Chemical precipitation at extreme fluoride concentration and potential recovery of CaF2 particles by fluidized-bed homogenous crystallization process

Excessive and industrial advances have increased fluoride quantity in the effluents. However, the environmental carrying capacity for fluoride is relatively slim immediately affecting both aquatic and terrestrial animals while its transport can further contaminate the water source. To protect the public and the environment, different environmental agencies globally set their respective effluent standard restricting F- concentration to 15 mg/L as the median value. However, various processes from previous investigations have mostly been limited in treating 100–1000 mg F-/L with secondary pollution commonly overlooked. Re-assessing the available defluoridation technologies, chemical precipitation has still been the most feasible among the technologies, especially extremely high fluoride concentrations. In this study, fluoride removal through chemical precipitation was investigated using conventional precipitation and fluidized-bed homogeneous crystallization. Parameters such as a wide range of initial concentrations from 100 to10,000 mg/L and pH 2.0–11.0 under conventional precipitation were varied and analyzed. To reduce high water content sludge, a 550-mL cylindrical glass was modified to simulate a fluidized-bed reactor to investigate homogenous crystallization varying influent concentration, bed-support size, and fluid flow. Results showed that chemical precipitation could effectively remove fluoride even at very high fluoride concentrations ranging from 1,000 to 10,000 mg/L. Alternatively in the fluidized-bed granulation process, an initial very low flow without recirculation flow was required to initiate particle formation. The predominant size of the recovered particle was < 0.2 mm which was relatively heavy atypically not reaching the upper region of the reactor. Under the observed optimum condition with an initial fluoride concentration of 450 mg/L, both total removal and crystallization ratio could reach ∼ 98% efficiency lowering fluoride concentration to < 15.0 mg F-/L within 7 days.