Resources Recycling (자원리싸이클링)

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

DOI QR Code

A Modified Process for the Separation of Fe(III) and Cu(II) from the Sulfuric Acid Leaching Solution of Metallic Alloys of Reduction Smelted Spent Lithium-ion Batteries

폐리튬이온전지의 용융환원된 금속합금상의 황산침출액에서 철(III)과 구리(II)의 분리를 위한 공정 개선

  • Nguyen, Thi Thu Huong (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National UnIIiversity) ;
  • Tran, Thanh Tuan (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National UnIIiversity) ;
  • Lee, Man Seung (Department of Advanced Materials Science & Engineering, Institute of Rare Metal, Mokpo National UnIIiversity)
  • ;
  • ;
  • 이만승 (목포대학교 공과대학 신소재공학과)
  • Received : 2021.11.15
  • Accepted : 2021.11.26
  • Published : 2022.02.28
Download PDF
⟨ Previous Next ⟩

Abstract

The smelting reduction of spent lithium-ion batteries results in metallic alloys containing Co, Cu, Fe, Mn, Ni, and Si. A process to separate metal ions from the sulfuric acid leaching solution of these metallic alloys has been reported. In this process, ionic liquids are employed to separate Fe(III) and Cu(II). In this study, D2EHPA and Cyanex 301 were employed to replace these ionic liquids. Fe(III) and Cu(II) from the sulfate solution were sequentially extracted using 0.5 M D2EHPA with three stages of cross-current and 0.3 M Cyanex 301. The stripping of Fe(III) and Cu(II) from the loaded phases was performed using 50% (v/v) and 60% (v/v) aqua regia solutions, respectively. The mass balance results from this process indicated that the recovery and purity percentages of the metals were greater than 99%.

폐리튬이온전지를 용융환원시키면 구리, 코발트, 철, 망간, 니켈 및 규소를 함유한 금속합금을 얻는다. 금속합금의 황산침출용액에서 상기 금속을 분리하기 위한 공정을 개발하여 발표하였다. 이 공정에서는 철(III)과 구리(II)를 분리하기 위해 이온성액체를 사용하였다. 본 연구에서는 이온성액체를 대체하기 위해 D2EHPA와 Cyanex 301을 추출제로 사용했다. 철(III)과 구리(II)는 황산침출액으로부터 0.5 M의 D2EHPA에 의한 3단의 교차추출 및 0.3 M의 Cyanex 301로 분리하는 것이 가능했다. 유기상으로부터 철(III)과 구리(II)의 탈거는 각각 50%와 60%의 왕수로 가능했다. 연속실험의 물질수지로부터 금속의 회수율과 순도는 99%이상으로 확인되었다.

Keywords

Acknowledgement

This work was supported by the Technology Innovation Program (Development of Material Component Technology) (Project number: 20011183) funded by the Ministry of Trade, Industry & Energy (MOTIE, Korea).

References

  1. Gladysz, G.M., Chawla, K.K., 2014 : Voids in Material, Elsevier, pp.131-156.
  2. Raphel, D.P., 2020 : The recycling of lithium-ion batteries: A strategic pillar for the European battery alliance, Etudes de l'Ifri, Ifri, pp.1-49.
  3. Gaines, L., Richa, K., Spangenberger, J., 2018 : Key issues for Li-ion battery recycling, MRS Energy & Sustainability, 5, pp.1-14.
  4. Diekmanna, J., Hanisch, C., Frobose, L., et al., 2017 : Ecological recycling of lithium-ion batteries from electric vehicles with focus on mechanical processes, Journal of The Electrochemical Society, 164, pp.A6184-A6191. https://doi.org/10.1149/2.0271701jes
  5. Pagnanelli, F., Moscardini, E., Altimari, P., et al., 2017 : Leaching of electrodic powders from lithium-ion batteries: Optimization of operating conditions and effect of physical pretreatment for waste fraction retrieval, Waste Manag, 60, pp.706-715. https://doi.org/10.1016/j.wasman.2016.11.037
  6. Xiao, J., Li, J., Xu, Z., 2017 : Recycling metals from lithium-ion battery by mechanical separation and vacuum metallurgy, Journal of Hazardous Materials, 338, pp.124-131. https://doi.org/10.1016/j.jhazmat.2017.05.024
  7. Zhang, X., Xue, Q., Li, L., et al., 2016 : Sustainable recycling and regeneration of cathode scraps from industrial production of lithium-ion batteries, ACS Sustainable Chemistry & Engineering, 4, pp.1-26. https://doi.org/10.1021/acssuschemeng.5b01327
  8. Nayl, A.A., Elkhashab, R.A., Badawy, S.M., et al., 2014 : Acid leaching of mixed spent Li-ion batteries, Arabian Journal Chemistry, pp.1-28.
  9. Takacova, Z., Havlik, T., Kukurugya, F., et al., 2016 : Cobalt and lithium recovery from active mass of spent Li-ion batteries: Theoretical and experimental approach, Hydrometallurgy, 163, pp.9-17. https://doi.org/10.1016/j.hydromet.2016.03.007
  10. Meshram, P., Pandey, B.D., Mankhand, T.R., et al., 2016 : Acid baking of spent lithium ion batteries for selective recovery of major metals: A two-step process, Journal of Industrial and Engineering Chemistry, 43, pp.117-126. https://doi.org/10.1016/j.jiec.2016.07.056
  11. Zhang, X., Xie, Y., Cao, H., et al., 2014 : A novel process for recycling and resynthesizing LiNi1/3Co1/3Mn1/3O2 from the cathode scraps intended for lithium-ion batteries, Waste Management, 34, pp.1715-1724. https://doi.org/10.1016/j.wasman.2014.05.023
  12. Pant, D., Dolker, T., 2017 : Green and facile method for the recovery of spent lithium nickel manganese cobalt oxide (NMC) based lithium ion batteries, Waste Management, 60, pp.689-695. https://doi.org/10.1016/j.wasman.2016.09.039
  13. Nayl, A.A., Hamed, M.M., Rizk, S.E., 2015 : Selective extraction and separation of metal values from leach liquor of mixed spent Li-ion batteries, Journal of the Taiwan Institute of Chemical Engineers, 55, pp.119-125. https://doi.org/10.1016/j.jtice.2015.04.006
  14. Nguyen, V.T., Lee, J.C., Jeong, J., et al., 2014 : Selective recovery of cobalt, nickel and lithium from sulfate leachate of cathode scrap of Li-ion batteries using liquid-liquid extraction, Metals and Materials International, 20, pp.357-365. https://doi.org/10.1007/s12540-014-1016-y
  15. Chiu, K.L., Chen, W.S., 2017 : Recovery and separation of valuable metals from cathode materials of spent lithium-ion batteries (LIBs) by ion exchange, Science of Advanced Materials, 9, pp.2155-2160. https://doi.org/10.1166/sam.2017.3214
  16. Zheng, X., Zhu, Z., Lin, X., et al., 2018 : A mini-review on metal recycling from spent lithium ion batteries, Engineering, 4, pp.361-70. https://doi.org/10.1016/j.eng.2018.05.018
  17. Song, D., Wang, X., Zhou, E., et al., 2013 : Recovery and heat treatment of the Li(Ni1/3Co1/3Mn1/3)O2 cathode scrap material for lithium ion battery, Journal of Power Sources, 232, pp.348-352. https://doi.org/10.1016/j.jpowsour.2012.10.072
  18. Makuza, B., Tian, Q., Guo, X., et al., 2021 : Pyrometallurgical options for recycling spent lithium-ion batteries: A comprehensive review, Journal of Power Sources, 491, pp.229622. https://doi.org/10.1016/j.jpowsour.2021.229622
  19. Vanitha, M., Balasubramanian, N., 2013 : Waste minimization and recovery of valuable metals from spent lithium-ion batteries - A review, Environmental Technology Reviews, 2, pp.101-115. https://doi.org/10.1080/21622515.2013.853105
  20. Lin, J., Liu, C., Cao, H., et al., 2019 : Environmentally benign process on selective recovery of valuable metals from spent lithium-ion batteries by using conventional sulfation roasting, Green Chemistry, 21, pp.5904-5913. https://doi.org/10.1039/c9gc01350d
  21. Tuan, T.T, Hoon, H.S., Lee, M.S., 2021 : Co, Ni, Cu, Fe, and Mn integrated recovery process via sulphuric acid leaching from spent lithium-ion batteries smelted reduction metallic alloys, Mineral Processing and Extractive Metallurgy Review (accepted).
  22. Vogel, A.I., 1989 : Textbook of Quantitative Chemical analysis, fifth ed., Longman scientific & Technical, New York, pp.295-296.
  23. Tran, T.T., Iqbal, M., Lee, M.S., 2019 : Comparison of the extraction and stripp.ing behavior of iron(III) from weak acidic solution between ionic liquids and commercial extractants, Korean Journal of Metals and Materials, 57, pp.787-794. https://doi.org/10.3365/kjmm.2019.57.12.787
  24. Ciceri, D., Mason, L.R., Harvie, D.J.E., et al., 2014 : Extraction kinetics of Fe(III) by di-(2-ethylhexyl) phosphoric acid using a Y-Y shaped microfluidic device, Chemical Engineering Research and Design, 92, pp.571-580. https://doi.org/10.1016/j.cherd.2013.08.033
  25. Akhlaghi, M., Rashchi, F., Vahidi, E., 2010 : Stripp.ing of Fe((III) from D2EHPA using different reagents. XXV International Mineral Processing Congress (IMPC) 2010 Proceedings, pp.255-262.
  26. Liu, Y., Nam, S.H., Lee, M.S., 2014 : Stripp.ing of Fe(III) from the loaded mixture of D2EHPA and TBP with sulfuric acid containing reducing agents, Bulletin of the Korean Chemical Society, 35, pp.2109-2113. https://doi.org/10.5012/bkcs.2014.35.7.2109
  27. Lee, S.A., Lee, M.S., 2019 : Selective extraction of Cu(II) from sulfuric acid leaching solution od spent lithium ion batteries using Cyanex 301, Korean Journal of Metals and Materials, 57, pp.596-602. https://doi.org/10.3365/kjmm.2019.57.9.596
  28. 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.
  29. 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