我国内蒙古、陕西、山西等部分地区背景氟浓度偏高，致使以煤为原料的焦化行业废水通过膜处理后的浓盐水中含有高浓度的氟离子，结晶分盐是浓盐水实现“零排放”的必要手段，而过高的氟浓度会对浓盐水的处理产生不良影响。为了降低浓盐水中高浓度氟离子对蒸发器的腐蚀及其对分盐纯度的影响，以河北某焦化企业浓盐水为研究对象，基于浓盐水的水质特征以及课题组研发的高效除氟药剂，研究了共存离子SO4 2−、NO3 −、Cl−对除氟药剂效果的影响；采用SEM和EDS表征了除氟药剂及处理后絮体，分析了除氟的机理；探讨了CaCl2、PAC（聚合氯化铝）、除氟药剂一段法处理工艺对实际焦化浓盐水的处理效果；设计并优化了CaCl2+除氟药剂两段法除氟工艺及主要影响参数，分析了不同处理方案的经济成本。研究结果表明：浓盐水中3种主要的共存离子对除氟药剂效果影响的顺序为SO4 2−>NO3 −>Cl−；SEM和EDS分析表明F元素均匀分布于絮体中，可通过除氟药剂的表面吸附、表面络合、表面羟基交换等作用机理高效去除；CaCl2、PAC、除氟药剂一段法中，除氟药剂一段法效果最好，投加量为8 g/L时去除率达到92.3%；CaCl2+除氟药剂的两段除氟工艺能将氟离子质量浓度从238.27 mg/L降至10 mg/L以下；CaCl2投加量6 g/L和除氟药剂投加量2 g/L的方案处理成本最低，处理每吨焦化浓盐水为14.03元。CaCl2+除氟药剂的两段除氟工艺可经济高效地去除焦化浓盐水中高浓度氟离子，为焦化行业废水零排放提供技术参考。

Due to the high background fluoride content in part of China's Inner Mongolia, Shaanxi, Shanxi and other high-fluorine regions, the concentrated brine with high concentrations of fluoride ions was produced after membrane treatment of coking industry wastewater using coal as raw material. Crystallization and salt separation of brine salt is a necessary method to achieve "zero emission", but the excessive fluoride concentration can have adverse effects on the treatment of concentrated brine. In order to reduce the corrosion of evaporator caused by high concentration of fluoride ions in concentrated brine and its impact on the purity of salt separation, this paper took concentrated brine from a coking enterprise in Hebei, discussed the effects of co-existing ions SO4 2−, NO3 − and Cl− on defluorination agents based on the water quality characteristics of concentrated brine and the defluorination agent developed by our research group. Meanwhile, SEM and EDS were used to characterize the defluorination agents and treated flocs, and the mechanism of defluorination was analyzed. The defluorination effect of one stage treatment process with CaCl2, PAC and defluorination agent was compared. The combined process of CaCl2 and defluorination agent applied in the actual concentrated brine was designed and optimized, then analyzed the economic costs of different treatment schemes. The results showed that the influence order of the three co-existing ions on the effect of defluorination agent was SO4 2−>NO3 −>Cl−. SEM and EDS analysis indicated that F element was uniformly distributed in the floc and could be efficiently removed through the surface adsorption, surface complexation, and surface hydroxyl exchange mechanism. One stage treatment process with defluorination agent was better than the effect of CaCl2 or PAC, when the dosage of defluorination agent was 8 g/L, the removal rate reaches 92.3%. The combined process of CaCl2 and defluorination agent could reduce the concentration of fluoride ions from 238.27 mg/L to less than 10 mg/L. The combination cost of CaCl2 dosage of 6 g/L and fluoride removal agent dosage of 2 g/L was the lowest, which was 14.03 yuan per ton of coking concentrated brine. The two-stage defluorination process with CaCl2+defluorination agent can economically and efficiently remove high concentration fluoride ions from coking concentrated brine which can provide a technical reference for zero discharge of wastewater in the coking industry.