Synergistic Sequestration and Hydroxyapatite-Based Recovery of Phosphorus by the Coupling Process of CaCl2/Modified Oyster Shell and Circulating Fluidized Bed Reactor

A novel modified oyster shell (MOS-800) was developed to enhance phosphorus sequestration and recovery from wastewater. Approximately 33.3% of phosphate was eliminated by the MOS-800, which also exhibited excellent pH regulation capabilities. In semicontinuous tests, a synergistic phosphorus separation was achieved through the coupling process of CaCl2/MOS-800 and a circulating fluidized bed (CFB), resulting in an 86.5% phosphate separation. In continuous flow experiments, phosphorus elimination reached 98.2%. Material characterization revealed that hydroxyapatite (HAP) was the primary component of the crystallized products. Additionally, MOS-800 released 506.5–572.2 mg/g Ca2+ and 98.1 mg/g OH−. A four-stage heterogeneous crystallization mechanism was proposed for the coupling process. In the first stage, Ca2+ quickly reacted with phosphate to form Ca-P ion clusters, etc. In the second stage, these clusters packed randomly to form spherical amorphous calcium phosphate (ACP). In the third stage, the ACP spheres were transformed and rearranged into sheet-like HAP crystallites, Finally, in the fourth stage, the HAP crystallites aggregated on the surface of crystal seeds, also with the addition of crystal seeds and undissolved MOS-800, potentially catalyzing the heterogeneous crystallization. These findings suggest that the CaCl2/MOS-800/CFB system is a promising technique for phosphate recovery from wastewater.