Author Contributions
Conceptualization: R.P., S.K.; Methodology: R.P.; Investigation: R.P., S.K., A.C., R.M., and M.D., Resources: R.P.; Writing—original draft preparation: R.P.; Writing—review and editing: R.P., S.K., K.K., G.K., and M.D.; Visualization: R.P.; Supervision: R.P., S.K., and G.K.; Funding acquisition: A.C.
Funding
This activity has received funding from the European Institute of Innovation and Technology (EIT) under grant agreement No. 15038. This European body receives support from the Horizon 2020 research and innovation program. The work was also supported by own funds.
Conflicts of Interest
The authors declare no conflict of interest.
References
- European Commission. Communication from the Commission to the European Parliament, the Council, the European Economic and Social Committee and the Committee of the Regions on the 2017 List of Critical Raw Materials for the EU. COM(217) 490 Final; European Commission: Brussels, Belgium, 2017. [Google Scholar]
- Speirs, J.; Gross, B.; Gross, R.; Houari, Y. Energy Materials Availability; UK Energy Research Centre: London, UK, 2013. [Google Scholar]
- Dai, S.F.; Seredin, V.V.; Ward, C.R.; Jiang, J.H.; Hower, J.C.; Song, X.L.; Jiang, Y.F.; Wang, X.B.; Gornostaeva, T.; Li, X.; et al. Composition and modes of occurrence of minerals and elements in coal combustion products derived from high-Ge coals. Int. J. Coal Geol. 2014, 121, 79–97. [Google Scholar] [CrossRef]
- Font, O.; Querol, X.; Lopez-Soler, A.; Chimenos, J.M.; Fernandez, A.I.; Burgos, S.; Pena, F.G. Ge extraction from gasification fly ash. Fuel 2005, 84, 1384–1392. [Google Scholar] [CrossRef]
- Makowska, D.; Wieronska, F.; Strugala, A.; Kosowska, K. Germanium content in Polish hard coals. In Proceedings of the 1st International Conference on the Sustainable Energy and Environment Development (SEED), Krakow, Poland, 17–19 May 2016. [Google Scholar]
- Kul, A.; Topkaya, Y. Recovery of germanium and other valuable metals from zinc plant residues. Hydrometallurgy 2008, 92, 87–94. [Google Scholar] [CrossRef]
- Bayat, S.; Aghazadeh, S.; Noaparast, M.; Gharabaghi, M.; Taheri, B. Germanium separation and purification by leaching and precipitation. J. Cent. South Univ. 2016, 23, 2214–2222. [Google Scholar] [CrossRef]
- Fayram, T.S.; Anderson, C.G. The development and implementation of industrial hydrometallurgical gallium and germanium recovery. J. South. Afr. Inst. Min. Metall. 2008, 108, 261–271. [Google Scholar]
- Liu, F.P.; Liu, Z.H.; Li, Y.H.; Wilson, B.P.; Lundstrom, M. Recovery and separation of gallium(III) and germanium(IV) from zinc refinery residues: Part I: Leaching and iron(III) removal. Hydrometallurgy 2017, 169, 564–570. [Google Scholar] [CrossRef]
- Alfantazi, A.M.; Moskalyk, R.R. Processing of indium: A review. Miner. Eng. 2003, 16, 687–694. [Google Scholar] [CrossRef]
- Chmielarz, A.; Prajsnar, R.; Szołomicki, Z.; Becker, K.; Pietrek, W. A case study on indium recovery from by-product lead alloy. In Proceedings of the Pb-Zn, Duesseldorf, Germany, 14–17 June 2015; pp. 147–158. [Google Scholar]
- Howard, S.M. Ellingham Diagrams, Internet Resource for MET 320—Metallurgical Thermodynamics, South Dakota School of Mines and Technology, Rapid City, SD, USA. Available online: http://showard.sdsmt.edu/MET320/Handouts/EllinghamDiagrams/Ellingham_v22_Macro.pdf (accessed on 17 Dec 2018).
- Drzazga, M.; Prajsnar, R.; Chmielarz, A.; Benke, G.; Leszczyńska-Sejda, K.; Ciszewski, M.; Bilewska, K.; Krawiec, G. Germanium and Indium Recovery from Zinc Metallurgy by—Products—Dross Leaching in Sulphuric and Oxalic Acids. Metals 2018, 8, 1041. [Google Scholar] [CrossRef]
Figure 1.
The layout of the zinc refinery at HCM where byproduct alloys are prepared (GOB: good ordinary brand, SHG: special high grade).
Figure 2.
Installation for the thermal oxidation of PbSnIn and PbSnCuGeIn alloys. 1: kettle, 2: gas exhaust, 3: kettle hood, 4: inverter, 5: mixer, 6: supporting structure, 7: gas–air burner.
Figure 3.
Pyrometallurgical extraction of Zn, and also of In and Sn from the PbSnIn alloy.
Figure 4.
Pyrometallurgical extraction of Ge, In, and Sn from the PbSnCuGeIn alloy.
Figure 5.
Changes in the In and Sn contents in PbSnIn alloys during thermal oxidation, Tests 1–5.
Figure 6.
Change of Ge, In, and Zn content in the PbSnCuGeIn alloy during thermal oxidation, Test 4.
Figure 7.
Change of Ge, In, and Zn content in the PbSnCuGeIn alloy during thermal oxidation, Test 5.
Figure 8.
Diffraction pattern of the qualitative XRD phase analysis of the In <0.32-mm dross.
Figure 9.
Particle-size distribution of the In <0.32-mm dross.
Figure 10.
Diffraction pattern of the qualitative XRD phase analysis of the GeIn dross.
Table 1.
Annual output and chemical composition of the PbSnIn and PbSnCuGeIn alloys.
Alloy | Amount (tpa *) | Chemical Composition (wt %) |
---|
In | Ge | Sn | Pb | Cu | Zn | Sb | As | Bi | Ag |
---|
PbSnIn | 250 | 0.23 | 0.012 | 2.62 | 93.3 | 0.006 | 2.23 | 0.076 | <0.02 | 0.30 | – |
PbSnCuGeIn | 30 | 1.74 | 6.90 | 35.9 | 19.0 | 21.4 | 8.63 | 1.06 | 1.55 | 0.061 | 1.55 |
Table 2.
Chemical composition of the metal obtained from thermal PbSnIn oxidation.
Test No. | Mass (kg) | Chemical Composition (wt %) |
---|
Pb | Zn | Sn | In |
---|
1 | 703 | 98.20 | <0.010 | 1.650 | 0.020 |
2 | 693 | 98.10 | <0.010 | 1.560 | 0.020 |
3 | 632 | 98.50 | <0.010 | 1.170 | 0.020 |
4 | 642 | 98.40 | <0.010 | 1.320 | 0.018 |
5 | 449 | 98.60 | <0.010 | 1.080 | 0.013 |
Table 3.
The average chemical composition of the Zn drosses from the thermal oxidation of PbSnIn.
Test No. | Mass (kg) | Chemical Composition (wt %) |
---|
Zn | Pb | Sn | In | Ge | Na |
---|
1 | 47.20 | 31.50 | 17.00 | 2.510 | 0.141 | 0.303 | 18.30 |
2 | 39.70 | 30.90 | 29.30 | 2.140 | 0.138 | 0.270 | 13.00 |
3 | 63.30 | 30.70 | 16.60 | 4.820 | 0.162 | 0.200 | 19.40 |
4 | 57.00 | 36.70 | 9.240 | 4.550 | 0.064 | 0.196 | 20.50 |
5 | 29.00 | 37.20 | 6.800 | 7.960 | 0.154 | 0.395 | 17.10 |
Table 4.
The average chemical composition of the In <0.32-mm drosses from the thermal oxidation of PbSnIn alloy.
Test No. | Mass (kg) | Chemical Composition (wt %) |
---|
Pb | In | Sn | Zn |
---|
1 | 99.20 | 82.20 | 1.250 | 6.160 | 0.850 |
2 | 109.4 | 75.80 | 1.340 | 6.120 | 3.030 |
3 | 142.6 | 70.50 | 0.820 | 5.110 | 1.120 |
4 | 150.1 | 77.20 | 1.120 | 4.460 | 1.200 |
5 | 174.3 | 73.70 | 1.110 | 6.730 | 1.260 |
Table 5.
Chemical composition of the final metal from the thermal oxidation of the PbSnCuGeIn alloy.
Test No. | Chemical Composition (wt %) |
---|
Ge | In | Ag | Zn | Cu | Sn | Pb | Ni | Sb | As |
---|
1 | 4.89 | 1.98 | 0.98 | 1.81 | 15.7 | 40.7 | 31.2 | 0.20 | 0.60 | 0.048 |
2 | 2.19 | 2.12 | 1.10 | 0.58 | 18.8 | 44.4 | 28.8 | 0.21 | 0.66 | 0.077 |
3 | 0.27 | 0.63 | 1.26 | <0.01 | 20.3 | 47.1 | 29.0 | 0.25 | 0.69 | 0.13 |
4 | 0.01 | 0.015 | 1.87 | <0.01 | 29.0 | 49.4 | 18.2 | 0.36 | 0.84 | 0.21 |
5 | 0.01 | 0.06 | 1.76 | <0.01 | 30.8 | 50.2 | 15.8 | 0.37 | 0.80 | 0.16 |
Table 6.
Chemical composition of the oxide-GeIn dross <0.32 mm.
Test No. | Chemical Composition (wt %) |
---|
Ge | In | Sn | Cu | Pb | Zn | Ag | Ga | Fe | Sb | Na |
---|
1 | 11.1 | 3.74 | 27.7 | 15.1 | 21.0 | 17.6 | 0.67 | 0.43 | 0.41 | 0.72 | 0.49 |
3 | 11.7 | 4.09 | 27.2 | 10.3 | 17.2 | 8.12 | 0.50 | 0.26 | 1.49 | 0.51 | 2.20 |
4 | 10.5 | 2.74 | 28.7 | 10.6 | 18.0 | 9.23 | 0.68 | 0.28 | 0.74 | 0.58 | 1.96 |
5 | 11.6 | 2.45 | 28.5 | 9.32 | 20.9 | 7.09 | 0.66 | 0.47 | 0.67 | 0.55 | 2.55 |
Table 7.
Chemical composition of the sodium–GeIn dross.
Test No. | Chemical Composition (wt %) |
---|
Ge | In | Sn | Cu | Pb | Zn | Ag | Ga | Fe | Sb | Na |
---|
2 | 12.2 | 2.52 | 21.1 | 10.9 | 14.0 | 5.94 | 0.53 | 0.66 | 0.28 | 0.51 | 13.0 |
© 2019 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/).