2018 Volume 59 Issue 2 Pages 290-296
We investigated the recovery of calcium fluoride (CaF2) from highly concentrated hexafluorosilicic acid wastewater by neutralization–purification. Neutralization was achieved by dosing calcium hydroxide, whereas purification was carried out by alkaline leaching with sodium hydroxide. X-ray diffraction, X-ray absorption fine structure, mineral liberation analyzer, Fourier transform infrared spectroscopy and Inductively-coupled plasma atomic emission spectroscopy were used to quantify the neutralization and leaching performance and to elucidate their mechanisms. The precipitation behavior was strongly dependent on the calcium (Ca)/silicon (Si) molar ratio. For a Ca/Si ratio of 1.12, approximately 25% of the total fluorine was precipitated selectively as CaF2. By increasing the Ca/Si ratio to 3.91, the recovery yield increased to 100% because of the precipitation of CaSiF6 and the hydrolytic decomposition of hexafluorosilicate ion (SiF62−) to CaF2. The hydrolytic decomposition of SiF62− resulted in the precipitation of silicon dioxide on the surface of the previously formed CaF2. Alkaline leaching by sodium hydroxide at 70℃ resulted in an efficient removal of the silicon phase from the neutralized sludge with the formation of a CaF2 product with a grade above 90%. Leaching parameters, such as the kinetic constant and the activation energy, were determined by assuming first-order kinetics. The residual silicon phase in the final product could not be dissolved because of the formation of non-leachable SiO32−.