Feasibility Study of Methanesulfonic Acid (MSA),  an Alternative Lixiviant to Improve Conventional Sulfuric Acid Leaching of NCM Black Mass

Hyewon Jung; Jeseung Lee; Ganghoon Song; Minseo Park; Junmo Ahn

doi:10.7844/kirr.2024.33.1.58

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2024 Vol.33, Issue 1 Preview Page Next Page

Feasibility Study of Methanesulfonic Acid (MSA), an Alternative Lixiviant to Improve Conventional Sulfuric Acid Leaching of NCM Black Mass NCM Black Mass 황산침출 개선을 위한 대체침출제 메탄술폰산의 적용가능성 연구

28 February 2024. pp. 58-68

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Abstract

Critical minerals such as nickel, cobalt and lithium, are known as materials for cathodic active materials of lithium ion batteries. The consumption of the minerals is expected to grow with increasing the demands of electric vehicles, resulting from carbon neutrality. Especially, the demand for LIB (lithium ion battery) recycling is expected to increase to meet the supply of nickel, cobalt and lithium for LIB. The recycling of EOL (end-of-life) LIB can be achieved by leaching EOL LIB using inorganic acid such as HCl, HNO₃ and H₂SO₄, which are regarded as hazardous materials. In the present study, the potential use of MSA (Methanesulfonic acid), as an alternative lixiviant replacing sulfuric acid was investigated. In addition, leaching behaviors of NCM black mass leaching with MSA was also investigated by studying various leaching factors such as chemical concentration, leaching time, pulp density (P/D) and temperatures. The leaching efficiency of nickel (Ni), cobalt (Co), lithium (Li), and manganese (Mn) from LIB was enhanced by increasing concentration of lixiviant and reductant, leaching time and temperature. The maximum leaching of the metals was above 99% at 80℃. In addition, MSA can replace sulfuric acid to recover Ni, Co, Li, Mn from NCM black mass.

Keywords

Methanesulfonic acid

NCM Black mass

Alternative lixiviant

LIB Recycling

Hydrometallurgy

핵심광물인 니켈, 코발트, 리튬은 NCM계 리튬이온배터리(이하 LIB)의 양극소재로 알려져 있다. 탄소중립 기조에 따라 전기자동차의 보급량 증가로 핵심광물 수요도 증가할 것으로 예상된다. 하지만, LIB용 핵심광물 Li, Co, Ni의 수요대비 공급 부족으로 인해, 폐리튬이온배터리(EOL LIB)의 리싸이클링 수요가 증가할 것으로 예상된다. EOL LIB(폐 LIB) 재활용은 유해화학물질 무기산 침출제인 염산(HCl), 질산(HNO₃), 황산(H₂SO₄)을 침출공정에 적용하여 재활용한다. 본 연구에서는 친환경 대체침출제 메탄술폰산(이하 MSA)의 적용 가능성을 검토하였다. 또한, 침출제 농도, 환원제 농도, 침출시간, 광액농도(P/D), 온도 등의 침출인자가 NCM Black mass 침출에 미치는 영향을 연구하였다. 침출실험 결과, 침출제와 환원제 농도, 침출시간, 침출온도가 증가함에 따라 목적금속 Ni, Li, Co, Mn의 침출률이 향상됨을 확인하였고, 금속의 최대 침출률은 80℃에서 99% 이상으로 나타났다. 또한, MSA는 NCM Black mass 대상 침출에 적용하여 Ni, Li, Co, Mn을 회수할 수 있음을 확인하였다.

키워드

메탄술폰산

NCM Black Mass

대체침출제

리튬이온배터리 재활용

습식제련

References

Akcil, A., Erust, C., Gahan, C.S., et al., 2015 : Precious metal recovery from waste printed circuit boards using cyanide and non-cyanide lixiviants - A review, Waste Management, 45, pp.258-271. 10.1016/j.wasman.2015.01.01725704926

Zhang, X., Zhang, C., Zheng, F., et al., 2019 : Alkaline electrochemical leaching of Sn and Pb from the surface of waste printed circuit board and the stripping of gold by methanesulfonic acid, Environmental Progress & Sustainable Energy, 39(2), e13324. 10.1002/ep.13324

Golmohammadzadeh, R., Rashchi, F., and Vahidi, E., 2017 : Recovery of lithium and cobalt from spent lithium-ion batteries using organic acids: Process optimization and kinetic aspects, Waste Management, 64, pp.244-254. 10.1016/j.wasman.2017.03.03728365275

Okonkwo, E.G., Wheatley, G., Liu, Y., et al., 2023 : Green and efficient recovery of valuable metals from spent lithium-ion batteries using molasses: Parametric optimization and performance evaluation, Hydrometallurgy, 222, 106168. 10.1016/j.hydromet.2023.106168

Wang, B., Lin, X.-Y., Tang, Y., et al., 2019 : Recycling LiCoO₂ with methanesulfonic acid for regeneration of lithium-ion battery electrode materials, Journal of Power Sources, 436, 226828. 10.1016/j.jpowsour.2019.226828

Gratz, E., Sa, Q., Apelian, D., et al., 2014 : A closed loop process for recycling spent lithium ion batteries, Journal of Power Sources, 262, pp.255-262. 10.1016/j.jpowsour.2014.03.126

Chagnes, A., and Pospiech, B., 2013 : A brief review on hydrometallurgical technologies for recycling spent lithium-ion batteries, Journal of Chemical Technology & Biotechnology, 88(7), pp.1191-1199. 10.1002/jctb.4053

Binnemans, K., and Jones, P.T., 2022 : Methanesulfonic Acid (MSA) in Hydrometallurgy, Journal of Sustainable Metallurgy, 9(1), pp.26-45. 10.1007/s40831-022-00641-6

Duggan, J., 2005 : The potential for landfill leachate treatment using willows in the UK-A critical review, Resources, Conservation and Recycling, 45(2), pp.97-113. 10.1016/j.resconrec.2005.02.004

Innocenzi, V., De Michelis, I., and Vegliò, F., 2017 : Design and construction of an industrial mobile plant for WEEE treatment: Investigation on the treatment of fluorescent powders and economic evaluation compared to other e-wastes, Journal of the Taiwan Institute of Chemical Engineers, 80, pp.769-778. 10.1016/j.jtice.2017.09.019

Golmohammadzadeh, R., Faraji, F., and Rashchi, F., 2018 : Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review, Resources, Conservation and Recycling, 136, pp.418-435. 10.1016/j.resconrec.2018.04.024

Li, L., Ge, J., Wu, F., et al., 2010 : Recovery of cobalt and lithium from spent lithium ion batteries using organic citric acid as leachant, Journal of Hazardous Materials, 176(1-3), pp.288-293. 10.1016/j.jhazmat.2009.11.02619954882

Li, L., Lu, J., Ren, Y., et al., 2012 : Ascorbic-acid-assisted recovery of cobalt and lithium from spent Li-ion batteries, Journal of Power Sources, 218, pp.21-27. 10.1016/j.jpowsour.2012.06.068

Li, L., Qu, W., Zhang, X., et al., 2015 : Succinic acid-based leaching system: A sustainable process for recovery of valuable metals from spent Li-ion batteries, Journal of Power Sources, 282, pp.544-551. 10.1016/j.jpowsour.2015.02.073

Tran, T.T., Moon, H.S., and Lee, M.S., 2021 : Comparison of the Chemical Reactivity between Sulfuric and Methanesulfonic Acids as a Leaching Agent, Resources Recycling, 30(3), pp.41-46. 10.7844/kirr.2021.30.3.41

Yadav, P., Jie, C.J., Tan, S., et al., 2020 : Recycling of cathode from spent lithium iron phosphate batteries, Journal of Hazardous Materials, 399, 123068. 10.1016/j.jhazmat.2020.12306832521319

Kim, Y.E., Byun, M.Y., Baek, J.H., et al., 2020 : Recovery of Metallic Pd with High Purity from Pd/Al₂O₃ Catalyst by Hydrometallurgy in HCl, Clean Technology, 26(4), pp.270-278.

Vieceli, N., Benjamasutin, P., Promphan, R., et al., 2023 : Recycling of Lithium-Ion Batteries: Effect of Hydrogen Peroxide and a Dosing Method on the Leaching of LCO, NMC Oxides, and Industrial Black Mass, ACS Sustainable Chemistry & Engineering, 11, pp.9662-9673. 10.1021/acssuschemeng.3c01238

Wu, L., Chen, K., Cheng, S., et al., 2008 : Thermal decomposition of hydrogen peroxide in the presence of sulfuric acid, Journal of Thermal Analysis and Calorimetry, 93(1), pp.115-120. 10.1007/s10973-007-8829-6

McKee, D., 1969 : Catalytic decomposition of hydrogen peroxide by metals and alloys of the platinum group, Journal of Catalysis, 14(4), pp.355-364. 10.1016/0021-9517(69)90326-1

Information

Publisher :The Korean Institute of Resources Recycling
Publisher(Ko) :한국자원리싸이클링학회
Journal Title :Resources Recycling
Journal Title(Ko) :자원리싸이클링
Volume : 33
No :1
Pages :58-68
Received Date : 2024-01-24
Revised Date : 2024-02-17
Accepted Date : 2024-02-19
DOI :https://doi.org/10.7844/kirr.2024.33.1.58

Resources Recycling ISSN:2765-3439(Print) 2765-3447(Online) 자원리싸이클링

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