纳米羟基磷灰石去除地浸铀矿山退役采区地下水中铀的性能及机理

Performance and mechanism of nano-hydroxyapatite in removing uranium from groundwater in decommissioned in situ leaching uranium mining areas

  • 摘要: 针对地浸铀矿山退役采区铀污染地下水问题,采用凝胶法制备了纳米羟基磷灰石(hydroxyapatite,HAP)材料,并研究了反应时间、六价铀U(Ⅵ)初始质量浓度ρ0、反应温度及干扰离子等因素对U(Ⅵ)去除效果的影响,探讨了HAP去除U(Ⅵ)的反应动力学和热力学行为。通过X射线衍射(XRD)、傅里叶变换红外光谱(FTIR)、扫描电镜(SEM)、X射线光电子能谱(XPS)等测试技术,对HAP去除U(Ⅵ)前后的产物进行了表征,进一步阐明了HAP去除U(Ⅵ)的机理。最后,评价了HAP对真实地浸铀矿山退役采区地下水的修复效果。研究结果表明:pH=3.0的酸性U(Ⅵ)溶液,反应在120 min内达到吸附平衡,HAP对U(Ⅵ)的去除率为96.87%,其最大吸附容量达40.36 mg/g;pH=7.0的中性U(Ⅵ)溶液,反应在360 min内达到吸附平衡,HAP对U(Ⅵ)的去除率为96.04%,展现出了优异的吸附性能。不同干扰离子对HAP去除U(Ⅵ)的效果存在差异,在pH=3.0时,Al3+对HAP去除U(Ⅵ)的效果具有抑制作用;在pH=7.0时,\mathrmHCO_3^- 对HAP去除U(Ⅵ)的效果具有抑制作用,而\mathrmPO_4^3- 则具有促进作用。不同pH条件下,HAP去除U(Ⅵ)的机理也存在差异,在pH=3.0时,其去除U(Ⅵ)的机理主要通过HAP的溶解−沉淀、表面络合和离子交换实现;而在pH=7.0时,则以表面络合和离子交换为主导。HAP对实际铀污染地下水同样表现出良好的处理效果:在酸性条件下(ρ0=10.05 mg/L,pH=2.86),HAP对U(Ⅵ)的去除率达87.5%;在CO2+O2中性环境下(ρ0=10.3 mg/L,pH=7.58),其去除率达到94.5%。综上,HAP具有良好的吸附U(Ⅵ)的能力和环境适应性,可作为地浸铀矿山退役采区地下水中铀污染的修复材料。

     

    Abstract: This study addresses the issue of uranium-contaminated groundwater in decommissioned in-situ leaching uranium mining areas. Nano-hydroxyapatite (HAP) was synthesized using the gel method, and its ability to remove U(Ⅵ) was investigated by studying the effects of factors such as reaction time, initial U(Ⅵ) mass concentration, reaction temperature, and interfering ions. The reaction kinetics and thermodynamic behavior of HAP in U(Ⅵ) removal were also explored. The results before and after U(Ⅵ) removal by HAP were characterized using X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X-ray photoelectron spectroscopy (XPS), to elucidate the mechanism of U(Ⅵ) removal by HAP. Finally, the effectiveness of HAP for the remediation of real groundwater from decommissioned in situ uranium mining areas was evaluated. The results showed that in an acidic U(Ⅵ) solution (pH=3.0), adsorption equilibrium was reached within 120 min, with a U(Ⅵ) removal rate of 96.87% and a maximum adsorption capacity of 40.36 mg/g. In a neutral U(Ⅵ) solution (pH=7.0), adsorption equilibrium was achieved within 360 minutes, with a U(Ⅵ) removal rate of 96.04%, demonstrating excellent adsorption performance. The influence of various interfering ions on U(Ⅵ) removal by HAP was also investigated. At pH=3.0, Al3+ ions inhibited U(Ⅵ) removal, while at pH=7.0, \mathrmHCO_3^- ions had an inhibitory effect, whereas \mathrmPO_4^3- ions facilitated U(Ⅵ) removal. The mechanisms of U(Ⅵ) removal by HAP also varied under different pH conditions: at pH=3.0, the removal mechanism was mainly based on HAP dissolution-precipitation, surface complexation, and ion exchange; at pH=7.0, surface complexation and ion exchange dominated. HAP also demonstrated excellent performance in the treatment of real uranium-contaminated groundwater. Under acidic conditions (ρ0=10.05 mg/L, pH=2.86), the U(Ⅵ) removal rate reached 87.5%. In a CO2+O2 neutral environment (ρ0=10.3 mg/L, pH=7.58), the removal rate increased to 94.5%. In conclusion, HAP shows strong adsorption capacity for U(Ⅵ) and good environmental adaptability, making it a promising material for the remediation of uranium-contaminated groundwater in decommissioned in-situ leaching uranium mining areas.

     

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