Germanium recovery from zinc calcines using a hydrometallurgical procedure
DOI:
https://doi.org/10.3989/revmetalm.e281.1726Keywords:
Germanium, Germanium(IV) oxide, Ionic liquid, Leaching, Precipitation, Solvent extraction, Zinc calcinesAbstract
In the final stage of zinc calcines processing, zinc is recovered by zinc electrowinning. However, the presence of germanium in the electrolyte seriously affects the current density in the electrowinning step. Since germanium is a critical and strategic material for the European Union according to the most recent foresight studies, this research has focused on an alternative route for the treatment of germanium concentrates (0.1 %wt Ge) obtained after the roasting step in conventional zinc processes. The results showed that this concentrate can be treated by leaching in mild acidic medium (90% germanium efficiency)-solvent extraction with an ionic liquid and alkaline stripping (99% germanium recovery), followed by neutralization and precipitation steps to yield GeO2 as end-product. The overall germanium recovery was around 85%.
Downloads
References
Alguacil, F.J., Robla, J.I. (2024). Some recent advances in germanium recovery from various resources. Metals 14 (15), 559. https://doi.org/10.3390/met14050559
Alkatsev, V.M., Alkatsev, M.I., Lin'kov, V.A., Darchiev, I.V. (2014). Influence of impurities in electrolyte (tin, germanium, and antimony) on current efficiency within electrowinning of zinc. Russ. J. Non-ferrous Metals 55, 327-330. https://doi.org/10.3103/S1067821214040026
Alumaa, P., Pentchuk, J. (1998). Ionic strength dependence of heavy metal tartrate complex stabilities. Cromatographia 47, 77-80. https://doi.org/10.1007/BF02466789
Arroyo, F., Fernández-Pereira, C. (2008). Hydrometallurgical recovery of germanium from coal gasification fly ash. Solvent extraction method. Ind. Eng. Chem. Res. 47, 3186-3191. https://doi.org/10.1021/ie7016948
Chen, W.-S., Chang, B.-C., Chiu, K.-L. (2017). Recovery of germanium from waste optical fibers by hydrometallurgical method. J. Environ. Chem. Eng. 5 (5), 5215-5221. https://doi.org/10.1016/j.jece.2017.09.048
Chen, C., Zhen, Y., Li, C., Wei, C., Li, M., Deng, Z., Li, X. (2023a). Leaching behavior of germanium presented in different phases from zinc oxide dust under atmospheric acid leaching conditions. IJCRE 21 (10), 1199-1210. https://doi.org/10.1515/ijcre-2023-0011
Chen, S., Zeng, X., Liang, Q., Hu, L., Chen, S., He, D., Han, Y., Zhao, Z., Huang, R., Huang, Y., Zhou, S., Wang, J., Wang, R., Shu, J., Chen, M. (2023b). Zinc efficiently extracted from zinc calcine by reduced wet grinding: ZnFe2O4 to ZnO and Fe3O4. J. Clean. Prod. 399, 136536. https://doi.org/10.1016/j.jclepro.2023.136536
Dhiman, S., Gupta, B. (2020). Recovery of pure germanium oxide from Zener diodes using a recyclable ionic liquid Cyphos IL 104. J. Environ. Manag. 276, 111218. https://doi.org/10.1016/j.jenvman.2020.111218 PMid:32882518
Drzazga, D., Ciszewski, M., Kozłowicz, S., Maj, I., Ochmański, M., Radoń, A. (2024a). Leaching of liquation-feeding furnace dross as a first step for germanium recovery. BMC Res. Notes 17, 180. https://doi.org/10.1186/s13104-024-06832-6 PMid:38926863 PMCid:PMC11201904
Drzazga, M., Ciszewski, M., Kozłowicz, S., Kasiero, S. (2024b). Comparison of germanium recovery from copper(II) sulfate-based solution using tertiary amine and oxime extractant. Miner. Eng. 218, 108984. https://doi.org/10.1016/j.mineng.2024.108984
Eriksson, G. (1979). An algorithm for the computation of aqueous multi-component, multiphase equilibria. Anal. Chim. Acta 112 (4), 375-383. https://doi.org/10.1016/S0003-2670(01)85035-2
Everest, D.A., Harrison, J.C. (1960). The chemistry of quadrivalent germanium. Part VIII. Complexes of germanium with tartaric, lactic and mucic acid. J. Chem. Soc. 3752-3758. https://doi.org/10.1039/jr9600003752
Fernández-Pereira, C., Leiva, C., Luna-Galiano, Y., Vilches, L.F., Arroyo, F. (2024). Improved recycling of a gasification fly ash: An integrated waste management approach within the framework of a circular economy. Waste Manag. 187, 31-38. https://doi.org/10.1016/j.wasman.2024.06.029 PMid:38986400
Gaurav Nalam, P., Das, D., Tan, S., Ramana, C.V. (2022). Controlled phase stabilization enabled tunable optical properties of nanocrystalline GeO2 films. ACS Appl. Electron. Mater. 4, 3115-3124. https://doi.org/10.1021/acsaelm.2c00549
Geng, X., Liu, Y., Zhang, W., Wang, L., Wen, J., Sun, J. (2022). Recent advances in the recovery of germanium during the zinc refining process. Chem. Eng. J. 446, 137445. https://doi.org/10.1016/j.cej.2022.137445
Geng, X., Wu, C., Qu, W., Zhang, W., Cai, L., Yu, Y., Wang, L. (2025). Major obstacles hindering gallium and germanium leaching in the zinc refining process. Chem. Eng. Sci. 302 Part A, 120793. https://doi.org/10.1016/j.ces.2024.120793
Grohol, M., Veeh, C. (2023). Study on the Critical Raw Materials for the EU 2023. Final Report; European Commission. Directorate-General for Internal Market, Industry, Entrepreneurship and SMEss, Publications Office of the European Union: Luxembourg,
Guo, Z., Qin, Z., Liu, S., Zhang, W., Zheng, C., Wang, H. (2024). Solvent extraction of gallium and germanium using a novel hydroxamic acid extractant. Minerals 14 (11), 1147. https://doi.org/10.3390/min14111147
Haghighi, H.K., Irannajad, M., Moradkhani, D. (2018a). Permeation and modeling studies on Ge(IV) facilitated transport using trioctylamine through supported liquid membrane. Korean J. Chem. Eng. 35, 53-60. https://doi.org/10.1007/s11814-017-0265-0
Haghighi, H.K., Irannajad, M., Fortuny, A., Sastre, A.M. (2018b). Recovery of germanium from leach solutions of fly ash using solvent extraction with various extractants. Hydrometallurgy 175, 164-169. https://doi.org/10.1016/j.hydromet.2017.11.006
Haghighi, H.K., Irannajad, M., Fortuny, A., Sastre, A.M. (2018c). Mathematical modeling for facilitated transport of Ge(IV) through supported liquid membrane containing Alamine 336. Chem. Pap. 72, 955-970. https://doi.org/10.1007/s11696-017-0332-3
Haghighi, H.K., Irannajad, M., Fortuny, A., Sastre, A.M. (2019a). Non-dispersive selective extraction of germanium from fly ash leachates using membrane-based processes. Sep. Sci. Technol. 54 (17), 2879-2894. https://doi.org/10.1080/01496395.2018.1555170
Haghighi, H.K., Irannajad, M., Fortuny, A., Sastre, A.M. (2019b). Selective separation of germanium(IV) from simulated industrial leachates containing heavy metals by non-dispersive ionic extraction. Miner. Eng. 137, 344-353. https://doi.org/10.1016/j.mineng.2019.04.021
Haghighi, H.K., Irannajad, M., Sastre, A.M. (2019c). Germanium transport across supported liquid membrane with Cyanex 923: mathematical modeling. Trans. Nonferrous Met. Soc. China 29 (9), 1956-1966. https://doi.org/10.1016/S1003-6326(19)65103-4
Haghighi, H.K., Irannajad, M., Coll, M.T., Sastre, A.M. (2019d). Non-dispersive extraction of Ge(IV) from aqueous solutions by Cyanex 923: Transport and modeling studies. Metals 9 (6), 676. https://doi.org/10.3390/met9060676
He, C., Qi, M., Liu, Y., Liu, Z., Wei, Y., Fujita, T., Wang, G., Ma, S., Yang, W., Gan, J. (2024). Highly selective separation of germanium from sulfuric solution using an anion exchange D201·7 resin with tartaric acid. Hydrometallurgy 224, 106230. https://doi.org/10.1016/j.hydromet.2023.106230
Hintersatz, C., Tsushima, S., Kaufer, T., Kretzschmar, J., Thewes, A., Pollmann, K., Jain, R. (2024). Efficient density functional theory directed identification of siderophores with increased selectivity towards indium and germanium. J. Hazard. Mater. 478, 135523. https://doi.org/10.1016/j.jhazmat.2024.135523 PMid:39178780
Hong, Y., Di, H., Li, S., Yang, K., Zhang, L. (2023). Mechanism of extracting germanium from Ge-containing solution with tannins. Metals 13 (4), 774. https://doi.org/10.3390/met13040774
Hu, S., Lu, Z., Li, X., Yang, R., Wei, C., Deng, Z., Li, M. (2025). Recovery of germanium from zinc smelting leachates: a review. Environ. Chem. Lett. 23, 1341-1379. https://doi.org/10.1007/s10311-025-01844-5
Ichino, R., Cachet, C., Wiart, R. (1995). Influence of Ge4+ and Pb2+ ions on the kinetics of zinc electrodeposition in acidic sulphate electrolyte. J. Appl. Electrochem. 25, 556-564. https://doi.org/10.1007/BF00573213
Ingri, N., Dahlen, J., Buchardt, O., Kvande, P.C., Meisingseth, E. (1963). Equilibrium studies of polyanions. 12. Polygermanates in Na(Cl) medium. Acta. Chem. Scand. 17, 597-616. https://doi.org/10.3891/acta.chem.scand.17-0597
Janjam, S.V.S.B., Peddeti, S., Roy, D., Babu S.V. (2008). Tartaric acid as a complexing agent for selective removal of tantalum and copper in CMP. Electrochem. Solid State. Lett. 11 (12), H327-H330. https://doi.org/10.1149/1.2980345
Jiang, T., Wang, P., Liu, Z., Zhang, W., Liu, F., Liao, C. (2025). Unconventional technologies for the separation of germanium and gallium from solutions: A review. Sep. Purif. Technol. 377 (Part 3), 134399. https://doi.org/10.1016/j.seppur.2025.134399
Kosova, T.B., Dem'yanets, L.N. (1991). Hydrothermal Chemistry and Growth of Hexagonal Germanium Dioxide. In: Bagdasarov, K.S.; Lube, É.L. (eds) Growth of Crystals. Vol 16. Springer, Boston, MA. https://doi.org/10.1007/978-1-4615-3662-8_6
Kumar, A., Dhiman, S., Kumar, R., Gupta, H. (2025). Recovery of germanium from waste optical fibres using phosphonium ionic liquid. J. Clean. Prod. 505, 145466. https://doi.org/10.1016/j.jclepro.2025.145466
Liang, M., Hong, Y., Di, H., Yang, K., Zhang, L. (2024a). Mechanism of germanium adsorption by iron hydroxide colloids during the leaching process of secondary zinc oxide. Langmuir 40 (25), 13167-13176. https://doi.org/10.1021/acs.langmuir.4c01167 PMid:38860465
Liang, M., Dai, J., Di, H., Zhu, K., Yang, K., Zhang, L. (2024b). Mechanism and kinetic study on ultrasonically enhanced reduction leaching of zinc suboxide. Langmuir 40 (36), 19155-19165. https://doi.org/10.1021/acs.langmuir.4c02307 PMid:39195735
Liem, D.H (1971). High-speed computers as a supplement to graphical methods. 12. Application of LETAGROP to data for liquid-liquid distribution equilibria. Acta Chem. Scand. 25, 1521-1534. https://doi.org/10.3891/acta.chem.scand.25-1521
Liu, N., Zhu, Y.X., Deng, Z., Zhen, Y., Wei, C., Li, X., Li, M. (2024). Dissociation of germanium-containing insoluble mineral phases in zinc oxide dust. Can. Metall. Q. 64, 296-305. https://doi.org/10.1080/00084433.2024.2357514
Menendez, F.J.S., Menendez, F.M.S., De La Cuadra, A., Tamargo, F.A., Lorenzo, L.P., Valcarcel, M.R., Fernandez, V.A. (1989). Process for the recovery of germanium from solutions that contain it. US Patent 4,886,648. 12/12/1989.
Patel, M., Karamalidis, A.K. (2024). Fixed-bed column adsorption of Ge(IV) using catechol-based adsorbents and aqueous complexation modeling to understand Ge(IV) selectivity. Sep. Purif. Technol. 351, 128106. https://doi.org/10.1016/j.seppur.2024.128106
Peng, Z., Wang, S., Wu, Y., Liu, X., Liu, H., Zhang, D., Fu, L. (2024a). Synthesis of novel MOF for adsorption of germanium: Kinetics, isotherm and thermodynamics. Microporous Mesoporous Mater. 363, 112826. https://doi.org/10.1016/j.micromeso.2023.112826
Peng, Z., Wang, S., Wu, Y., Liu, X., Zhu, M., Li, P., Fu, L. (2024b). Novel Zr-based MOF with ortho-hydroxyl group selectively traps germanium from aqueous media. Sep. Purif. Technol. 338, 126477. https://doi.org/10.1016/j.seppur.2024.126477
Pittman, A.S., Sun, Z., Zhou, F., Wu, J., Cheng, H., Tao, Z.-M., Gui, Y., Cao, Y. (2025). Efficient and selective of indium and germanium from environmental wastewater using a novel covalent organic framework composite. Surf. Interfaces 72, 107157. https://doi.org/10.1016/j.surfin.2025.107157
Pokrovski, G.S., Schott, J. (1998). Experimental study of the complexation of silicon and germanium with aqueous organic species: implications for germanium and silicon transport and Ge/Si ratio in natural waters. Geochim. Cosmochim. Acta 62, 3413-3428. https://doi.org/10.1016/S0016-7037(98)00249-X
Puigdomenech, I. (2004). Make equilibrium diagrams using sophisticated algorithms (MEDUSA), Inorganic Chemistry. Royal Institute of Technology, Stockholm, Sweden. https://www.kth.se/che/medusa.
Ritcey, G.M., Ashbrook, A.W. (1984). Solvent Extraction. Part I. Elsevier. Amsterdam. The Netherlands
Rudnik, E. (2025). Challenges and opportunities in hydrometallurgical recovery of germanium from coal by-products. Molecules 30 (8), 1695. https://doi.org/10.3390/molecules30081695 PMid:40333657 PMCid:PMC12029668
Shen, S., Gao, L., Li, S., Liu, Y., Mao, H., Xu, K. (2025). Synthesis of hydroxyl-rich alginate adsorbents with selective adsorption performance of germanium from alkaline solution. Inorg. Chem. Commun. 181 (Part 2), 115333. https://doi.org/10.1016/j.inoche.2025.115333
Song, L., Di, H., Liang, M., Zenga, Y., Yang, K., Zhang, L. (2023). Study on ultrasonic depolymerization of Si-Ge precipitation in zinc oxide dust leaching process. Arabian J. Chem. 16, 105016. https://doi.org/10.1016/j.arabjc.2023.105016
Song, L., Zeng, Y., Dai, J., Liu, K., Yang, K., Zhang, L. (2025). Ultrasonic synergistic oxidation technology: Kinetics and mechanism of germanium leaching from high-sulfur germanium-bearing dust. Chem. Eng. Sci. 314, 121795. https://doi.org/10.1016/j.ces.2025.121795
Tang, H., Liu, B., Zhang, X., Li, L., Zhang, Z., Guan, Q. (2025). Extraction of Ge and synchronous activation of humic acid in germanium bearing lignite via oxidation leaching. Fuel Proc. Technol. 272, 108216. https://doi.org/10.1016/j.fuproc.2025.108216
Vancea, C., Ciocarlie, L., Negrea, A., Mosoarca, G., Ciopec, M., Duteanu, N., Negrea, P., Pascu, B., Nemes, N.-S. (2024). Evaluation of functionalized Amberlite type XAD7 polymeric resin with L-valine amino acid performance for gallium recovery. Polymers 16 (6), 837. https://doi.org/10.3390/polym16060837 PMid:38543442 PMCid:PMC10975911
Van Roosendael, S., Roosen, J., Banerjee, D., Binnemans, K. (2019). Selective recovery of germanium from iron-rich solutions using a supported ionic liquid phase (SILP). Sep. Purif. Technol. 221, 83-92. https://doi.org/10.1016/j.seppur.2019.03.068
Vereycken, W., De Belder, M., Riaño, S., Van Gerven, T., Binnemans, K. (2022). Extraction behavior and purification of germanium using an undiluted quaternary ammonium ionic liquid in combination with a complexing agent. Ind. Eng. Chem. Res. 61 (15), 5295-5305. https://doi.org/10.1021/acs.iecr.1c04940
Wang, P., Liu, Z., Zhang, T., Liu, Z., Zhu, D., Jiang, T. (2023). Extraction mechanism of germanium in sulfate solutions using a tertiary amine (N235)-based solvent extraction system. Sep. Purif. Technol. 311, 123305. https://doi.org/10.1016/j.seppur.2023.123305
Wei, Q., Zeng, Z., Ding, S., Shen, Z., Song, W., Wang, Y., Nzila, C., Chow, C.W.K. (2025). Functionalization of rice husk for high selective extraction of germanium. Processes 13 (5), 1367. https://doi.org/10.3390/pr13051367
Wu, H., Hu, L., Zhang, Z., Guo, W., Chen, W., Yu, J., Feng, G., Chi, R., Pan, Z. (2024). Highly effective and selective recovery of germanium from coal acid leaching solution by trihydroxyl functionalized titanium dioxide. Coll. Surf. A Physicochem. Eng. Asp. 70 (Part 2), 135130. https://doi.org/10.1016/j.colsurfa.2024.135130
Xu, Y., Xia, H., Zhang, Q., Zhang, L. (2024). An original strategy and evaluation of a reaction mechanism for recovering valuable metals from zinc oxide dust containing intractable germanide. J. Hazard. Mater. 468, 133766. https://doi.org/10.1016/j.jhazmat.2024.133766 PMid:38368683
Zhang, T., Jiang, T., Liu, Z. (2021). Extraction behavior of germanium from synthetic leaching solution of secondary zinc oxide in tertiary amine (N235)-trioctyl phosphate (TOP) system. Min. Eng. 160, 106682. https://doi.org/10.1016/j.mineng.2020.106682
Zhang, Z., Teng, D., Fan, G., Cao, Y., Liu, J., Li, P. (2024). Co-extraction of germanium and nitrogen-rich humic acid from germanium-rich lignite by ammonoxidation. Fuel 66, 131361. https://doi.org/10.1016/j.fuel.2024.131361
Zhang, Z., Fan, G., Zhou, G., Teng, D., Nan, H., Li, P., Cao, Y., Liu, J. (2025a). Kill two birds with one stone: Efficient leaching of germanium and recovery of lignite from germanium-rich lignite by thionyl chloride. Sep. Purif. Technol. 354 (Part 1), 128703. https://doi.org/10.1016/j.seppur.2024.128703
Zhang, X., Wang, Z., Li, Z. (2025b). Research progress of ionic liquids in recycling waste lithium-ion batteries: from metal extraction to material regeneration. Ser. Purif. Technol. 379 (Part 1), 134850 https://doi.org/10.1016/j.seppur.2025.134850
Downloads
Published
How to Cite
Issue
Section
License
Copyright (c) 2026 Consejo Superior de Investigaciones Científicas (CSIC)

This work is licensed under a Creative Commons Attribution 4.0 International License.
© CSIC. Manuscripts published in both the printed and online versions of this Journal are the property of Consejo Superior de Investigaciones Científicas, and quoting this source is a requirement for any partial or full reproduction.
All contents of this electronic edition, except where otherwise noted, are distributed under a “Creative Commons Attribution 4.0 International” (CC BY 4.0) License. You may read the basic information and the legal text of the license. The indication of the CC BY 4.0 License must be expressly stated in this way when necessary.
Self-archiving in repositories, personal webpages or similar, of any version other than the published by the Editor, is not allowed.







