Study of microscopic properties and heavy metal solidification mechanism of electrolytic manganese residue-based cementitious materials

Electrolytic manganese residue (EMR) is a solid waste that contains a significant amount of soluble manganese and ammonia nitrogen, which can pose risks to human health if improperly disposed of. This study aimed to prepare cementitious materials containing abundant ettringite crystals by mixing EMR with various proportions of granulated blast furnace slag (GBFS) and alkaline activators (CaO, Ca(OH)₂, clinker, NaOH). The resulting cementitious material not only utilized a substantial amount of EMR but also exhibited comparable strength to ordinary Portland cement. The optimal ratios were determined through mechanical testing. Additionally, the leaching toxicity of cementitious materials was assessed using ICP-MS (inductively coupled plasma mass spectrometer) tests. The microscopic properties, hydration, and mechanism of heavy metal solidification in the cementitious materials were evaluated using XRD (X-ray diffraction), SEM (scanning electron microscope), EDS (energy-dispersive spectrometer), FTIR (Fourier transform infrared spectroscopy), and TG (thermogravimetric) techniques. The results showed that the optimal ratio for the cementitious materials was 60% EMR, 36% GBFS, and 4% Ca(OH)₂. The hardened mortar exhibited compressive strengths of 34.43 MPa, 41.3 MPa, and 50.89 MPa at 3 days, 7 days, and 28 days, respectively, with an EMR utilization rate of 60%. The hydration products of EMR-based cementitious materials were C-(A)-S-H, AFt, and ferromanganese compounds, which contribute to the mechanical strength. The Mn²⁺ and NH₄⁺-N contents of raw EMR were 1220 and 149 mg/L, respectively. Nonetheless, the leaching of Mn²⁺ and NH₄⁺-N in the alkali-EMR-GBFS system was significantly below the limits set by the Chinese emission standard GB8978-1996. Within this system, C-(A)-S-H and AFt could physically adsorb and displace heavy metals, Ca₆Mn₂(SO₄)₂(SO₃)₂(OH)₁₂·24H₂O could replace Al ions with Mn ions, and ferromanganese compounds Fe₂Mn(PO₄)₂(OH)₂·(H₂O)₈ and MnFe₂O₄ could chemically precipitate Mn²⁺.