黄河流域典型煤矿矿井水协同除浊除氟药剂的制备及应用

黄河流域是我国煤炭潜力最大的区域，矿井水涌水量大但资源利用率不高，尤其在干旱和半干旱的高氟地区，矿井水中氟离子超标已成为制约提高矿井水资源利用率的主要因素之一。采用正交试验筛选出高效除氟药剂的5种组分〔聚合氯化铝（PAC）、聚合硅酸铝、硝酸镁、聚合氯化铁、羧甲基淀粉钠〕，采用单因素试验探讨了不同制备条件和反应条件对除氟效果的影响，并通过X射线能谱分析（EDS）、X射线光电子能谱（XPS）和傅里叶变换红外光谱（FT-IR）表征探讨了除氟机理。结果表明：在金属总量M/Si、Al/Mg、Al/Fe的摩尔比分别为43、40、40条件下研制的除氟药剂，均可将含氟废水中氟离子浓度由20 mg/L降至1.0 mg/L以下，达到GB 3838—2002《地表水环境质量标准》Ⅲ类中氟化物浓度限值要求（1.0 mg/L）；当除氟药剂投加量为1.25 g/L，初始pH为2~12，悬浮物浓度为100~2 000 mg/L，聚丙烯酰胺（PAM）投加量为0.4 mg/L时，处理后上清液剩余氟离子浓度均可控制在1.0 mg/L以下，氟离子去除率达95%以上；除氟药剂中Al、Si元素起到重要的除氟作用，主要通过形成Al—F—Al等金属络合物沉淀被去除；将除氟药剂应用于黄河流域某煤矿含氟矿井水的处理，在除氟药剂投加量为400 mg/L、PAM投加量为0.2 mg/L时，氟离子浓度从5.6 mg/L降至0.85 mg/L，并协同将矿井水浊度从500 NTU降至4.59 NTU，吨水处理药剂成本为1.602元。该除氟药剂在黄河流域含氟矿井水处理中具有较好的应用潜力。

Research on the preparation and application of collaborative turbidity and fluorine removal agents for typical coal mine water in the Yellow River basin

The Yellow River basin is the region with the greatest coal potential in China. Although the amount of coal mine water inflow is large, the resource utilization rate is not high and, especially in arid and semi-arid areas with high fluorine content, the excessive fluoride ions in coal mine water have become one of the main factors restricting the improvement of mine water resource utilization rate. Orthogonal experiments were used to screen out five components of efficient defluorination agents, including polyaluminium chloride (PAC), poly-aluminum silicate, magnesium nitrate, poly-ferric chloride (PFC), and carboxyl methyl starch sodium. The single factor experimental method was used to explore the effects of different preparation and reaction conditions on the defluorination effect, and the defluorination mechanism was preliminarily explored through X-ray energy spectrum analysis (EDS), X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FT-IR) characterization. The experimental results showed that the fluoride removal agent developed under the conditions of the total amount of metal to Si molar ratio of 43, Al/Mg molar ratio of 40, and Al/Fe molar ratio of 40 could reduce the concentration of fluoride ions in wastewater from 20 mg/L to below 1.0 mg/L, meeting the Class Ⅲ water fluoride limit requirements (1.0 mg/L) of Environmental Quality Standards for Surface Water (GB 3838-2002). When the dosage of the fluoride removal agent was 1.25 g/L, the initial pH was 2-12, the suspended solids concentration was 100-2 000 mg/L, and the polyacrylamide (PAM) dosage was 0.4 mg/L, the residual fluoride ion concentration in the supernatant after treatment could be controlled below 1.0 mg/L, and the fluoride removal rate could reach over 95%. Al and Si elements of the defluorination agent played an important role in defluorination, and their mechanism was mainly through the formation of metal complexes such as Al-F-Al for precipitation and removal. Applying defluorination agents to the treatment of fluorinated mine water in a certain coal mine in the Yellow River Basin, the concentration of fluoride ions decreased from 5.6 mg/L to 0.85 mg/L when the dosage of defluorination agents was 400 mg/L and PAM was 0.2 mg/L. Simultaneously, the turbidity of mine water could be reduced from 500 NTU to 4.59 NTU. The cost of water treatment agents per ton was 1.602 yuan. The defluorination agent has good application potential in the treatment of mine water containing fluorine in the Yellow River basin.