Utilizing the ozonation pathway for enhanced conversion of manganese dithionate to manganese dioxide from acid leaching solution: Insights into mechanism and kinetics

Abstract

In response to the fact that the presence of manganese dithionate (MnS₂O₆) leads to a series of adverse impacts, especially lower purity of manganese sulfate (MnSO₄) and disruption of its recovery, advanced oxidation methods such as ozonation system are used to manage MnS₂O₆ in the leaching solution, replacing conventional methods. To ascertain the conversion rate and kinetics of MnS₂O₆ during the ozonation process, we explored the factors influencing its removal rate, including ozone dosage, manganese dithionate concentration, sulfuric acid concentration, and reaction temperature. Batch experiments were conducted to determine the reaction rate constant of ozone (k) and activation energy (E_a) obtained from intermittent experimental data fitting, revealing a least-squares exponential conversion relationship between k and the MnS₂O₆ removal amount, wherein an increase in the aforementioned factors led to an enhanced MnS₂O₆ conversion rate, exceeding 99.3%. The formation mechanism of the ozone products proposed during the experiment was summarized and proposed as follows: 1) Mn²⁺ was directly oxidized to MnO₂, and 2) SO₄²⁻ was obtained by the catalytic oxidation of S₂O₆²⁻ with HO• from O₃ decomposition. According to the kinetics analysis, the pre-exponential factor and total activation energy of the ozonation kinetics equation were 1.0×10²³ s⁻¹ and 177.28 kJ/mol, respectively. Overall, the present study demonstrates that O₃ as an oxidizing agent can effectively facilitate MnS₂O₆ disproportionation while preventing the release of the secondary pollutant, SO₂ gas.

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