Turning harmful Mn2+ to treasure: In-situ formed ε-MnO2 for removing heavy metals from acid mine drainage

Abstract

Acid mine drainage (AMD) contains high concentrations of heavy metals, causing serious environmental pollution. Current neutralization techniques fail to recover and utilize valuable heavy metals, and generate large quantities of hazardous sludge. Manganese (Mn) is generally present at high levels in AMD. Therefore, this paper proposed a technology to recover Mn from AMD, by adding KMnO4 to converting Mn into ε-MnO2. Ultra-Violet C (UVC) was used to photolyze the residual KMnO4. The study then evaluated the processes and mechanisms involved in the technology. The photolysis of KMnO4 in strong acidic conditions was determined, and new mechanisms were proposed. MnO2 produced by the photolysis process was formed through the reaction between Mn(III) and KMnO4. In the absence of KMnO4, Mn(III) underwent further photolysis and was reduced to Mn2+. The maximum adsorption capacities of in-situ formed ε-MnO2 for Pb2+, Cd2+, and Fe3+ were 449.80, 122.05, and 779.88 mg/g, respectively. Higher Mn-OH levels and MnO2 regeneration were crucial in improving adsorption performance. Proton exchange and inner-circle complexation were the main pathways for Pb2+ and Cd2+ adsorption by in-situ formed ε-MnO2. A phase transformation occurred when a substantial amount of Fe3+ was adsorbed, leading to the gradual transformation to MnFe binary oxides. When applying in-situ formed ε-MnO2 technology for actual AMD treatment, 98.62 % of Mn in AMD was recovered within 24 h in the presence of ε-MnO2 for possible further reuse in industries, with a final recovery of 0.76 kg/m3. Further, this technique removed other heavy metals and reduced the sludge volume by 20.99 % when used as a pre-treatment step for neutralization. These results demonstrated the broad potential of this treatment technology.