磁性微孔类甲酸镧制备及其高效除氟性能研究

Synthesis of magnetic microporous lanthanum formate for rapid and high-capacity fluoride removal

  • 摘要: 含氟工业废水治理是目前众多企业关注的热点问题,尤其是混凝沉淀出水中氟难以达标。采用水热合成法制备磁性微孔类甲酸镧除氟剂(FML),利用单因素实验探讨不同镧含量和反应条件对氟吸附效果的影响,并通过X射线衍射仪(XRD)、场发射扫描电镜-能谱仪(FESEM-EDS)、微孔物理吸附仪(BET)、傅里叶红外光谱仪(FTIR)、Zeta电位分析仪表征FML的晶体结构、表面吸附位点、比表面积及孔径分布和表面电荷特性,探讨FML对氟吸附机理。结果表明:FML0.5、FML1.0、FML1.5和FML2.0(含氯化镧物质的量分别为0.5、1.0、1.5、2.0 mmol)吸附氟速率逐次增加,均可将含氟废水中氟浓度从5.0 mg/L降低至1.0 mg/L以下,达到GB 3838—2002《地表水环境质量标准》Ⅲ类水质标准中氟化物浓度限值要求(低于1.0 mg/L);在pH为6.32,温度为318 K,氟初始浓度为10.0 mg/L,FM2.0投加量为0.2 g/L反应条件下,FML2.0对氟的去除率为99%以上,最大氟吸附量为138.3 mg/g;阴离子对氟吸附过程影响表现为\mathrmCO_3^2- >\mathrmSO_4^2- >Cl;氟离子去除机制主要通过静电引力作用被吸附到FML表面上并取代FML表面吸附位点羟基基团。FML2.0对氟的吸附动力学和吸附热力学分别遵循伪二级动力学反应模型和Langmuir模型,说明该吸附过程以化学吸附和单层吸附为主,属于吸热反应,温度越高越有利于吸附。将FML2.0应用于工业含氟废水经混凝沉淀出水的处理,在FML2.0投加量为0.2 mg/L时,反应60 min后出水中氟浓度由9.80 mg/L降低到0.78 mg/L,表明该除氟剂具有较好的应用前景。

     

    Abstract: The treatment of fluorine-containing industrial wastewater is a hot issue for many enterprises, especially the difficulty in meeting the standard for coagulation-precipitation effluent. Magnetic microporous lanthanum formate defluorinator (FML) was prepared using the hydrothermal synthesis method. The influence of different lanthanum contents and reaction conditions on fluorine adsorption was investigated by single factor experiment. The crystal structure, surface adsorption sites, specific surface area and pore size distribution, and surface charge characteristics of FML were characterized by X-ray diffractometer (XRD), field emission scanning electron microscopy- energy dispersive spectrometer (FESEM-EDS), microporous physical adsorption analyzer (BET), Fourier transform infrared spectrometer (FTIR), and zeta potential analyzer, and the adsorption mechanism of FML on fluorine was discussed. The results showed that: The fluoride adsorption rates of FML0.5, FML1.0, FML1.5 and FML2.0 gradually increased, all of which could reduce the fluorine concentration in fluorine-containing wastewater from 5.0 mg/L to less than 1.0 mg/L, and meet the fluoride concentration limit (1.0 mg/L) in Class Ⅲ standard of Environmental Quality Standards for Surface Water (GB 3838-2002). Under the reaction conditions of pH 6.32, temperature 318 K, 10.0 mg/L of initial fluorine concentration and 0.2 g/L of FM2.0, the removal rate of fluorine by FML2.0 was more than 99%, and the maximum adsorption capacity of fluorine was 138.3 mg/g. The decreasing rule of anion effect on fluorine adsorption was \mathrmCO_3^2- >\mathrmSO_4^2- >Cl. The removal mechanism of fluoride ions was mainly achieved by electrostatic attraction, which adsorbed onto the surface of FML and replaced the hydroxyl groups at the adsorption sites on the FML surface. The adsorption kinetics and thermodynamics of fluorine by FML2.0 followed the pseudo-second-order kinetic reaction model and Langmuir model, respectively. The adsorption process mainly consisted of chemisorption and monolayer adsorption, belonging to endothermic reactions. The higher the temperature, the more favorable the adsorption. FML2.0 was applied to the treatment of fluorine-containing industrial wastewater by coagulation and sedimentation. When the dosage of FML2.0 was 0.2 g/L, the fluorine concentration in the effluent was reduced from 9.80 mg/L to 0.78 mg/L after 60 min of reaction, indicating that the defluorinator has a good application prospect.

     

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