Abstract
Extraction of Mn(II) and Co(II) from chloride solutions in the system with a hydrophobic deep eutectic solvent (HDES) based on di(2-ethylhexyl)phosphoric acid (D2EHPA) and menthol is studied depending on the aqueous phase acidity, the HDES composition, the concentration of chloride ions, and the volume ratio of the system phases. The extraction mechanism for the studied metals is established. A thermodynamic analysis of the extraction process in the proposed system is carried out. Evaluation of the possibility of reusing the HDES D2EHPA/menthol on the example of the extraction of Mn(II) ions is performed for the first time. The potential for the application of the proposed HDES for isolation of metals from aqueous solutions is demonstrated.
REFERENCES
Golmohammadzadeh, R., Faraji, F., and Rashchi, F., Recovery of lithium and cobalt from spent lithium ion batteries (LIBs) using organic acids as leaching reagents: A review, Resour., Conserv. Recycl., 2018, vol. 136, pp. 418–435. https://doi.org/10.1016/j.resconrec.2018.04.024
Pham, H.D., Horn, M., Fernando, J.F.S., Patil, R., Phadatare, M., Golberg, D., Olin, H., and Dubal, D.P., Spent graphite from end-of-life Li-ion batteries as a potential electrode for aluminium ion battery, Sustainable Mater. Technol., 2020, vol. 26, article no. e00230. https://doi.org/10.1016/j.susmat.2020.e00230
Garole, D.J., Hossain, R., Garole, V.J., Sahajwalla, V., Nerkar, J., and Dubal, D.P., Recycle, recover and repurpose strategy of spent Li-ion batteries and catalysts: Current status and future opportunities, ChemSusChem, 2020, vol. 13, no. 12, pp. 3079–3100. https://doi.org/10.1002/cssc.201903213
Or, T., Gourley, S.W.D., Kaliyappan, K., Yu, A., and Chen, Z., Recycling of mixed cathode lithium-ion batteries for electric vehicles: Current status and future outlook, Carbon Energy, 2020, vol. 2, no. 1, pp. 6–43. https://doi.org/10.1002/cey2.29
Neumann, J., Petranikova, M., Meeus, M., Gamarra, J.D., Younesi, R., Winter, M., and Nowak, S., Recycling of lithium-ion batteries—current state of the art, circular economy, and next generation recycling, Adv. Energy Mater., 2022, vol. 12, no. 17, article no. 2102917, pp. 1–26. https://doi.org/10.1002/aenm.202102917
Peeters, N., Binnemans, K., and Riaño, S., Solvometallurgical recovery of cobalt from lithium-ion battery cathode materials using deep-eutectic solvents, Green Chem., 2020, vol. 22, pp. 4210–4221. https://doi.org/10.1039/D0GC00940G
Pateli, I.M., Thompson, D., Alabdullah, S.S.M., Abbott, A.P., Jenkin, G.R.T., and Hartley, J.M., The effect of pH and hydrogen bond donor on the dissolution of metal oxides in deep eutectic solvents, Green Chem., 2020, vol. 22, pp. 5476–5486. https://doi.org/10.1039/D0GC02023K
Zinov’eva, I.V., Fedorov, A.Ya., Milevskii, N.A., Zakhodyaeva, Yu.A., and Voshkin, A.A., Dissolution of metal oxides in a choline chloride–sulphosalicylic acid deep eutectic solvent, Theor. Found. Chem. Eng., 2021, vol. 55, no. 4, pp. 663–670. https://doi.org/10.1134/S0040579521040370
Vasilyev, F., Virolainen, S., and Sainio, T., Numerical simulation of counter-current liquid–liquid extraction for recovering Co, Ni and Li from lithium-ion battery leachates of varying composition, Sep. Purif. Technol., 2019, vol. 210, pp. 530–540. https://doi.org/10.1016/j.seppur.2018.08.036
Vieceli, N., Nogueira, C.A., Pereira, M.F.C., Durão, F.O., Guimarães, C., and Margarido, F., Optimization of metals extraction from spent lithium-ion batteries by sulphuric acid and sodium metabisulphite through a techno-economic evaluation, J. Environ. Manage., 2018, vol. 228, pp. 140–148. https://doi.org/10.1016/j.jenvman.2018.08.085
Florindo, C., Branco, L.C., and Marrucho, I.M., Quest for green-solvent design: from hydrophilic to hydrophobic (deep) eutectic solvents, ChemSusChem, 2019, vol. 12, no. 8, pp. 1549–1559. https://doi.org/10.1002/cssc.201900147
Zhu, A., Bian, X., Han, W., Cao, D., Wen, Y., Zhu, K., and Wang, S., The application of deep eutectic solvents in lithium-ion battery recycling: A comprehensive review, Resour., Conserv. Recycl., 2023, vol. 188, article no. 106690. https://doi.org/10.1016/j.resconrec.2022.106690
Milevskii, N.A., Zinov’eva, I.V., Zakhodyaeva, Yu.A., and Voshkin, A.A., Separation of Li(I), Co(II), Ni(II), Mn(II), and Fe(III) from hydrochloric acid solution using a menthol-based hydrophobic deep eutectic solvent, Hydrometallurgy, 2022, vol. 207, article no. 105777. https://doi.org/10.1016/j.hydromet.2021.105777
Kozhevnikova, A.V., Zinov’eva, I.V., Zakhodyaeva, Yu.A., Baranovskaya, V.B., and Voshkin, A.A., Application of hydrophobic deep eutectic solvents in extraction of metals from real solutions obtained by leaching cathodes from end-of-life Li-ion batteries, Processes, 2022, vol. 10, no. 12, article no. 2671, pp. 1–14. https://doi.org/10.3390/pr10122671
Tereshatov, E.E., Boltoeva, M.Yu., and Folden III, C.M., First evidence of metal transfer into hydrophobic deep eutectic and low-transition-temperature mixtures: Indium extraction from hydrochloric and oxalic acids, Green Chem., 2016, vol. 18, no. 17, pp. 4616–4622. https://doi.org/10.1039/C5GC03080C
Van Osch, D.J.G.P., Parmentier, D., Dietz, C.H.J.T., Van Den Bruinhorst, A., Tuinier, R., and Kroon, M.C., Removal of alkali and transition metal ions from water with hydrophobic deep eutectic solvents, Chem. Commun., 2016, vol. 52, no. 80, pp. 11987–11990. https://doi.org/10.1039/C6CC06105B
Ola, P.D. and Matsumoto, M., Use of deep eutectic solvent as extractant for separation of Fe (III) and Mn (II) from aqueous solution, Sep. Sci. Technol., 2019, vol. 54, no. 5, pp. 759–765. https://doi.org/10.1080/01496395.2018.1517796
Schaeffer, N., Martins, M.A.R., Neves, C.M.S.S., Pinho, S.P., and Coutinho, J.A.P., Sustainable hydrophobic terpene-based eutectic solvents for the extraction and separation of metals, Chem. Commun., 2018, vol. 54, no. 58, pp. 8104–8107. https://doi.org/10.1039/C8CC04152K
Schmuch, R., Wagner, R., Hörpel, G., Placke, T., and Winter, M., Performance and cost of materials for lithium-based rechargeable automotive batteries, Nat. Energy, 2018, vol. 3, no. 4, pp. 26–278. https://doi.org/10.1038/s41560-018-0107-2
Vieceli, N., Reinhardt, N., Ekberg, C., and Petranikova, M., Optimization of manganese recovery from a solution based on lithium-ion batteries by solvent extraction with D2EHPA, Metals, 2020, vol. 11, no. 1, article no. 54, pp. 1–20. https://doi.org/10.3390/met11010054
Hoh, Y.-C., Chuang, W.-S., Lee, B.-D., and Chang, C.-C., The separation of manganese from cobalt by D2EHPA, Hydrometallurgy, 1984, vol. 12, pp. 375–386. https://doi.org/10.1016/0304-386X(84)90008-2
Zinov’eva, I.V., Kozhevnikova, A.V., Milevskii, N.A., Zakhodyaeva, Yu.A., and Voshkin, A.A., Extraction of Cu(II), Ni(II), and Al(III) with the deep eutectic solvent D2EHPA/menthol, Theor. Found. Chem. Eng., 2022, vol. 56, no. 2, pp. 221–229. https://doi.org/10.1134/S0040579522020178
Ivanov, A.V., Figurovskaya, V.N., and Ivanov, V.M., Molecular absorption spectroscopy of 4-(2-pyridilazo) resorcinol complexes as an alternative to atomic-absorption spectroscopy, Vestn. Mosk. Univ., Ser. 2: Khim., 1992, vol. 33, no. 6, pp. 570–574.
Jin, Y., Ma, Y., Weng, Y., Jia, X., and Li, J., Solvent extraction of Fe3+ from the hydrochloric acid route phosphoric acid by D2EHPA in kerosene, J. Ind. Eng. Chem., 2014, vol. 20, no. 5, pp. 3446–3452. https://doi.org/10.1016/j.jiec.2013.12.033
Yudaev, P.A., Kolpinskaya, N.A., and Chistyakov, E.M., Organophosphorous extractants for metals, Hydrometallurgy, 2021, vol. 201, article no. 105558. https://doi.org/10.1016/j.hydromet.2021.105558
Gammons, C.H. and Seward, T.M., Stability of manganese (II) chloride complexes from 25 to 300°C, Geochim. Cosmochim. Acta, 1996, vol. 60, no. 22, pp. 4295–4311. https://doi.org/10.1016/S0016-7037(96)00275-X
Coleman, J.S., Chloride complexes of cobalt(II) in anion and cation exchangers, J. Inorg. Nucl. Chem., 1966, vol. 28, no. 10, pp. 2371–2378. https://doi.org/10.1016/0022-1902(66)80128-8
Liu, X., Zang, S., Fang, D., Li, J., and Wang, L., Thermodynamics of solvent extraction of rare and scattered metal-indium with diethylhexylmonothiophosphoric acid, Chem. Res. Chin. Univ., 2006, vol. 22, no. 1, pp. 111–113. https://doi.org/10.1016/S1005-9040(06)60057-3
Liu, Y., Tong, L.-H., Inoue, Y., and Hakushi, T., Thermodynamics of solvent extraction of metal picrates with crown ethers: Enthalpy–entropy compensation. Part 2. Sandwiching 1 : 2 complexation, J. Chem. Soc., Perkin Trans. 2, 1990, no. 7, pp. 1247–1253. https://doi.org/10.1039/P29900001247
Yuan, X., Cai, Y., Chen, L., Lu, S., Xiao, X., Yuan, L., and Feng, W., Phosphine oxides functionalized pillar[5]arenes for uranyl extraction: Solvent effect and thermodynamics, Sep. Purif. Technol., 2020, vol. 230, article no. 115843. https://doi.org/10.1016/j.seppur.2019.115843
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The research has been performed under grant no. 20-13-00387 of the Russian Science Foundation, https://rscf.ru/en/project/20-13-00387/.
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Zinov’eva, I.V., Salomatin, A.M., Kozhevnikova, A.V. et al. Extraction of Mn(II) and Co(II) from Chloride Solutions with the Di(2-ethylhexyl)phosphoric Acid/Menthol Deep Eutectic Solvent. Theor Found Chem Eng 57, 442–449 (2023). https://doi.org/10.1134/S0040579523040504
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DOI: https://doi.org/10.1134/S0040579523040504