Resources Recycling (자원리싸이클링)

The Korean Institute of Resources Recycling (한국자원리싸이클링학회)
권호 표지
DOI QR코드

DOI QR Code

Separation of Co(II), Ni(II), and Cu(II) from Sulfuric Acid Solution by Solvent Extraction

황산용액에서 용매추출에 의한 코발트(II), 니켈(II) 및 구리(II) 분리

  • Moon, Hyun Seung (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National University) ;
  • Song, Si Jeong (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National University) ;
  • Tran, Thanh Tuan (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National University) ;
  • Lee, Man Seung (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National University)
  • 문현승 (목포대학교 공과대학 신소재공학과) ;
  • 송시정 (목포대학교 공과대학 신소재공학과) ;
  • ;
  • 이만승 (목포대학교 공과대학 신소재공학과)
  • Received : 2021.09.18
  • Accepted : 2021.12.08
  • Published : 2022.02.28
Download PDF
⟨ Previous Next ⟩

Abstract

The smelting reduction of spent lithium-ion batteries results in metallic alloys of cobalt, nickel, and copper. To develop a process to separate the metallic alloys, leaching of the metallic mixtures of these three metals with H2SO4 solution containing 3% H2O2 dissolved all the cobalt and nickel, together with 9.6% of the copper. Cyanex 301 selectively extracted Cu(II) from the leaching solution, and copper ions were completely stripped with 30% aqua regia. Selective extraction of Co(II) from a Cu(II)-free raffinate was possible using the ionic liquid ALi-SCN. Three-stage cross-current stripping of the loaded ALi-SCN by a 15% NH3 solution resulted in the complete stripping of Co(II). A process was proposed to separate the three metal ions from the sulfuric acid leaching solutions of metallic mixtures by employing solvent extraction.

폐리튬이온배터리를 고온에서 용융환원시키면 코발트, 니켈 및 구리 금속합금상을 얻을 수 있다. 이러한 금속합금상으로부터 금속을 분리회수하기 위한 공정을 개발하기 위해 코발트, 니켈 및 구리 금속을 혼합한 금속혼합물을 3% 과산화수소를 함유한 2 M 황산용액으로 침출하면 9.6%의 구리와 함께 코발트와 니켈이 모두 침출된다. 침출용액에서 Cyanex 301로 구리(II)가 선택적으로 추출되었으며, 30% 왕수로 구리(II)를 탈거했다. 구리가 분리된 여액에서 이온성액체인 ALi-SCN으로 Co(II)를 선택적으로 추출했으며, 15%의 암모니아용액으로 3단의 교차식 탈거를 통해 모두 탈거했다. 본 연구를 통해 코발트, 니켈 및 구리 금속혼합물의 황산침출액에서 용매추출로 세 금속을 분리할 수 있는 공정을 제안했다.

Keywords

Acknowledgement

본 연구는 2021년도 산업통상자원부 및 산업기술평가관리원(KEIT) 연구비 지원에 의한 연구결과 (과제번호 20011183)이며 이에 감사드립니다.

References

  1. Natarajan, S., Aravindan, V., 2018 : Burgeoning prospects of spent lithium-ion batteries in multifarious applications, Advanced Energy Materials, 8(33), pp.1-16.
  2. Or, T., Gourley, S. W. D., Kaliyappan, K., et al., 2019 : Recycling of mixed cathode lithium-ion batteries for electric vehicles: Current status and future outlook, Carbon Energy, pp.6-43.
  3. Shin, S. M., Kim, N. H., Sohn, J. S., et al., 2005 : Development of a metal recovery process from Li-ion battery wastes, Hydrometallurgy, 79, pp.172-181. https://doi.org/10.1016/j.hydromet.2005.06.004
  4. Yusupov, T. S., Isupov, V. P., Vladimirov, A. G., et al., 2015 : Analysis of Material Composition and Dissociation Potential of Minerals in Mine Waste to Assess Productivity of Lithium Concentrates, Journal of Mining Science, 51(6), pp.1242-1247. https://doi.org/10.1134/s106273911506054x
  5. Swain, B., Jeong, J., Lee, J. C., et al., 2008 : Development of process flow sheet for recovery of high pure cobalt from sulfate leach liquor of LIB industry waste: A mathematical model correlation to predict optimum operational conditions, Separation and Purification Technology, 63(2), pp.360-369. https://doi.org/10.1016/j.seppur.2008.05.022
  6. Reddy, R. G., Chaubal, P., Plstorius, P. C., et al., 2016 : Chemistry and Materials Science: Professional, The Minerals, Metals & Materials Society, 978-3-319-48769-4.
  7. Li, J., Wang, G., Xu, Z., 2015 : Environmentally-friendly oxygen-free roasting/wet magnetic separation technology for in situ recycling cobalt, lithium carbonate and graphite from spent LiCoO2/graphite lithium batteries, Journal of Hazardous Materials, 302, pp.97-104. https://doi.org/10.1016/j.jhazmat.2015.09.050
  8. Lv, W., Wang, Z., Cao, H., et al., 2017 : A Critical review and analysis on the recycling of spent Lithium-ion batteries, ACS Sustainable Chemistry & Engineering, 6(2), pp.1504-1521. https://doi.org/10.1021/acssuschemeng.7b03811
  9. Xu, Jinqiu., Thomas, H. R., Francis, R. W., et al., B., 2008 : A review of processes and technologies for the recycling of lithium-ion secondary batteries, Journal of Power Sources, 177(2), pp.512-527. https://doi.org/10.1016/j.jpowsour.2007.11.074
  10. Garcia, E. M., Taroco, H. A., Matencio, T., et al., 2012 : Electrochemical recycling of cobalt from spent cathodes of lithium-ion batteries: its application as supercapacitor, Journal of Applied Electrochemistry, 42, pp.361-366. https://doi.org/10.1007/s10800-012-0419-z
  11. Garcia, E. M., Taroco, H. A., Matencio, T., et al., 2011 : Electrochemical recycling of cobalt from spent cathodes of lithium-ion batteries: its application as coating on SOFC interconnects, Journal of Applied Electrochemistry, 41, 1373. https://doi.org/10.1007/s10800-011-0339-3
  12. Garcia, E. M., Santos, J. S., Pereira, E. C., et al., 2008 : Electrodeposition of cobalt from spent Li-ion battery cathodes by the electrochemistry quartz crystal microbalance technique, Journal of Power Sources, 185(1), pp.549-553. https://doi.org/10.1016/j.jpowsour.2008.07.011
  13. Moon, H. S., Song, S. J., Tran, T. T., et al., 2021 : Leaching of Cobalt and Nickel from Metallic Mixtures by Inorganic and Organic Acid Solutions, Resources Recycling, 30(2), pp.53-60. https://doi.org/10.7844/KIRR.2021.30.2.53
  14. Tran, T. T., Moon, H. S., Lee, M. S., 2020 : Separation of Cobalt, Nickel, and Copper from Synthetic Metallic Alloy by Selective Dissolution with Acid Solutions Containing Oxidizing Agent, Mineral Processing and Extractive Metallurgy Review, pp.1-13.
  15. Rybka, P., Regel-Rosocka, M., 2012 : Nickel and Cobalt Extraction from Chloride Solutions with Quaternary Phosphonium Salts, Separation Science and Technology, 47(9), pp.1296-1302. https://doi.org/10.1080/01496395.2012.672532
  16. Lee, S. A., Lee, M. S., 2019 : Selective Extraction of Cu(II) from Sulfuric Acid Leaching Solutions of Spent Lithium Ion Batteries Using Cyanex 301, Korean Journal of Metals and Materials, 57(9), pp.596-602. https://doi.org/10.3365/kjmm.2019.57.9.596
  17. Sole, K. C., Hiskey, J. B., 1995 : Solvent extraction of copper by Cyanex 272, Cyanex 302 and Cyanex 301, Hydrometallurgy, 37, pp.129-147. https://doi.org/10.1016/0304-386X(94)00023-V
  18. Tran T.T., Moon H.S., Lee M.S., 2021 : Recovery of cobalt, nickel and copper compounds from UHT processed spent lithium-ion batteries by hydrometallurgical process, Mineral Processing and Extractive Metallurgy Review, pp.1-13.
  19. Moon, H. S., Song, S. J., Tran, T. T., et al., 2020 : Solvent extraction separation of Co(II) and Ni(II) from weak hydrochloric acid solution with ionic liquids synthesized from organophosphorus acids, Resources Recycling, 30(2), pp.53-60. https://doi.org/10.7844/KIRR.2021.30.2.53