新型calix[4]biscrown超分子识别材料制备及其吸附铷和铯性能研究

doi:10.11949/0438-1157.20201732

摘要/Abstract

摘要：

稀有金属铷和铯是重要战略资源，盐湖卤水中含有一定量铷和铯。因其组成与碱性介质的复杂性，铷铯的分离与回收极富挑战性，尚未有效解决。本文基于固定化与真空活化灌注技术将超分子衍生物杯[4]双冠6（BC6）和杯[4]双冠5（BC5）负载于高分子介孔载体XAD-7孔道中，制备与表征了新型超分子识别材料BC6/XAD-7和BC5/XAD-7。研究了水相pH和温度变化对BC6/XAD-7和BC5/XAD-7吸附典型碱金属和碱土金属离子性能的影响，考察了BC6/XAD-7和BC5/XAD-7随接触时间变化吸附铷和铯动力学行为，获得了最佳吸附条件，明确了提取钾后余液中以超分子识别材料吸附分离铯和铷的技术可行性，提出了有效吸附分离铯和铷的CREC技术流程，为应用新型超分子识别材料于盐湖卤水中吸附分离铯和铷提供理论与实验依据。

关键词: 超分子材料, 吸附, 盐湖卤水, 铷, 铯

Abstract:

Rb and Cs are important strategic resources. The effective separation of Rb and Cs from brine has been challenging work that has not been solved due to the complexity of the compositions in alkaline medium. For this purpose, a new supramolecular material BC6/XAD-7 or BC5/XAD-7 was prepared and characterized by vacuum impregnating and immobilizing BC6 or BC5 into the pores of mesoporous XAD-7 carrier. The adsorption of Rb, Cs and other typical metals on BC6/XAD-7 or BC5/XAD-7 was investigated by examining the influence of pH in aqueous phase and temperature. The adsorption kinetics of Rb and Cs onto BC6/XAD-7 and BC5/XAD-7 with the change of contact time was studied. The optimum adsorption conditions were obtained. The technical feasibility of the adsorption of Cs and Rb by the materials from a solution after K removal was confirmed. A technical process entitled CREC was proposed. It provides theoretical and experimental basis for the application of new supramolecular recognition materials in the adsorption and separation of cesium and rubidium in salt lake brine.

Key words: supramolecular material, adsorption, brine, rubidium, cesium

中图分类号:

TQ 028.8

侯林怡, 王一宁, 张安运, 苏佳天. 新型calix[4]biscrown超分子识别材料制备及其吸附铷和铯性能研究[J]. 化工学报, 2021, 72(6): 3063-3073.

HOU Linyi, WANG Yining, ZHANG Anyun, SU Jiatian. Preparation of new calix[4]biscrown supramolecular recognition materials for the adsorption of rubidium and cesium[J]. CIESC Journal, 2021, 72(6): 3063-3073.

图/表 12

图1 BC6和BC5合成技术路线

Fig.1 Synthetic technical route of BC6 and BC5

图2 calix[4]biscrown衍生物的分子结构

Fig.2 Molecular structure of calix[4]biscrown derivative

图3 BC6、BC5、XAD-7、BC6/XAD-7和BC5/XAD-7的SEM图

Fig.3 SEM images of BC6, BC5, XAD-7, BC6/XAD-7 and BC5/XAD-7

图4 BC6、BC5、XAD-7、BC6/XAD-7和BC5/XAD-7的XRD谱图

Fig.4 XRD patterns of BC6, BC5, XAD-7, BC6/XAD-7 and BC5/XAD-7

图5 BC6/XAD-7、BC5/XAD-7和XAD-7于77 K条件下的N2吸附-脱附曲线和孔径分布

Fig.5 N2 adsorption-desorption curves and pore size distribution of BC6/XAD-7, BC5/XAD-7 and XAD-7 at 77 K

表1 XAD-7、BC6/XAD-7和BC5/XAD-7的比表面积、孔径及孔体积

Table 1 Specific surface area, pore size and pore volume of XAD-7, BC6/XAD-7 and BC5/XAD-7

样品	比表面积/(m²/g)	最可几孔径/nm	孔体积/(cm³/g)
XAD-7	348.5	39.48	0.70
BC6/XAD-7	204.9	31.22	0.64
BC5/XAD-7	188.78	31.18	0.67

图6 BC6、XAD-7和BC6/XAD-7的FT-IR谱图

Fig.6 FT-IR spectra of BC6，XAD-7 and BC6/XAD-7

图7 接触时间对超分子识别材料吸附性能的影响

Fig.7 The influence of contact time on the adsorption performance of supramolecular recognition materials

图8 pH变化对超分子识别材料吸附性能的影响

Fig.8 The influence of pH on the adsorption performance of supramolecular recognition materials

图9 温度变化对超分子识别材料吸附性能的影响

Fig.9 The influence of temperature on the adsorption of supramolecular recognition materials

图10 BC6/XAD-7和BC5/XAD-7吸附性能比较

Fig.10 Comparison of the adsorption of BC6/XAD-7 and BC5/XAD-7

图11 超分子识别材料BC6/XAD-7或BC5/XAD-7吸附分离铯和铷的CREC流程

Fig.11 An advanced CREC process for cesium and rubidium separation by extraction chromatography by BC6/XAD-7 or BC5/XAD-7

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