The Application of Calcium Phosphate Precipitation Chemistry to Phosphorus Recovery: The Influence of Organic Ligands

Abstract

This paper describes current knowledge of phosphate precipitation chemistry in the context of phosphorus recovery from wastewaters, and presents experimental results on the effect of organic species, as key potential inhibitors, to the precipitation of calcium phosphate. The supersaturation required for precipitation at 25°C, pH 7, 0.1 M ionic strength and near-stoichiometric (for hydroxylapatite) calcium to phosphate molar ratio was determined under spontaneous precipitation conditions. The experiments were carried out in air. The phase precipitating at the critical concentration was allowed to grow under constant supersaturation. The influence of organic ligands on the precipitation was investigated using two small molecular weight organic ligands, acetate and citrate, present at a concentration of 10−3 M. The precipitate was studied using X-ray diffraction and scanning electron microscopy. Good reproducibility of the experiments, which were carried out in triplicate, was observed. The study assessed the supersaturation necessary for spontaneous precipitation of hydroxylapatite to be 10.93, calculated using a solubility constant of log K=−57.74. The required supersaturation was not affected by the presence of acetate. However, citrate was found to increase the supersaturation required for precipitation to 11.73. It is likely that this increase is due to binding of citrate on the active growth sites of newly formed nuclei, thereby inhibiting precipitation. All experiments showed formation of a single phase: micro-crystalline hydroxylapatite.