Low-cost chitosan-calcite adsorbent development for potential phosphate removal and recovery from wastewater effluent

Phosphorous (P) recovery from wastewater will become increasingly vital in the future as terrestrial rock phosphate deposits are expended. Effective management of P as a critical resource will require new techniques to recover P from wastewater, ideally in a form that can be used in agriculture as fertiliser. In this study, batch and fixed-bed column conditions were tested using a novel KOH deacetylated calcite-chitosan based adsorbent (CCM) for P removal from aqueous solutions and wastewater effluents. The unique characteristics of this adsorbent as a phosphate adsorbent were the result of rich surface functionality (amine and sulphur functional groups of the chitosan and proteins) and the CaCO₃ content (providing donor ligands; and additionally beneficial if the material were used as fertiliser, buffering soil acidification caused by nitrogen application). The maximum P adsorption capacity was determined to be 21.36 mgP/g (at 22 °C) and the endodermic process reached equilibrium after 120 min. The experimental data was best described using a Langmuir isotherm and a pseudo-second order kinetic model. The diffusion kinetic analysis highlighted the importance of both film and intraparticle mass-transport. Material characterisation suggested that the adsorption process involved interactions between P and functional groups (mostly -NH₃⁺) due to electrostatic interaction on the chitosan chain or involved ligand exchange with CO₃^2-. Analysis of materials using X-Ray Powder Diffraction (XRPD) and Thermogravimetric Analysis (TGA) indicated a microprecipitation-type mechanism may occur through the formation of hydroxylapatite (Ca₅(PO₄)₃(OH)). Desorption studies demonstrated that the P-laden CCM (derived from crab carapace) had the potential to be reused in soil amendment as a slow-release P fertiliser. The effects of different operating parameters were explored in a fixed-bed column, and the experimental data fitted well to the Clark model (R² = 0.99). The CCM also showed excellent P adsorption potential from secondary and final wastewater effluent in dynamic conditions, even at low P concentrations. Finally, a scale-up approach with cost analysis was used to evaluate the price and parameters needed for a potential large-scale P recovery system using this adsorbent.