Abstract
Cu-removal operation is one of the vital purifying processes for the nickel electrolysis anolyte. Different from the nickel concentrate-activated anode slime-sulfurous acid, NiS and MnS, hydrogen sulfide (H2S) introduced less metal impurities into the systems. And the precipitation theory is the main principles of nickel purification method utilizing H2S in removing Cu from the anolyte rather than these replacement reactions. The Solubility Product Constant (Ksp) of CuS is lower than NiS, which indicates that the precipitate of CuS can be highly efficiently and selectively formed and easily removed from the nickel anolyte. In this research, the effects of mole ratio of [H2S]/[Cu], pH, temperature, potential–pH diagrams and the precipitates of metal sulfides were investigated. The experimental results show that the H2S was a potential successor as the highly efficient and selective Cu-removal reagent. The concentration of Cu2+ in Watts can be reduced to lower than 0.002 g/L, and the mass ratios of Cu/Ni in this precipitate are larger than 15 in the low pH state (1.0–1.5). S, CuS, Cu2S, NiS, NiS2 or Ni3S2 may be presented and coexisted in the region that concluded from the analysis of potential–pH diagram. The XRD analysis of precipitates indicated that it was composed by CuS and NiSO4·6H2O. The XPS measurement shows that the valence states of Cu and Ni are Cu2+ and Cu+ and Ni2+, respectively. The valence state of S includes the S2−, Sx2− and SO42− states. Therefore, H2S can highly efficient and selective remove the Cu2+ from the low pH nickel Watts solution, and which can be applied on the nickel anolyte purification in the future.
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Ban S, Jiang X, Yi Y, Zhou J (2021) Study on copper removal from nickel electrolyte under acidic condition. Nonferr Metal Equip 35: 25–28. https://doi.org/10.19611/j.cnki.cn11-2919/tg.2021.05.006
Brullas E, Rambla J, Casado J (1999) Nickel electrowinning using a Pt catalysed hydrogen-diffusion anode. Part I: effect of chloride and sulfate ions and a magnetic field. J Appl Electrochem 29:1367–1376. https://doi.org/10.1023/A:1003852924383
Chapoy A, Mohammadi AH, Tohidi B, Valtz A, Richon D (2005) Experimental measurement and phase behavior modeling of hydrogen sulfide-water binary system. Ind Eng Chem Res 44:7567–7574. https://doi.org/10.1021/IE050201H
Chen X, Chen A, Zhao Z, Liu X, Shi Y, Wang D (2013) Removal of Cu from the nickel electrolysis anolyte using nickel thiocarbonate. Hydrometallurgy 133:106–110. https://doi.org/10.1016/j.hydromet.2012.12.007
Chen A, Zhao Z, Chen X, Liu X, Cao C (2014) Decoppering capability of nickel thiocarbonate in nickel electrolyte. Hydrometallurgy 144–145:23–26. https://doi.org/10.1016/j.hydromet.2014.01.013
Duan Z, Sun R, Liu R, Zhu C (2007) Accurate thermodynamic model for the calculation of H2S solubility in pure water and brines. Energy Fuels 21:2056–2065. https://doi.org/10.1021/ef070040p
Estay H, Barros L, Troncoso E (2021) Metal sulfide precipitates: recent breakthroughs and future outlooks. Minerals 11:1385. https://doi.org/10.3390/min11121385
Hoare JP (1986) On the role of boric acid in the watts bath. J Electrochem Soc 133:2491–2494. https://doi.org/10.1149/1.2108456
Hosseini M, Rahimi R, Ghaedi M (2020) Hydrogen sulfide solubility in different ionic liquids: an updated database and intelligent modeling. J Mol Liq 317:113984. https://doi.org/10.1016/j.molliq.2020.113984
Izaki M, Khoo PL, Shinagawa T (2021) Review-Solution electrochemical process for fabricating metal oxides and the thermodynamic design. J Electrochem Soc 168:112510. https://doi.org/10.1149/1945-7111/ac371a
Ji J, Cooper WC, Dreisinger DB, Peters E (1995) Surface pH measurements during nickel electrodeposition. J Appl Electrochem 25:642–650. https://doi.org/10.1007/BF00241925
Jiang L, **n Y, Chou I, Sun R (2020) Raman spectroscopic measurements of H2S solubility in pure water over a wide range of pressure and temperature and a refined thermodynamic model. Chem Geo 555:119816. https://doi.org/10.1016/j.chemgeo.2020.119816
Kelsall GH, Thompson I (1993) Redox chemistry of H2S oxidation in the British Gas Stretford Process Part I: thermodynamics of sulphur-water systems at 298 K. J App Electrochem 23:279–286. https://doi.org/10.1007/BF00296682
Lewis AE (2010) Review of metal sulphide precipitates. Hydrometallurgy 104:222–234. https://doi.org/10.1016/j.hydromet.2010.06.010
Lewis A, van Hille R (2006) An exploration into the sulphide precipitation method and its effect on metal sulphide removal. Hydrometallurgy 81:197–204. https://doi.org/10.1016/j.hydromet.2005.12.009
Li L, Chen X, Liu X, Zhao Z (2014) Removal of Cu from the nickel electrolysis anolyte using amorphous MnS. Hydrometallurgy 146:149–153. https://doi.org/10.1016/j.hydromet.j.hydromet.2014.04.004
Macdonald DD, Syrett BC (1979) Potential–pH diagrams for iron and nickel in high salinity genothermal brine containing low concentrations of hydrogen sulfide. Corrosion 35:471–475. https://doi.org/10.5006/0010-9312-35.10.471
Mamiyev ZQ, Balayeva NO (2016) CuS nanoparticles synthesized by a facile chemical route under different pH conditions. Mendeleev Commun 26:235–237. https://doi.org/10.1016/j.mencom.2016.05.004
Masar M, Urbanek M, Urbanek P, Machovska Z, Maslik J, Yadav RS, Skoda D, Machovsky M, Kuritka I (2019) Synthesis, characterization and examination of photocatalytic performance of hexagonal covellite CuS nanoplates. Mater Chem Phy 237:121823. https://doi.org/10.1016/j.matchemphys.2019.121823
Renzoni LS (1969) Extractive metallurgy at international nickel—A half century of progress. Canad J Chem Eng 47:3–11. https://doi.org/10.1002/cjce.5450470101
Safrani T, Jopp J, Golan Y (2013) A comparative study of the structure and optical properties of copper sulfide thin films chemically deposited on various substrates. RSC Adv 3:23066–23074. https://doi.org/10.1039/c3ra42528b
Sharma N, Tiwari S, Saxena R (2016) On-line solid phase extraction method based on flow injection-FAAS using 1,10-phenanthroline modified chelating resin for chromium speciation in industrial water samples. RSC Adv 6:10775–10782. https://doi.org/10.1039/c6ra01286h
Shea D, Helz GR (1988) The solubility of copper in sulfidic waters: sulfide and polysulfide complexes in equilibrium with covellite. Geochim Et Cosmochim Acta 52:1815–1825. https://doi.org/10.1016/0016-7037(88)90005-1
Soldatov VS, Shunkevich AA, Sergeev GI (1988) Synthesis, structure and properties of new fibrous ion-exchangers. React Polym 7:159–172. https://doi.org/10.1016/0016-7037(88)90005-1
Sonai Muthu N, Gopalan M (2019) Mesoporous nickel sulphide nanostructures for enhanced supercapacitor performance. Appl Surf Sci 480:186–198. https://doi.org/10.1016/j.apsusc.2019.02.250
Stefaniak J, Karwacka S, Janiszewska M, Dutta A, Rene ER, Regel-Rosocka M (2020) Co(II) and Ni(II) transport from model and real sulfate solutions by extraction with bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272). Chemosphere 254:126869. https://doi.org/10.1016/j.chemosphere.2020.126869
Wang D, Lu J, Li Y, Zhao C, Zheng J, Chen Z, Guo Y (2015) The influence of additives on copper removing and electrolytic nickel’s quality. Mater Rep 29:280–283.
Xue J, Zhong H, Wang S, Long D (2019) Influence mechanism of sulfide ions during manganese electrodeposition. J Wuhan Univ Technol Mater Sci Ed 34:1451–1459. https://doi.org/10.1007/s11595-019-2212-x
Zeng W, Guo W, Li B, Wei Z, Dionysiou DD, **ao R (2021) Kinetics and mechanistic aspects of removal of heavy metal through gas-liquid sulfide precipitates: a computational and experimental study. J Hazard Mater 408:124868. https://doi.org/10.1016/j.jhazmat.2020.124868
Zhao S (2012) Research progress of copper removal from nickel electrolyte. Hunan Nonferr Metals 28:19–25.
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This work was financially supported by LICP Cooperation Foundation for Young Scholars (HZJJ20-09), Lanzhou Chengguan District Science and Technology Planning Project (2021-5-1).
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Lu, X., Li, Y., Zhang, A. et al. Highly efficient and selective removal of copper from low pH nickel Watts solution through hydrogen sulfide. Chem. Pap. 77, 6707–6715 (2023). https://doi.org/10.1007/s11696-023-02970-6
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DOI: https://doi.org/10.1007/s11696-023-02970-6