Aging of solidified/stabilized electrolytic manganese solid waste with accelerated carbonation and aging inhibition

High concentrations of soluble Mn in electrolytic manganese solid waste (EMSW) in soil cause the severe contamination in China. Calcium oxide and magnesium oxide-dominated stabilizers are suitable for the solidification/stabilization (s/s) of EMSW. However, the long-term performance of s/s using those two types of stabilizer is problematic. The aim of this study was to develop an accelerated aging method to simulate the long-term natural carbonation of solidified/stabilized EMSW. The joint use of accelerated carbonation, leaching test, mineralogical analysis, and microstructural observation was applied to assess the long-term performance of the s/s EMSW system. On an accelerated carbonation test for solidified/stabilized EMSW, an increase in Mn leaching from 13.6 to 408 mg/kg and a 1.5-2.3 decrease in pH was achieved by using CaO-dominated stabilizers, while an increase in manganese (Mn) from 30 to 266 mg/kg and a decrease in pH of 0.17-0.68 was seen using MgO-dominated stabilizers. CaO+Na₃PO₄ and CaO+CaCO₃ were exceptions in that the leaching value of soluble Mn was lower after carbonation. Mineralogical analysis showed that rhodochrosite in the carbonated s/s system was generated not only from the reduction of hausmannite but also from the reversible reaction between Mn(OH)₂ and MnCO₃. Carbonation destroyed the tight particle structure resulting in a porous and loose structure. As for s/s EMSW treated by MgO-dominated stabilizers, carbonation affected the agglomerating structure and mineralogical composition by increasing magnesium (Mg) migration, thereby forming hydromagnesite that had weak binding ability and a nested porous shape. Therefore, carbonation by itself does not cause deterioration to s/s products of the soluble Mn but does have significant effects on the microstructure and mineralogical composition. It is recommended to add Na₃PO₄ or CaCO₃ into a single CaO stabilized EMSW system to prevent aging of the system, allow formation of Mn phosphate precipitates, and improve the absorption and oxidation of soluble Mn(II).