Leaching behavior of germanium presented in different phases from zinc oxide dust under atmospheric acid leaching conditions

Chunlin Chen; Yong Zhen; Chunlin Li; Chang Wei; Minting Li; Zhigan Deng; Xingbin Li

doi:10.1515/ijcre-2023-0011

Article

Leaching behavior of germanium presented in different phases from zinc oxide dust under atmospheric acid leaching conditions

Chunlin Chen , Yong Zhen , Chunlin Li , Chang Wei , Minting Li , Zhigan Deng and Xingbin Li

Published/Copyright: September 28, 2023

Published by

Become an author with De Gruyter Brill

Submit Manuscript Author Information

From the journal International Journal of Chemical Reactor Engineering Volume 21 Issue 10

Abstract

Recovering germanium from zinc oxide dust (ZOD) produced from Pb–Zn smelter is an important pathway to extract germanium. However, the leaching efficiency of industrial germanium production is not satisfactory (usually less than 75 %). Therefore, the leaching behavior of Ge in different phases was discovered in this work. Ge in the ZOD mainly occurs in oxide, sulfide, silicate, and solid insoluble. The potential decides the oxidative dissolution of sulfide. The leaching recovery of zinc and germanium were 90 % and 80 % with oxidant, and 78 % and 80 % without oxidant, respectively. The effect sequence of oxidant type on the Zn leaching efficiency was MnO₂ > H₂O₂ ≈ oxygen > air, but the type and addition of oxidant had no obvious effect on the leaching recovery of germanium. The final pH of leaching slurry limits the dissolution of oxide and hydrolysis-polymerization of impurity ions (such as Fe(III) and Si). Decreasing the final pH is beneficial to the leaching reaction of Zn and Ge. The germanium presented in oxide and sulfide is easy to leach, while the leaching of germanium existed in silicate and solid insoluble is relatively difficult. The structure of aluminate can be destroyed effectively using a 40 g/L HF solution. When the leaching percent of SiO₂ is 86.82 %, the leaching recovery of Ge is 96.57 %. For the ZOD with higher content of Fe and Si, germanium leaching is negatively correlated with the content of Fe and Si in the ZOD. The results provide a scientific basis for improving the leaching recovery of germanium.

Keywords: correlation; germanium leaching; limiting factor; phase; zinc oxide dust

Corresponding author: Chang Wei, Faculty of Metallurgy and Energy Engineering, Kunming University of Science and Technology, Kunming 650093, China, E-mail: weichang502@sina.cn

Funding source: National Natural Science Foundation of China

Award Identifier / Grant number: 52164039

Funding source: National Natural Science Foundation of China 51964031

Award Identifier / Grant number: Minting Li

Author contributions: All the authors have accepted responsibility for the entire content of this submitted manuscript and approved submission.
Research funding: This work was funded by the National Natural Science Foundation of China (Grants 52164039).
Conflict of interest statement: The authors declare that they have no known conflict financial interests or personal relationships that could have appeared to influence the work reported in this paper.

References

Abdel-latif, M. A. 2002. “Fundamentals of Zinc Recovery from Metallurgical Wastes in the Enviroplas Process.” Minerals Engineering 15 (11): 945–52. https://doi.org/10.1016/s0892-6875(02)00133-4.Search in Google Scholar

Belissont, R., M. Muñoz, M. C. Boiron, B. Luais, and O. Mathon. 2016. “Distribution and Oxidation State of Ge, Cu and Fe in Sphalerite by μ-XRF and K-Edge μ-XANES: Insights into Ge Incorporation, Partitioning and Isotopic Fractionation.” Geochimica et Cosmochimica Acta 177: 298–314. https://doi.org/10.1016/j.gca.2016.01.001.Search in Google Scholar

Carolan, D. 2017. “Recent Advances in Germanium Nanocrystals: Synthesis, Optical Properties and Applications.” Progress in Materials Science 90: 128–58. https://doi.org/10.1016/j.pmatsci.2017.07.005.Search in Google Scholar

Chen, X. Q., J. Z. Qu, Y. S. Zhang, L. L. Wu, and L. wang. 2021. “Analysis of the Global Germanium Resource Supply and Demand Situation from 2021 to 2035.” China Mining Magazine 30 (3): 37–42.Search in Google Scholar

Ding, W., S. X. Bao, Y. M. Zhang, and J. H. Xiao. 2022. “Mechanism and Kinetics Study on Ultrasound Assisted Leaching of Gallium and Zinc from Corundum Flue Dust.” Minerals Engineering 183: 107624. https://doi.org/10.1016/j.mineng.2022.107624.Search in Google Scholar

Geng, X. L., Y. Liu, W. Zhang, L. S. Wang, J. K. Wen, and J. Z. Sun. 2022. “Recent Advances in the Recovery of Germanium during the Zinc Refining Process.” Chemical Engineering Journal 446: 137445. https://doi.org/10.1016/j.cej.2022.137445.Search in Google Scholar

Haynes, W. M., D. R. Lide, and T. J. Bruno. 2016. CRC Handbook of Chemistry and Physics, 97th ed. Florida: CRC Press.10.1201/9781315380476Search in Google Scholar

Huang, T. L., Q. Cao, B. Jing, X. Y. Wang, D. Wang, and L. B. Liang. 2022. “Towards High-Performance Lithium-Sulfur Battery: Investigation on the Capability of Metalloid to Regulate Polysulfides.” Chemical Engineering Journal 430: 132677. https://doi.org/10.1016/j.cej.2021.132677.Search in Google Scholar

Hu, R. Z., W. C. Su, H. W. Qi, and X. W. Bi. 2000. “Geochemistry, Occurrence and Mineralization of Germanium.” Bulletin of Mineralogy, Petrology and Geochemistry 19 (4): 215–7.Search in Google Scholar

Jiang, T., T. Zhang, and Z. Y. Liu. 2020. “Recovery of Germanium via H2SO4/MnO2 Leaching-NaAc leaching/Na2CO3 Precipitation-Tri(octyl-Decyl) Amine Stepwise Solvent Extraction.” ACS Sustainable Chemistry & Engineering 8 (50): 18545–57. https://doi.org/10.1021/acssuschemeng.0c06526.Search in Google Scholar

Jiang, T., T. Zhang, and Z. Y. Liu. 2021. “Pb-based Aggregate, Ge-Galena Coexistence, and Ge-Anglesite Coprecipitate-Limitations and an Improvement of Germanium Recovery from Secondary Zinc Oxide via H2SO4 Leaching.” Hydrometallurgy 200: 105543. https://doi.org/10.1016/j.hydromet.2020.105543.Search in Google Scholar

Kaskiala, T. 2002. “Determination of Oxygen Solubility in Aqueous Sulphuric Acid Media.” Minerals Engineering 15 (11): 853–7. https://doi.org/10.1016/s0892-6875(02)00089-4.Search in Google Scholar

Li, M. T. 2012. “Study on Kinetics and Mechanism of Pressure Acid Leaching of Vanadium-Bearing Black Shale.” Kunming University of Science and Technology 45–7.Search in Google Scholar

Li, Z. X., C. Y. Wang, X. M. Yin, and M. Z. Gao. 2017. “Extraction of Germanium and Zinc from Germanium-Bearing Zinc Oxide Dust.” Nonferrous Metals 9: 45–7.Search in Google Scholar

Liang, D. Q., J. K. Wang, and Y. H. Wang. 2009. “Difference in Dissolution between Germanium and Zinc during the Oxidative Pressure Leaching of Sphalerite.” Hydrometallurgy 95 (1–2): 5–7. https://doi.org/10.1016/j.hydromet.2008.03.005.Search in Google Scholar

Licht, C., L. T. Peiró, and G. Villalba. 2015. “Global Substance Flow Analysis of Gallium, Germanium, and Indium: Quantification of Extraction, Uses, and Dissipative Losses within Their Anthropogenic Cycles.” Journal of Industrial Ecology 19 (5): 890–903. https://doi.org/10.1111/jiec.12287.Search in Google Scholar

Lin, Y., J. C. Nigel, L. C. Cristiana, Y. P. liu, Q. Zhang, T. P. liu, W. Gao, Y. L. Yang, and D. Leonid. 2011. “Trace and Minor Elements in Sphalerite from Base Metal Deposits in South China: A LA-ICPMS Study.” Ore Geology Reviews 39 (4): 188–217. https://doi.org/10.1016/j.oregeorev.2011.03.001.Search in Google Scholar

Liu, X., Y. S. Liu, M. M. Harris, J. H. Li, K. X. Wang, and J. S. Chen. 2018. “Germanium Nanoparticles Supported by 3D Ordered Macroporous Nickel Frameworks as High-Performance Free-Standing Anodes for Li-Ion Batteries.” Chemical Engineering Journal 354: 616–22. https://doi.org/10.1016/j.cej.2018.08.056.Search in Google Scholar

Luo, J. H., S. Rao, K. Ji, H. Y. Cao, Z. Q. Liu, D. X. Wang, X. Y. Yuan, and L. J. Daun. 2022. “Study on Gallium and Germanium Leaching from Zinc Refinery Residues through Combing Atmospheric Leaching with Oxygen Pressure Leaching.” Chinese Journal of Nonferrous Metals 32 (9): 2741–52.Search in Google Scholar

Markus, H., S. Fugleberg, D. Valtakari, T. Salmi, D. Y. Murzin, and M. Lahtinen. 2004. “Reduction of Ferric to Ferrous with Sphalerite Concentrate, Kinetic Modelling.” Hydrometallurgy 73 (3–4): 269–82. https://doi.org/10.1016/j.hydromet.2003.11.002.Search in Google Scholar

Nelson, J. J. M., and E. J. Schelter. 2019. “Sustainable Inorganic Chemistry: Metal Separations for Recycling.” Inorganic Chemistry 58 (2): 979–90. https://doi.org/10.1021/acs.inorgchem.8b01871.Search in Google Scholar PubMed

Nguyen, T. H., and M. S. Lee. 2020. “A Review on Germanium Resources and its Extraction by Hydrometallurgical Method.” Mineral Processing and Extractive Metallurgy Review 42 (6): 406–26. https://doi.org/10.1080/08827508.2020.1756795.Search in Google Scholar

Peng, R. Q. 2003. Metallurgy of Lead and Zinc. Beijing: Metallurgical Industry Press.Search in Google Scholar

Pokrovski, G. S., and J. Schott. 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.” Geochimica et Cosmochimica Acta 62 (21–22): 3413–28. https://doi.org/10.1016/s0016-7037(98)00249-x.Search in Google Scholar

Peng, R. Q., H. J. Ren, and X. P. Zhang. 2003. Metallurgy of Lead and Zinc. Beijing: Sicence Press.Search in Google Scholar

Pokrovski, G. S., F. Martin, J. L. Hazemann, and J. Schott. 2000. “An X-Ray Absorption Fine Structure Spectroscopy Study of Germanium-Organic Ligand Complexes in Aqueous Solution.” Chemical Geology 163 (1–4): 151–65. https://doi.org/10.1016/s0009-2541(99)00102-3.Search in Google Scholar

Song, L. T., H. K. Di, M. Liang, K. Yang, and L. B. Zhang. 2022. “Ultrasonic-enhanced Sulfuric Acid Leaching Kinetics of High-Grade Germanium-Containing Materials.” Chemical Engineering and Processing-Process Intensification 178: 109045. https://doi.org/10.1016/j.cep.2022.109045.Search in Google Scholar

Tromans, D. 1998a. “Oxygen Solubility in Inorganic Solutions: Concentration, Temperature and Pressure Effects.” Hydrometallurgy 50 (3): 279–96. https://doi.org/10.1016/s0304-386x(98)00060-7.Search in Google Scholar

Tromans, D. 1998b. “Temperature and Pressure Dependent Solubility of Oxygen in Water: A Thermodynamic Analysis.” Hydrometallurgy 48 (3): 327–42. https://doi.org/10.1016/s0304-386x(98)00007-3.Search in Google Scholar

Wang, Y. F., H. B. Wang, B. S. Zhang, and L. Zhao. 2011. “Comprehensive Recovery of Ga & Ge in Zinc Metallurgy.” Nonferrous Metals 11: 38–40.Search in Google Scholar

Wang, P., L. Y. Chen, J. P. Ge, W. J. Cai, and W. Q. Chen. 2019. “Incorporating Critical Material Cycles into Metal-Energy Nexus of China’s 2050 Renewable Transition.” Applied Energy 253: 113612. https://doi.org/10.1016/j.apenergy.2019.113612.Search in Google Scholar

Wardell, M. P., and C. F. Davidson. 1987. “Acid Leaching Extraction of Ga and Ge.” Journal of Occupational Medicine 39: 39–41. https://doi.org/10.1007/bf03258061.Search in Google Scholar

Xin, C. F., H. Y. Xia, Q. Zhang, L. B. Zhang, and W. Zhang. 2021. “Leaching of Zinc and Germanium from Zinc Oxide Dust in Sulfuric Acid-Ozone Media.” Arabian Journal of Chemistry 14 (12): 103450. https://doi.org/10.1016/j.arabjc.2021.103450.Search in Google Scholar

Xin, C. F., H. Y. Xia, G. Y. Jiang, Q. Zhang, L. B. Zhang, Y. J. Xu, and W. C. Cai. 2022. “Mechanism and Kinetics Study on Ultrasonic Combined with Oxygen Enhanced Leaching of Zinc and Germanium from Germanium Containing Slag Dust.” Separation and Purification Technology 302: 122167. https://doi.org/10.1016/j.seppur.2022.122167.Search in Google Scholar

Xu, Y. J., H. Y. Xia, Q. Zhang, W. C. Cai, G. Y. Jiang, and L. B. Zhang. 2022. “Efficient Recovery of Valuable Metals from Lead-Zinc Smelting By-Products by Ultrasonic Strengthening.” Minerals Engineering 190: 107915. https://doi.org/10.1016/j.mineng.2022.107915.Search in Google Scholar

Zhang, L. B., W. Q. Guo, J. H. Peng, J. Li, G. Lin, and X. Yu. 2016a. “Comparison of Ultrasonic-Assisted and Regular Leaching of Germanium from By-Product of Zinc Metallurgy.” Ultrasonics Sonochemistry 31: 143–9. https://doi.org/10.1016/j.ultsonch.2015.12.006.Search in Google Scholar PubMed

Zhang, M. F., Z. G. Zhou, S. F. Xiong, Y. J. Gong, and G. L. Chen. 2016b. “A Typomorphic Study of Sphalerite from the Huize Lead-Zinc Deposit, Yunnan Province.” Acta Petrologica et Mineralogica 35 (1): 111–23.Search in Google Scholar

Zhang, L. G., Q. M. Song, and Z. M. Xu. 2019a. “Thermodynamics, Kinetics Model, and Reaction Mechanism of Low-Vacuum Phosphate Reduction Process for Germanium Recovery from Optical Fiber Scraps.” ACS Sustainable Chemistry & Engineering 7 (2): 2176–86. https://doi.org/10.1021/acssuschemeng.8b04882.Search in Google Scholar

Zhang, T., T. Jiang, and Z. Y. Liu. 2019b. “Recovery of Ge (IV) from Synthetic Leaching Solution of Secondary Zinc Oxide by Solvent Extraction Using Tertiary Amine (N235) as Extractant and Trioctyl Phosphate (TOP) as Modifier.” Minerals Engineering 136: 155–60. https://doi.org/10.1016/j.mineng.2019.03.011.Search in Google Scholar

Zhang, X. Y., Z. L. Bu, S. Q. Lin, Z. W. Chen, W. Li, and Y. Z. Pei. 2020. “GeTe Thermoelectrics.” Joule 4 (5): 986–1003. https://doi.org/10.1016/j.joule.2020.03.004.Search in Google Scholar

Zhu, Y. X., Z. G. Deng, W. Chang, Y. L. Li, M. Zhang, and W. L. Zhao. 2021. “Leaching Germanium-Containing Zinc Oxide Dust by Atmospheric Oxygen Enrichment.” Chinese Journal of Nonferrous Metals 31 (4): 995–1006.Search in Google Scholar

Received: 2023-01-15

Accepted: 2023-05-29

Published Online: 2023-09-28

You are currently not able to access this content.

Articles in the same Issue

https://doi.org/10.1515/ijcre-2023-0011

Keywords for this article

correlation; germanium leaching; limiting factor; phase; zinc oxide dust