464882Search in Google Scholar
Zhang WS, Cheng CY. Manganese metallurgy review, Part III: Manganese control in zinc and copper electrolytes. Hydrometallurgy 2007; 89: 178–188.10.1016/j.hydromet.2007.08.011Search in Google Scholar
Zhang QB, Hua YX. Effect of Mn2+ ions on the electrodeposition of zinc from acidic sulfate solutions. Hydrometallurgy 2009; 99: 249–254.10.1016/j.hydromet.2009.09.002Search in Google Scholar
Zhang W, Houlachi G. Electrochemical studies of the performance of different Pb-Ag anodes during and after zinc electrowinning. Hydrometallurgy 2010; 104: 129–135.10.1016/j.hydromet.2010.05.007Search in Google Scholar
Zhang W, Lafront AM, Ghali E, Houlachi G. Influence of malonic acid and triethylbenzylammonium chloride on Zn electrowinning in zinc electrolyte. Hydrometallurgy 2009; 99: 181–188.10.1016/j.hydromet.2009.08.003Search in Google Scholar
Zhang YC, Chen BM, Yang HT, Huang H, Guo ZC. Anodic behaviour and microstructure of Al/Pb-Ag-Co anode during zinc electrowinning. J Cent South Univ 2014; 21: 83–88.10.1007/s11771-014-1919-2Search in Google Scholar
Zhong XC, Yu XY, Liu ZW, Jiang LX, Li J, Liu YX. Comparison of corrosion and oxygen evolution behaviours between cast and rolled Pb-Ag-Nd anodes. Int J Miner Metall Mater 2015; 22: 1067–1075.10.1007/s12613-015-1169-9Search in Google Scholar
©2019 Walter de Gruyter GmbH, Berlin/Boston