To address the environmental hazards caused by the industrial discharge of fluoride-containing wastewater, the effects of calcium-fluoride ratio, pH value, reaction temperature, and reaction time on fluoride removal efficiency were investigated by simulating the calcium salt precipitation reaction process of fluorine-containing wastewater. The relationship between the particle number density and the growth rate of calcium fluoride nuclei under various factors was analyzed by using the particle number balance model. The relative growth kinetic equation of calcium fluoride nucleation and its corresponding sensitivity coefficient under each condition were obtained, and the characteristics of crystallization products were characterized by XRD and SEM-EDS. The crystallization behavior of calcium fluoride in the chemical precipitation reaction of NaF and CaCl2 was clarified. The results showed that when the calcium-fluorine ratio was 2, the pH value was 7, the reaction temperature was 60℃, and the reaction time was 60 min, the fluoride ion concentration in the treated wastewater was decreased from the initial fluoride ion concentration of 5000.00 mg/L to 8.82 mg/L using CaCl2 as a calcium salt precipitant. The fluoride removal rate was 99.82%. Under these conditions, the nucleation rate of calcium fluoride precipitation was 0.19470 */(mL?min) and the growth rate was 2.952×10-3 μm/min. The relationship between the sensitivity coefficients of each factor was ipH<iT<0<it<iCa/F. The calcium-fluorine ratio and time were conducive to the nucleation of calcium fluoride crystals, and moderate pH and temperature were conducive to the growth of calcium fluoride crystals. The final precipitation product is calcium fluoride, and its surface microstructure consisted of an agglomerate structure composed of spherical calcium fluoride clusters.
HUANG Si-Yun
,
QIAN Yu-Peng
,
ZHANG Yu-Qian
,
JIE Lei
,
LI Jun-Xiao
. Study on crystallization behavior of calcium fluoride particles in fluorine-containing wastewater[J]. The Chinese Journal of Process Engineering, 2025
, 25(11)
: 1195
-1203
.
DOI: 10.12034/j.issn.1009-606X.224386