Submitted:
30 June 2025
Posted:
01 July 2025
You are already at the latest version
Abstract

Keywords:
1. Introduction
2. Materials and Methods
2.1. Materials
2.2. Leaching Experiments and Methods
3. Results and Discussions
3.1. Sulfuric Acid Leaching of ZFR
3.1.1. Effect of Temperature
3.1.2. Effect of Sulfuric Acid Concentration
3.1.3. Effect of the Solid-to-Liquid Ratio
3.1.4. Effect of Reaction Time
- Sulfuric acid concentration is a critical factor determining the metal extraction efficiency. A minimum initial concentration of 200 g/L is required to achieve complete dissolution of copper, iron, and zinc.
- Temperature plays a major role in the leaching process. Practically complete leaching of the ZFR requires a minimum temperature of 90 °C.
- The solid-to-liquid ratio significantly affects metal extraction only under atmospheric leaching conditions, with lower ratios favouring higher extraction rates.
- The optimal leaching duration under atmospheric conditions is approximately 3 hours while under autoclave conditions, 1 hour is sufficient to achieve high extraction rates. Beyond this timeframe, only marginal improvements in metal recovery are observed.
- Autoclave leaching offers higher process rates and allows operation at higher pulp densities, increasing overall efficiency. However, it requires specialized pressure-resistant equipment, which raises the cost of implementation.
3.1.5. Characterization of the Products of Sulfuric Acid Leaching
3.2. Precipitation of Hematite
3.2.1. Effect of Temperature and Seeds Concentration
3.3. Chloride Leaching of Pb Cake
3.3.1. Effect of NaCl Concentration
3.3.2. Effect of HCl Concentration
3.3.3. Effect of Temperature
3.3.4. Effect of Time
3.3.5. Effect of Solid:Liquid Ratio
3.3. Cementation of Lead and Silver from Chloride Leachate
3.4. Hydrometallurgical Process Scheme for ZFR Treatment
3. Conclusions
Author Contributions
Funding
Institutional Review Board Statement
Informed Consent Statement
Data Availability Statement
Acknowledgments
Conflicts of Interest
Abbreviations
| ZFR | Zinc Ferrite Residue |
| SEM | Scanning electron microscope |
| EDS | Energy Dispersive X-ray Spectroscopy |
| ICP-OES | Inductively Coupled Plasma Optical Emission Spectroscopy |
| XRD | X-ray diffraction |
References
- Kozlov, P. The Waelz Process; Ore and Metals Publishing House: Moscow, Russia, 2003; pp. 96–101. [Google Scholar]
- Berdiyarov, B.T. Analysis of the possibility of increasing the degree of zinc Waelz and reducing metal losses during Waelz. Tech. Sci. Innov. 2021, 2021, Article 7. [Google Scholar] [CrossRef]
- Stoychev, S.; Minchev, E.; Kyurkchiev, A.; Radonov, G. Technologies for treatment of zinc-containing waste from metallurgy in KCM AD. In PbZn 2020: 9th International Symposium on Lead and Zinc Processing; Siegmund, A., Alam, S., Grogan, J., Kerney, U., Shibata, E., Eds.; Springer: Cham, Switzerland, 2020; pp. 625–638. [Google Scholar] [CrossRef]
- Glinin, A.; Nikolic, M.; Kleppinger, R.; Oeters, F. Outotec® Ausmelt technology for treating zinc residues. World Metall.–Erzmetall 2013, 66, 231–236. [Google Scholar]
- Hughes, S.; Reuter, M.A.; Baxter, R.; Kaye, A. Ausmelt technology for lead and zinc processing. In Proceedings of the Lead and Zinc 2008 Conference, Johannesburg, South Africa, 25–27 February 2008; The Southern African Institute of Mining and Metallurgy: Johannesburg, South Africa, 2008. [Google Scholar]
- Hoang, J.; Reuter, M.A.; Matusewicz, R.; Hughes, S.; Piret, N. Top submerged lance direct zinc smelting. Miner. Eng. 2009, 22, 742–751. [Google Scholar] [CrossRef]
- Yan, H.; Chai, L.; Peng, B.; Li, M.; Peng, N.; Hou, D. A novel method to recover zinc and iron from zinc leaching residue. Miner. Eng. 2014, 55, 103–110. [Google Scholar] [CrossRef]
- Hu, M.; Peng, B.; Chai, L.; Li, Y.; Peng, N.; Yuan, Y.; Chen, D. High-zinc recovery from residues by sulfate roasting and water leaching. JOM 2015, 67, 2333–2339. [Google Scholar] [CrossRef]
- Jiang, G.; Peng, B.; Liang, Y.; Chai, L.; Wang, Q.; Li, Q.; Hu, M. Recovery of valuable metals from zinc leaching residue by sulfate roasting and water leaching. Trans. Nonferrous Met. Soc. China 2017, 27, 1180–1187. [Google Scholar] [CrossRef]
- Li, Y.; Liu, H.; Peng, B.; Min, X.; Hu, M.; Peng, N.; Yuan, Y. Study on separating of zinc and iron from zinc leaching residues by roasting with ammonium sulphate. Hydrometallurgy 2015, 157, 75–81. [Google Scholar] [CrossRef]
- Güler, E.; Seyrankaya, A.; Çoçen, İ. Hydrometallurgical evaluation of zinc leach plant residue. Asian J. Chem. 2011, 23, 4565–4570. [Google Scholar]
- Turan, M.D.; Altundoğan, H.S.; Tümen, F. Recovery of zinc and lead from zinc plant residue. Hydrometallurgy 2004, 75, 169–176. [Google Scholar] [CrossRef]
- Zhang, F.; Wei, C.; Deng, Z.; Li, X.; Li, C.; Li, M. Reductive leaching of indium-bearing zinc residue in sulfuric acid using sphalerite concentrate as reductant. Hydrometallurgy 2016, 161, 102–106. [Google Scholar] [CrossRef]
- Fan, Y.; Liu, Y.; Niu, L.; Zhang, W.; Zhang, Z. Reductive leaching of indium from zinc-leached residue using galena as reductant. Miner. Eng. 2021, 163, 106777. [Google Scholar] [CrossRef]
- Fan, Y.Y.; Liu, Y.; Niu, L.P.; Jing, T.L.; Zhang, W.G.; Zhang, T.A. Reductive leaching of indium-bearing zinc ferrite in sulfuric acid using sulfur dioxide as a reductant. Hydrometallurgy 2019, 186, 192–199. [Google Scholar] [CrossRef]
- Zhang, C.; Min, X.; Zhang, J.; Wang, M.; Fei, J.; Li, Y. Enhanced cadmium extraction from zinc neutral leaching residue using sulfur dioxide. Sep. Sci. Technol. 2015, 50, 2688–2696. [Google Scholar] [CrossRef]
- Alizadeh, R.; Rashchi, F.; Vahidi, E. Recovery of zinc from leach residues with minimum iron dissolution using oxidative leaching. Hydrometallurgy 2019, 188, 35–42. [Google Scholar] [CrossRef]
- Silwamba, M.; Ito, M.; Hiroyoshi, N.; Tabelin, C.B.; Hashizume, R.; Fukushima, T.; Park, I.; Jeon, S.; Igarashi, T.; Sato, T.; et al. Alkaline leaching and concurrent cementation of dissolved Pb and Zn from zinc plant leach residues. Minerals 2022, 12, 393. [Google Scholar] [CrossRef]
- Erdem, M.; Yurten, M. Kinetics of Pb and Zn leaching from zinc plant residue by sodium hydroxide. J. Min. Metall. Sect. B-Metall. 2015, 15, 89–95. [Google Scholar] [CrossRef]
- Ashtari, P.; Pourghahramani, P. Selective mechanochemical alkaline leaching of zinc from zinc plant residue. Hydrometallurgy 2015, 156, 165–172. [Google Scholar] [CrossRef]
- Wang, Y.; Jiang, K.; Ma, H.; Qin, S. The behavior of zinc and iron in neutralized residue during pressure leaching. Min. Metall. Explor. 2022, 39, 1–8. [Google Scholar] [CrossRef]
- Wang, Y.; Wang, H.; Li, X.; Zheng, C. Study on the improvement of the zinc pressure leaching process. Hydrometallurgy 2020, 195, 105400. [Google Scholar] [CrossRef]
- Sethurajan, M.; Lens, P.N.L.; Rene, E.R.; van de Vossenberg, J.; Huguenot, D.; Horn, H.A.; Figueiredo, L.H.A.; van Hullebusch, E.D. Bioleaching and selective biorecovery of zinc from zinc metallurgical leach residues from the Três Marias zinc plant (Minas Gerais, Brazil). J. Chem. Technol. Biotechnol. 2017, 92, 512–521. [Google Scholar] [CrossRef]
- Ruiz, M.C.; Zapata, J.; Padilla, R. Effect of variables on the quality of hematite precipitated from sulfate solutions. Hydrometallurgy 2007, 89, 32–39. [Google Scholar] [CrossRef]
- Ozberk, E.; Collins, M.J.; Makwana, M.; Masters, I.M.; Pulenberg, R.; Bahl, W. Zinc pressure leaching at the Ruhr-Zink refinery. Hydrometallurgy 1995, 39, 53–61. [Google Scholar] [CrossRef]
- Li, C.; Wei, C.; Yi, S.; Fan, G.; Deng, Z.; Li, X.; Li, M. Formation of iron hydroxysulphate phases in the hematite process by hydrolysis of ferric sulphate. Hydrometallurgy 2019, 189, 105112. [Google Scholar] [CrossRef]
- Cheng, T.C. Production of hematite in acidic zinc sulphate media. Can. J. Mater. Eng. 2002, 1–10, p–36. [Google Scholar]
- Raghavan, R.; Mohanan, P.K.; Swarnkar, S.R. Hydrometallurgical processing of lead-bearing materials for the recovery of lead and silver as lead concentrate and lead metal. Hydrometallurgy 2000, 58, 103–116. [Google Scholar] [CrossRef]
- Farahmand, F.; Moradkhani, D.; Safarzadeh, M.S.; Rashchi, F. Brine leaching of lead-bearing zinc plant residues: Process optimization using orthogonal array design methodology. Hydrometallurgy 2009, 95, 316–324. [Google Scholar] [CrossRef]
- Motamedizadeh, M.; Azizi, A.; Bahri, Z. Recycling lead from a zinc plant residue (ZPR) using brine leaching and cementation with aluminum powder. Environ. Sci. Pollut. Res. 2021, 28, 42121–42134. [Google Scholar] [CrossRef]
- Behnajady, B.; Moghaddam, J. Chloride leaching of lead and silver from refractory zinc plant residue. Res. J. Chem. Environ. 2011, 15, 473–480. [Google Scholar]
- Kazakova, N.; Lucheva, B.; Iliev, P. A study on the cementation process of non-ferrous metals from a brine leaching solution. J. Chem. Technol. Metall. 2020, 55, 223–227. [Google Scholar]

















| Zn | Fe | Cu | Pb | Ag | Mn | S | Si | Ca | Al |
|---|---|---|---|---|---|---|---|---|---|
| 18.12 | 29.81 | 1.30 | 7.43 | 0.0154 | 1.84 | 3.52 | 3.27 | 2.21 | 1.11 |
| Type of leaching | Products | Chemical composition, mass % | ||||
|---|---|---|---|---|---|---|
| Fe | Zn | Pb | Cu | Ag | ||
| Atmospheric leaching | Solution g/L | 27.64 | 17.81 | - | 1.25 | - |
| Insoluble residue % | 7.98 | 1.13 | 26.84 | 0.17 | 0.0554 | |
| Autoclave leaching | Solution g/L | 27.59 | 17.76 | - | 1.26 | - |
| Insoluble residue % | 9.12 | 1.47 | 30.53 | 0.168 | 0.0634 | |
| Element | Weight % (Atmospheric leaching) |
Weight % (Autoclave leaching) |
|---|---|---|
| Pb | 29.48 | 25.77 |
| Fe | 7.51 | 9.78 |
| Zn | 2.03 | 1.86 |
| S | 5.46 | 5.42 |
| O | 38.59 | 40.78 |
| Si | 12.42 | 11.15 |
| Al | 1.32 | 1.47 |
| Ca | 0.43 | 1.22 |
| K | 0.00 | 0.66 |
| Na | 0.32 | 0.63 |
| Mg | 0.12 | 0.58 |
| Mn | 1.99 | 0.36 |
| Cu | 0.33 | 0.33 |
| Element | Weight % |
| Fe | 75.28 |
| O | 23.28 |
| S | 0.90 |
| Si | 0.29 |
| Pb | 0.21 |
| Ca | 0.04 |
| Zn | Fe | Cu | Pb | Ag | |
| Insoluble residue, % | 1.35 | 7.98 | 0.19 | 1.57 | 0.016 |
| Solution, g/L | 0.40 | 3.61 | 0.07 | 25.98 | 0.046 |
| Element | Weight % |
|---|---|
| Fe | 15.70 |
| Pb | 1.50 |
| Zn | 4.82 |
| S | 1.67 |
| Si | 25.57 |
| Al | 3.58 |
| O | 44.33 |
| Ti | 1.02 |
| Mg | 0.87 |
| Ca | 0.76 |
| Na | 0.19 |
| Zn | Fe | Cu | Pb | Ag |
|---|---|---|---|---|
| 0.39 | 0.21 | 0.22 | 84.75 | 0.1740 |
Disclaimer/Publisher’s Note: The statements, opinions and data contained in all publications are solely those of the individual author(s) and contributor(s) and not of MDPI and/or the editor(s). MDPI and/or the editor(s) disclaim responsibility for any injury to people or property resulting from any ideas, methods, instructions or products referred to in the content. |
© 2025 by the authors. Licensee MDPI, Basel, Switzerland. This article is an open access article distributed under the terms and conditions of the Creative Commons Attribution (CC BY) license (http://creativecommons.org/licenses/by/4.0/).