三元超分子识别材料制备及其基础吸附特性研究
发布时间：2018-07-17 15:17
【摘要】：90Sr、137Cs是放射性高释热核素,在最终地质处置中对高放废液(Highly active liquid waste,HLW)固化体的安全性存在潜在的危害,其有效分离是国际分离科学与技术前沿领域尚未攻克的热点和难点问题之一,以新材料、新技术和新方法为手段,是从HLW中高效分离回收Cs、Sr的有效途径。本文基于杯芳冠醚及冠醚衍生物超分子主体,通过制备与表征其高分子基超分子识别材料,研究Cs、Sr及典型共存元素的主-客体识别及吸附行为,为寻找出色的超分子识别材料有效分离Cs、Sr提供理论与实验依据。主要研究结果如下:1.合成 了六种 Calix[4]crown 衍生物:杯[4]双冠-6(Calix[4]BisCrown-6,BC6)、杯[4]双冠-5、(Calix[4]BisCrown-5,BC5)、25,27-二(正丙氧基)杯[4]芳烃-26,28-冠-6(nProCalix[4]MonoCrown-6,BnPC6)、25,2,27(异丙氧基)杯[4]芳烃-26,28-冠-6(iProCalix[4]MonoCrown-6,BiPC6)、25,27-二(癸氧基)杯[4]芳烃-26,28-冠-6(NonyloxyCalix[4]MonoCrown-6,NoNC6)和25,227-(十十烷氧基)杯[4]芳烃-26,28-冠-6(DodecyloxyCalix[4]MonoCrown-6,DoDC6);以1H NMR、ESI-MMS、元素分析和SEM等手段,对其组成和结构进行了表征。2.以独有的真空活化灌注技术,将冠醚衍生物如二环己基-18-冠-6(DCH18C6,DC)和 4'4"(5")-二叔丁基二环己基-18-冠-6(DtBuCH18C6,DT)和上述合成的杯芳冠醚同时导入并固定化在多孔高分子载体XAD-7上,制备了 7种新型三元高分子基超分子识别材料(Calix[4]Crown/Crown-ether/XAD-7);以SEM、N2吸附-脱附等温曲线、XRD和TG-DSC等手段表征了材料结构和组成,考察了材料复合机理。结果表明:通过分子间的相互作用力超分子主体能与XAD-7有效复合,形成含有丰富孔径的新型介孔材料。3.研究了三元高分子基超分子识别材料对模拟高放废液中Cs、Sr和Rb等20种典型金属离子的吸附行为;考察了 HNO3浓度、接触时间、温度及pH等因素变化对功能材料吸附性能的影响。结果表明:7种材料的吸附行为受介质酸度和 pH 影响较大。BnPDTX7、DoDDTX7、BC6DCX7、BnPDCX7、NoNDTX7和BC6DCX7对Cs、Sr、Rb、Ba和K有较为显著的吸附行为,BC5DTX7对K和Rb有显著的吸附行为,它们对其余15种被试验金属离子均表现为弱吸附或基本不吸附。4.研究了三元超分子识别材料的吸附等温线、吸附动力学及吸附热力学模型,提出并讨论了吸附机理。结果表明:相对于Freundlich模型,高分子基超分子识别材料的吸附更符合Langmuir模型;符合准二级动力学模型;且吸附过程表现为单分子层化学吸附。
[Abstract]:90Sr ~ (137Cs) is a radionuclide with high release heat. In the final geological disposal, there is a potential hazard to the safety of high level active liquid waste liquid (HLW) solidification. Its effective separation is one of the hot and difficult problems that have not been solved in the frontier field of international separation science and technology. By means of new materials, new technologies and new methods, it is an effective way to efficiently separate and recover CSN Sr from HLW. Based on the supramolecular host of calix aryl crown ether and its derivatives, the host-guest recognition and adsorption behavior of CSN Sr and its typical co-existing elements were studied by preparing and characterizing their polymer based supramolecular recognition materials. It provides theoretical and experimental basis for the effective separation of CSN Sr with excellent supramolecular recognition materials. The main results are as follows: 1. 鍚堟垚 浜嗗叚绉，
本文编号：2130073
[Abstract]:90Sr ~ (137Cs) is a radionuclide with high release heat. In the final geological disposal, there is a potential hazard to the safety of high level active liquid waste liquid (HLW) solidification. Its effective separation is one of the hot and difficult problems that have not been solved in the frontier field of international separation science and technology. By means of new materials, new technologies and new methods, it is an effective way to efficiently separate and recover CSN Sr from HLW. Based on the supramolecular host of calix aryl crown ether and its derivatives, the host-guest recognition and adsorption behavior of CSN Sr and its typical co-existing elements were studied by preparing and characterizing their polymer based supramolecular recognition materials. It provides theoretical and experimental basis for the effective separation of CSN Sr with excellent supramolecular recognition materials. The main results are as follows: 1. 鍚堟垚 浜嗗叚绉，
本文编号：2130073
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