Ca-driven stable regulatory of alkalinity within desilication products: Experimental, modeling, transformation mechanism and DFT study

Abstract

The prevalent pH rebound phenomenon in the bauxite residue alkalinity regulation is primarily caused by the presence of alkaline minerals, including sodalite and cancrinite. Calcium ion is widely used to remove the free alkali for reducing the alkalinity of bauxite residue, but its underlying mechanism on alkaline minerals is still unclear. In this work, we investigated the action mechanism of calcium ion on sodalite and cancrinite by various microspectroscopic methods, and then employed spin-polarized density functional theory (DFT) calculations to reveal the reaction pathways of calcium ion substitution and migration in minerals. The calcium ion can effectively regulate the stability of alkaline minerals by inhibiting alkaline ions release, which respectively enters sodalite and cancrinite by displacing Na adsorbed inside the mineral lattice and on the mineral surface. The entered calcium ion acts as competitive protection against sodium during the neutralization process, thus inhibiting the proton-promoted dissolution of sodalite and cancrinite. Moreover, the amount of entry calcium ion controls their acid neutralization ability. DFT calculations revealed calcium ions readily replaced sodium on the internal channels of minerals rather than on the surface. These new findings contribute to the understanding of potential options to directly stabilize critical alkaline components in bauxite residue.