二氧化硅-海藻酸钙负载磷钨酸铵复合吸附剂制备及其吸附Cs+的研究

Preparation of Ammonium Phosphotungstate Composite Loaded with Silica-calcium Alginate Hybrid Material and Its Adsorption Performance for Cs+

  • 摘要: 高放废液中放射性铯的分离提取对于高放废液的安全处置具有重要意义。针对利用粉末状无机离子交换剂去除高放废液中Cs+所面临的机械强度差、易造成工业柱堵塞的问题,本研究采用溶胶-凝胶法将磷钨酸铵细晶封装到二氧化硅-海藻酸钙杂化材料中,制备了一种毫米级新型磷钨酸铵复合吸附剂。通过SEM、FT-IR、XRD、XRF、N2-吸附/解吸等温线、颗粒强度测定仪等表征手段研究了吸附剂的结构特性,并结合静态吸附实验和动态柱吸附实验考察了所制备吸附剂在强酸性溶液中对Cs+的吸附性能。表征结果显示,支撑材料中二氧化硅的加入可有效改善海藻酸盐基质的机械性能。Cs+在磷钨酸铵复合吸附剂上的吸附动力学过程符合准二级动力学模型,吸附可在12 h内达到平衡。在3.0 mol/L的HNO3溶液中,该吸附剂对Cs+的静态和动态交换容量分别达22.9 mg/g和17.3 mg/g。磷钨酸铵复合吸附剂对Cs+表现出较高的选择性,模拟高放废液中Cs+与其他金属离子的分离因子均大于42。以上结果表明本文所制备的吸附剂具有较好的工业应用潜力。

     

    Abstract: The separation and extraction of radioactive cesium is of great significance for the safe disposal of high-level liquid waste (HLLW). Although ammonium phosphotungstate (AWP) has shown notable selectivity for Cs+ adsorption in HLLW, the micro-crystalline structure and fine powder morphology of AWP limit its industrial application with column separation. Therefore, it is important to prepare AWP-based adsorbents into a usable form to improve their utilization. In this paper, a novel millimeter-sized AWP-based adsorbent, AWP-CaALG-SiO2 composite, was prepared by encapsulating the fine crystals of AWP exchanger into a calcium alginate-silica matrix. The prepared composite was characterized using scanning electron microscopy (SEM), Fourier transform infrared (FT-IR) spectra, X-ray fluorescence (XRF), X-ray diffraction (XRD), N2 adsorption/desorption isotherms and the universal testing machine, and its adsorption performance for Cs+ in strong acidic solution was determined using both batch-type and dynamic column experiments in terms of the kinetics, equilibrium capacity and selectivity. The characterization results indicate that the addition of silica in the fabrication significantly improves the mechanical strength of composite in comparison to those without silica. The adsorption of Cs+ on AWP-CaALG-SiO2 composite could reach equilibrium within 12 h, and the adsorption kinetics follows a non-linear pseudo-second order rate equation. The distribution coefficient of Cs+ is high even in extreme acidic condition (about 150 mL/g in 8.0 mol/L HNO3 solution). The adsorption capacity of Cs+ increases significantly with the increase of initial Cs+ concentration, and the adsorption of Cs+ on AWP-CaALG-SiO2 composite can be well fitted with the Langmuir model, indicating a homogeneous single-layer adsorption process. The maximum adsorption capacity of AWP-CaALG-SiO2 composite for Cs+ is determined to be 22.9 mg/g with batch-type experiment in 3.0 mol/L HNO3 solution. In addition, the composite shows excellent selectivity toward Cs+ uptake over 8 co-existing metal ions in simulated HLLW, as evidenced by a Kd value of 772 mL/g and SF values all above 42. The dynamic column experiment shows that the composite can serve as the stationary phase in columns to effectively remove Cs+ with the maximum dynamic adsorption capacity of 17.3 mg/g. This work not only develops a granulated AWP-based composite for the selective capture of Cs+ from strongly acidic HLLW, but also provids insights into the design of high-mechanical strength ion-exchange materials for radiocesium decontamination with their practical applications.

     

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