Abstract
To improve the recycling efficiency of rejected electrolytic manganese metal (EMM) scrap that contains excessive sulfur, a high-temperature experiment and mathematical model reflecting the mechanism of sulfur transfer from the molten manganese metal to the molten slag were elaborated. A MoSi2 electrical resistance furnace filled with argon protective gas was first employed to perform the desulfurization experiment at 1673 K (1400 °C). Four different fluorine slags with the CaO content ranging from 0 to 20 pct were used in the experiment. A mathematical model of the rejected EMM scrap desulfurization, based on the two-film theory, was established. It adequately described the thermodynamics and kinetics of the rejected EMM scrap desulfurization reaction. In particular, it captured the influence of the interfacial tension between the molten slag and molten manganese for the sulfur transfer process. A comparative analysis of measured and calculated results proved the model feasibility: it took into account the effects of the holding temperature, slag CaO content, the initial sulfur content in rejected EMM scrap, and slag/manganese mass ratio on the desulfurization efficiency. The results indicate that CaO could promote the desulfurization of the manganese metal. The sulfur removal ratio is 58.01 pct with a CaO-free slag at 1673 K (1400 °C), while the ratio increases to 84.58 pct if the CaO content rises to 20 pct. At higher temperatures, the CaO content in the slag can be appropriately reduced. High slag/manganese mass ratios were found to benefit the sulfur removal, while the CaO content in the slag could be adjusted according to the initial sulfur content in the rejected EMM scrap.
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The authors appreciate the financial support from the National Natural Science Foundation of China (Grant No. 51804227).
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Manuscript submitted August 8, 2020, accepted February 15, 2021.
Appendix A: Calculation of Surface Tension of Molten Slag and Molten Manganese
Appendix A: Calculation of Surface Tension of Molten Slag and Molten Manganese
The model takes into account the surface tension effect on the interfacial area during the desulfurization process. As mentioned above, the molten slag and molten manganese interfacial tension strongly influence the interface area. In the present work, the interfacial tension is treated as a function of temperature and is related to the surface tension of the molten slag and molten manganese:[45,46,47,48,49]
where \( \gamma_{\text{ms}} \) denotes the interfacial tension between the molten slag and molten manganese; \( \phi \) is the slag system interaction, while \( \gamma_{\text{m}} \) is the surface tension of molten manganese, which is determined by the temperature as follow:
The molten slag surface tension coefficient \( \gamma_{\text{s}} \) is related to the slag composition and temperature:
where \( \gamma_{i}^{ 0} \) represents the surface tension coefficient of pure CaO, MnO, CaF2, and Al2O3 melts, which are the constituents of the slag and were affected by the temperature as shown in Table AI.[48,49] Superscripts “surf” and “bulk” indicate the surface and bulk, respectively. \( A_{i} \) is the molar surface area in a monolayer of each component; \( N_{0} \) is Avogadro’s number, and \( V_{i} \) is the temperature-dependent molar volume of each component, as displayed in Table AII.[48]\( X_{i}^{\text{surf}} \) is the molar fraction of the components in the surface; \( X_{i}^{\text{bulk}} \) is the molar fraction of the components in bulk; \( R_{\text{A}} \) is the radius of the cation (\( R_{\text{Ca}}^{{ 2 { + }}} \), \( R_{\text{Mn}}^{{ 2 { + }}} \) or \( R_{\text{Al}}^{3 + } \)), and \( R_{\text{X}} \) is the radius of the anion (\( R_{\text{O}}^{2 - } \), or \( R_{\text{F}}^{ - } \)) in slag, as given in Table AIII.[48]
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Lu, R., Li, G., Gao, Y. et al. Investigation on Desulfurization of Rejected Electrolytic Manganese Metal Scrap: Experiment and Mathematical Modeling. Metall Mater Trans B 52, 1626–1639 (2021). https://doi.org/10.1007/s11663-021-02129-2
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DOI: https://doi.org/10.1007/s11663-021-02129-2