机械化学活化对离子交换树脂模型腐蚀膜溶解的影响

M. Palamarchuk, D. Shlyk, S. Bratskaya
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摘要

在运行和中间储存过程中形成的无机沉积物含有放射性核素,在核电厂特殊水净化过滤器中使用的废离子交换树脂的化学净化过程中去除放射性核素已被证明是一项挑战。在这种沉积物中,腐蚀基团的放射性核素(58.60Co, 54Mn, 51Cr)通常位于难溶性氧化铁的晶格中。本文讨论了利用机械化学活化来净化被结构材料活化腐蚀产物沉积污染的废离子交换树脂的可能性。以KU-2-8阳离子交换剂表面天然和合成的57Co标记磁铁矿样品作为模型沉积。结果表明,机械化学活化时间的增加导致磁铁矿在基于乙二胺四乙酸二钠盐(Trilon B)和硝酸的模型去污溶液中的溶解速率增加。结果表明,使用Trilon B时,磁铁矿的溶解效率更高,这可以解释为氧化表面与有机络合剂之间的相互作用。可以假设,磁铁矿在干燥试剂(Trilon B、草酸、抗坏血酸和柠檬酸)存在下的机械化学活化过程中发生固相反应。因此,在低磁铁矿/溶液比下,在氧化物表面形成的难溶壳阻碍了溶解。与无试剂活化不同,对于在草酸存在下活化的磁铁矿,溶液/磁铁矿比的增加促进了氧化铁的溶解。以模型阳离子交换剂为例,结果表明,在草酸存在下,对含有活化腐蚀产物沉积物的废离子交换树脂进行机械化学活化后,去污率和效率显著提高。
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Influence of mechanochemical activation on dissolving model corrosion films formed on ion-exchange resins using Trilon B
Inorganic deposits formed during operation and intermediate storage contain radionuclides, whose removal during the chemical decontamination of spent ion-exchange resins used in filters for special water purification at nuclear power plants has proved to be a challenge. In such deposits, radionuclides of the corrosion group (58.60Co, 54Mn, 51Cr) are typically located in the crystal lattice of poorly soluble iron oxides. The present work discusses the possibility of using mechanochemical activation in the decontamination of spent ion-exchange resins polluted with deposits of activated corrosion products from structural materials. Samples of natural and synthesised on the surface of the KU-2-8 cation exchanger in the presence of the 57Co label magnetites were used as model deposits. It was shown that an increase in the duration of mechanochemical activation leads to an increase in the dissolution rate of magnetite in model decontamination solutions based on еthylenediaminetetraacetic acid disodium salt (Trilon B) and nitric acid. It was shown that, when using Trilon B, magnetite dissolves more efficiently, which is explained by the interaction between the oxide surface and organic complexing agents. It can be assumed that solid-phase reactions occur during the mechanochemical activation of magnetite in the presence of dry reagents (Trilon B, oxalic, ascorbic and citric acids). Therefore, a poorly soluble shell formed on the oxide surface hinders the dissolution at a low magnetite/solution ratio. Unlike the reagent-free activation, for magnetite activated in the presence of oxalic acid, an increase in the solution/magnetite ratio promotes the dissolution of iron oxides. Using the example of a model cation exchanger, it was shown that the rate and efficiency of decontamination of spent ion-exchange resins polluted with deposits containing activated corrosion products increase significantly after mechanochemical activation in the presence of oxalic acid.
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