Microwave-assisted organic-acid leaching of major and critical elements from olivine: Characteristics, kinetics, and method comparison

Abstract

Olivine has become a promising source of Ni and Co for catering to the increased global demand for critical minerals in recent years. The performance of microwave-assisted leaching of major elements, including Mg, Si, Fe, and critical elements like Co and Ni, from olivine was compared with those of autoclave and conventional leaching methods in an organic acid medium. In addition, the effects of organic acid type, citric acid concentration, solid-to-liquid (S/L) ratio, reaction time, and reaction temperature were investigated using the response surface methodology with central composite design. Accordingly, the optimal conditions were determined as 0.84 M citric acid concentration, 2.6% S/L ratio, 29 min, and 178 °C. Compared with autoclave and conventional leaching techniques, microwave-assisted leaching resulted in a higher extraction of major and critical elements. The Avrami model was applied to fit the microwave-assisted leaching kinetics data and derive the kinetic parameters. The apparent activation energy values indicated that the microwave-assisted leaching process was diffusion-controlled. The characterization of solid residues resulting from the microwave-assisted leaching experiments indicated that the detachment of Si-rich layers from the surface of unreacted olivine particles during the reaction was the key factor enabling a greater degree of extraction, whereas Si-rich layers surrounded the unreacted olivine particles in the autoclave leaching method. This study provides valuable insights into the leaching characteristics and kinetics of the major and critical elements from olivine using microwave-assisted leaching in organic acid media. In addition, investigating the leaching of major elements is necessary because Ni and Co are well distributed in the olivine silicate structure. The resulting leachates containing major elements can also be used for carbon fixation.

Keywords

Microwave-assisted leaching / Olivine / Citric acid / Hydrometallurgy / Avrami model

References

[1] F. Wang, D. Dreisinger, An integrated process of CO2 mineralization and selective nickel and cobalt recovery from olivine and laterites, Chem. Eng. J. 451 (2023) 139002.

[2] F. Wang, D. Dreisinger, Carbon mineralization with concurrent critical metal recovery from olivine, Proc. Natl. Acad. Sci. USA 119 (32) (2022) e2203937119.

[3] F. Wang, D. Dreisinger, Y.C. Xiao, Accelerated CO2 mineralization and utilization for selective battery metals recovery from olivine and laterites, J. Clean. Prod. 393 (2023) 136345.

[4] F. Wang, D. Dreisinger, M. Jarvis, T. Hitchins, Kinetics and mechanism of mineral carbonation of olivine for CO2 sequestration, Miner. Eng. 131 (2019) 185-197.

[5] F. Wang, D. Dreisinger, M. Jarvis, T. Hitchins, L. Trytten, CO2 mineralization and concurrent utilization for nickel conversion from nickel silicates to nickel sulfides, Chem. Eng. J. 406 (2021) 126761.

[6] S. Ghaderi, B. Ji, D. Michael Veach, A.A. Park, J.Y. Meng, W.C. Zhang, A comprehensive study on the leaching characteristics and mechanisms of nickel and cobalt from olivine, Miner. Eng. 218 (2024) 108992.

[7] A.K. Barman, C. Varadachari, K. Ghosh, Weathering of silicate minerals by organic acids. I. Nature of cation solubilisation, Geoderma 53 (1-2) (1992) 45-63.

[8] S. Teir, H. Revitzer, S. Eloneva, C.J. Fogelholm, R. Zevenhoven, Dissolution of natural serpentinite in mineral and organic acids, Int. J. Miner. Process. 83 (1-2) (2007) 36-46.

[9] W. Astuti, T. Hirajima, K. Sasaki, N. Okibe, Comparison of effectiveness of citric acid and other acids in leaching of low-grade Indonesian saprolitic ores, Miner. Eng. 85 (2016) 1-16.

[10] R.M. Santos, A. Van Audenaerde, Y.W. Chiang, R.I. Iacobescu, P. Knops, T. Van Gerven, Nickel extraction from olivine: Effect of carbonation pre-treatment, Metals 5 (3) (2015) 1620-1644.

[11] L. Guo, J.R. Lan, Y.G. Du, T.C. Zhang, D.Y. Du, Microwave-enhanced selective leaching of arsenic from copper smelting flue dusts, J. Hazard. Mater. 386 (2020) 121964.

[12] H.C. Chen, Z.P. Wen, J.H. Pan, L. Zhang, X. He, D. Valeev, C.C. Zhou, Study on leaching behavior differences of rare earth elements from coal fly ash during microwave-assisted HCl leaching, Int. J. Coal Prep. Util. 43 (11) (2023) 1993-2015.

[13] R.K. Amankwah, G. Ofori-Sarpong, Microwave heating of gold ores for enhanced grindability and cyanide amenability, Miner. Eng. 24 (6) (2011) 541-544.

[14] M. Al-Harahsheh, S.W. Kingman, Microwave-assisted leaching: A review, Hydrometallurgy 73 (3-4) (2004) 189-203.

[15] J. Chen, X.P. Li, L. Gao, S.H. Guo, F. He, Microwave treatment of minerals and ores: Heating behaviors, applications, and future directions, Minerals 14 (3) (2024) 219.

[16] S.D. Lin, K.Q. Li, Y. Yang, L. Gao, M. Omran, S.H. Guo, J. Chen, G. Chen, Microwave-assisted method investigation for the selective and enhanced leaching of manganese from low-grade pyrolusite using pyrite as the reducing agent, Chem. Eng. Process. Process. Intensif. 159 (2021) 108209.

[17] J.W. Choi, J.K. Bediako, J.H. Kang, C.R. Lim, Y.R. Dangi, H.J. Kim, C.W. Cho, Y.S. Yun, In-situ microwave-assisted leaching and selective separation of Au(III) from waste printed circuit boards in biphasic aqua regia-ionic liquid systems , Sep. Purif. Technol. 255 (2021) 117649.

[18] M. Al-Harahsheh, S. Kingman, S. Bradshaw, The reality of non-thermal effects in microwave assisted leaching systems? Hydrometallurgy 84 (1-2) (2006) 1-13.

[19] Y. Hua, Z. Lin, Z. Yan, Application of microwave irradiation to quick leach of zinc silicate ore, Miner. Eng. 15 (6) (2002) 451-456.

[20] F. Kukurugya, W. Wouters, J. Spooren, Microwave-assisted chloride leaching for efficient recovery of platinum group metals from spent automotive catalysts: An approach for chemical reagent reduction, Clean. Eng. Technol. 24 (2025) 100868.

[21] F. Tesfaye, D. Lindberg, J. Hamuyuni, P. Taskinen, L. Hupa, Improving urban mining practices for optimal recovery of resources from e-waste, Miner. Eng. 111 (2017) 209-221.

[22] V. Innocenzi, I. De Michelis, F. Vegliò, 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, J. Taiwan Inst. Chem. Eng. 80 (2017) 769-778.

[23] L. Rocchetti, F. Vegliò, B. Kopacek, F. Beolchini, Environmental impact assessment of hydrometallurgical processes for metal recovery from WEEE residues using a portable prototype plant, Environ. Sci. Technol. 47 (3) (2013) 1581-1588.

[24] Y.L. Yao, M.Y. Zhu, Z. Zhao, B.H. Tong, Y.Q. Fan, Z.S. Hua, Hydrometallurgical processes for recycling spent lithium-ion batteries: a critical review, ACS Sustain. Chem. Eng. 6 (11) (2018) 13611-13627.

[25] L.P. He, S.Y. Sun, Y.Y. Mu, X.F. Song, J.G. Yu, Recovery of lithium, nickel, cobalt, and manganese from spent lithium-ion batteries using l-tartaric acid as a leachant, ACS Sustain. Chem. Eng. 5 (1) (2017) 714-721.

[26] L. Li, Y.F. Bian, X.X. Zhang, Q. Xue, E.S. Fan, F. Wu, R.J. Chen, Economical recycling process for spent lithium-ion batteries and macro- and micro-scale mechanistic study, J. Power Sources 377 (2018) 70-79.

[27] X.P. Chen, C.B. Luo, J.X. Zhang, J.R. Kong, T. Zhou, Sustainable recovery of metals from spent lithium-ion batteries: a green process, ACS Sustain. Chem. Eng. 3 (12) (2015) 3104-3113.

[28] P. Meshram, A. Mishra, Abhilash, R. Sahu, Environmental impact of spent lithium ion batteries and green recycling perspectives by organic acids-a review, Chemosphere 242 (2020) 125291.

[29] R. Golmohammadzadeh, F. Rashchi, E. Vahidi, Recovery of lithium and cobalt from spent lithium-ion batteries using organic acids: Process optimization and kinetic aspects, Waste Manag. 64 (2017) 244-254.

[30] L. Li, J.B. Dunn, X.X. Zhang, L. Gaines, R.J. Chen, F. Wu, K. Amine, Recovery of metals from spent lithium-ion batteries with organic acids as leaching reagents and environmental assessment, J. Power Sources 233 (2013) 180-189.

[31] W.C. Zhang, X.B. Yang, R.Q. Honaker, Association characteristic study and preliminary recovery investigation of rare earth elements from Fire Clay seam coal middlings, Fuel 215 (2018) 551-560.

[32] K. Kirimura, Y. Honda, T. Hattori, 3.13-Citric acid, in: M. Moo-Young (Ed.), Comprehensive Biotechnology, Second edition., Academic Press, Burlington, 2011, pp. 135-142.

[33] W. Astuti, T. Hirajima, K. Sasaki, N. Okibe, Comparison of atmospheric citric acid leaching kinetics of nickel from different Indonesian saprolitic ores, Hydrometallurgy 161 (2016) 138-151.

[34] C. Mohanty, S.S. Behera, B. Marandi, S.K. Tripathy, P.K. Parhi, K. Sanjay, Citric acid mediated leaching kinetics study and comprehensive investigation on extraction of vanadium (V) from the spent catalyst, Sep. Purif. Technol. 276 (2021) 119377.

[35] M.M. Theron, J.F.R. Lues, Organic Acids and Food Preservation, first ed., CRC Press, Boca Raton, 2010.

[36] R.D. Short, F.R. Johannsen, C.E. Ulrich, A 6-month multispecies inhalation study with maleic anhydride, Fundam. Appl. Toxicol. 10 (3) (1988) 517-524.

[37] A. Hamidi, Y.S. Bastami, S. Shakibania, A. Mahmoudi, F. Rashchi, E. Vahidi, Fly ash treatment via conventional and microwave-assisted organic acid leaching: Kinetics and life cycle assessment, Environ. Sci. Pollut. Res. Int. 31 (20) (2024) 30039-30058.

[38] C. Sun, L. Xu, X. Chen, T. Qiu, T. Zhou, Sustainable recovery of valuable metals from spent lithium-ion batteries using DL-malic acid: Leaching and kinetics aspect, Waste Manag. Res 36 (2) (2018) 113-120.

[39] S. Ghaderi, W.C. Zhang, Microwave-assisted leaching of olivine: Investigation of leaching characteristics and kinetics of Mg, Si, Fe, co, and Ni, Miner. Eng. 228 (2025) 109344.

[40] J. Sun, W.L. Wang, Q.Y. Yue, Review on microwave-matter interaction fundamentals and efficient microwave-associated heating strategies, Materials 9 (4) (2016) 231.

[41] H. Chu, J. Lie, J.C. Liu, Rapid leaching of valuable metals from spent lithium-ion batteries with microwave irradiation using organic and inorganic acid, J. Sustain. Met. 7 (2) (2021) 630-641.

[42] X.K. Che, X.Z. Su, R.A. Chi, J.X. Yu, Microwave assisted atmospheric acid leaching of nickel from laterite ore, Rare Met. 29 (3) (2010) 327-332.

[43] S.X. Yan, C.H. Sun, T. Zhou, R.C. Gao, H.S. Xie, Ultrasonic-assisted leaching of valuable metals from spent lithium-ion batteries using organic additives, Sep. Purif. Technol. 257 (2021) 117930.

[44] L.Q. Zhuang, C.H. Sun, T. Zhou, H. Li, A.Q. Dai, Recovery of valuable metals from LiNi_0.5Co_0.2Mn_0.3O₂ cathode materials of spent Li-ion batteries using mild mixed acid as leachant , Waste Manag. 85 (2019) 175-185.

[45] S.Y. Li, W.C. Zhang, Y. Xia, Q. Li, Enhanced reducing capacity of citric acid for lithium-ion battery recycling under microwave-assisted leaching, Waste Manag. 189 (2024) 23-33.

[46] M.K. Sinha, R. Jordaan, W. Purcell, Hydrometallurgical recovery of manganese from ferruginous manganese ore by reductive-acid leaching with sodium dithionite, J. Sustain. Met. 8 (2) (2022) 783-794.

[47] O. Levenspiel, Chemical reaction engineering, Ind. Eng. Chem. Res. 38 (11) (1999) 4140-4143.

[48] B. Manoj, A.G. Kunjomana, K.A. Chandrasekharan, Chemical leaching of low rank coal and its characterization using SEM/EDAX and FTIR, J. Miner. Mater. Charact. Eng. 8 (10) (2009) 821-832.

[49] M.Y.A. Mollah, T.R. Hess, D.L. Cocke, Surface and bulk studies of leached and unleached fly ash using XPS, SEM, EDS and FTIR techniques, Cem. Concr. Res. 24 (1) (1994) 109-118.

[50] D. Kölbl, A. Memic, H. Schnideritsch, D. Wohlmuth, G. Klösch, M. Albu, G. Giester, M. Bujdoš, T. Milojevic, Thermoacidophilic bioleaching of industrial metallic steel waste product, Front. Microbiol. 13 (2022) 864411.

[51] R.D. Shannon, M.A. Subramanian, S. Hosoya, G.R. Rossman, Dielectric constants of tephroite, fayalite and olivine and the oxide additivity rule, Phys. Chem. Min. 18 (1) (1991) 1-6.

[52] Y. Yuan, Z.S. Shao, R.J. Qiao, X.S. Fei, J.X. Cheng, Thermal response and crack propagation of mineral components in olivine basalt under microwave irradiation, Arab. J. Geosci. 13 (14) (2020) 589.

[53] J.H. Forster, Dielectric Properties of Minerals and Ores and the Application of Microwaves for Assisted Comminution and Ore Sorting (Dissertation), University of Toronto, Toronto, Canada, 2023.

[54] T. Li, W. Wang, G.B. Chen, Q.H. Li, Effect of microwave heating on rock damage and energy evolution, Can. Geotech. J. 61 (11) (2024) 2523-2534.

[55] M.Z. Xie, F.Q. Liu, H.L. Zhao, C.Y. Ke, Z.Q. Xu, Mineral phase transformation in coal gangue by high temperature calcination and high-efficiency separation of alumina and silica minerals, J. Mater. Res. Technol. 14 (2021) 2281-2288.