Hydration process and fluoride solidification mechanism of multi-source solid waste-based phosphogypsum cemented paste backfill under CaO modification

Abstract

The large-scale, environmentally friendly utilization of phosphogypsum (PG) remains a global challenge. PG cemented paste backfill (PCPB) is a promising method to manage PG, but using ordinary Portland cement as the binder has drawbacks such as high cost, low mechanical strength, and high fluoride leaching risk. This paper presents a multi-source solid waste-based PCPB (MPCPB) material that enhances mechanical properties and reduces fluoride leaching risks. In MPCPB, industrial waste residues like steel slag (SS) and ground granulated blast furnace slag (GBFS) are used as precursors (SS: GBFS = 1:2). Additionally, 4–8 wt% CaO (relative to the dry weight of PG) is used as a neutralizing modifier and alkaline activator. The results indicate that an optimal amount of CaO can neutralize the residual acidity of PG, provide sufficient Ca(OH)2 for MPCPB hydration, and react with PG to produce significant amounts of AFt. Furthermore, CaO promotes the geopolymerization reaction between SS and GBFS, generating more calcium silicate hydrate (C-S-H) and calcium aluminate silicate hydrate (C-A-S-H) gels. Fluoride stabilization in MPCPB results from synergistic effects involving hydration reactions, complexation, ionic mobility, rearrangement, and physical adsorption. Notably, CaO enhances the conversion of free fluoride ions into stable compounds like fluorapatite, fluorite (CaF2), [AlF6]3-, and [FeF6]3- complexes. This approach offers a cost-effective, environmentally friendly, and efficient solution to the PG stockpiling challenge.