高放废液中Cs (I)的高效分离：新型杯状[4]芳烃-2,4-冠-6醚的合成、逆流萃取及Cs配合物的结构

IF 9 1区工程技术 Q1 ENGINEERING, CHEMICAL

Separation and Purification Technology Pub Date : 2024-12-25 DOI:10.1016/j.seppur.2024.131261

Haolong Wang , Tengfei Cui , Zhen Xu , Qing Chang , Qiang Jin , Zongyuan Chen , Zhijun Guo

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引用次数: 0

摘要

从高放废液（HLLW）中去除放射性铯同位素（如137Cs和135Cs）对核工业具有重要意义。本研究合成了四种新的具有苄基取代基的杯[4]芳烃-2,4-冠-6醚（C[4]C-6），分别为25,27-bis（苄基）杯[4]-冠-6 (Bn-C[4] -6), 25,27-bis（4-丁基-苄基）杯[4]-冠-6 （C4-Bn-C[4] -6）和25,27-bis（4-叔丁基-苄基）杯[4]-冠-6 (tBu-Bn-C[4] -6)，并筛选了它们作为HLLW中分离Cs+的萃取剂。与具有烷基取代基的同系物相比，该配体具有更好的萃取性能和更高的Cs选择性。新配体的高Cs选择性与紫外-可见滴定测定的Cs配合物的较大稳定性常数是一致的。采用配体作为萃取剂的多级逆流萃取工艺，模拟HLLW的Cs去除率为99.9 %。这些配体对HNO3具有良好的耐受性和良好的辐照稳定性，具有广阔的应用前景。此外，还研究了配体与Cs+的配位机理以及[Cs(Bn-C[4]C-6)(NO3)]·EtOAc和Cs(tBu-Bn-C[4]C-6)(NO3)（H2O）的晶体结构。结果证实Cs+与冠醚部分的6个给氧原子配位，并通过阳离子-π相互作用与两个旋转苯基环相互作用。硝酸盐阴离子与水分子以双齿或单齿方式参与配位，保证了Cs+的配位数为8。本研究表明，对于Cs+与HLLW的分离，苯基及其衍生物是除了传统长度不同的烷基之外，取代基团1,3-替代杯[4]芳烃-2,4冠-6配体的替代选择。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

Efficient separation of Cs (I) from high-level liquid Waste: Synthesis of new Calix[4]arene-2,4-crown-6 Ethers, counter-current extraction and structures of Cs complexes

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Efficient separation of Cs (I) from high-level liquid Waste: Synthesis of new Calix[4]arene-2,4-crown-6 Ethers, counter-current extraction and structures of Cs complexes

The removal of radioactive cesium isotopes, such as ¹³⁷Cs and ¹³⁵Cs, from high-level liquid waste (HLLW) is of great significance to nuclear industry. In this study, four new calix[4]arene-2,4-crown-6 ethers (C[4]C-6) with benzyl substituents, 25,27-bis(benzyloxy)calix[4]arene-crown-6 (Bn-C[4]C-6), 25,27-bis(4-methyl-benzyloxy)calix[4]arene-crown-6 (C1-Bn-C[4]C-6), 25,27-bis(4-butyl-benzyloxy)calix[4]arene-crown-6 (C4-Bn-C[4]C-6) and 25,27-bis(4-tert-butyl-benzyloxy)calix[4]arene-crown-6 (tBu-Bn-C[4]C-6), were synthesized and screened as extractants for Cs⁺ separation from HLLW. The ligands showed better extraction performance and higher Cs selectivity in comparison with their homologue with alkyl substituent. The higher Cs selectivity of the new ligands was in consistent with the larger stability constants of Cs complexes measured from UV–vis titrations. A multistage counter-current extraction process using the ligands as extractants resulted in a Cs removal of 99.9 % from the simulated HLLW. The ligands are promising for application because they also exhibit good tolerance to HNO₃ and satisfactory irradiation stability. Moreover, the coordination mechanism of the ligands with Cs⁺ and the crystal structures of [Cs(Bn-C[4]C-6)(NO₃)]·EtOAc and Cs(tBu-Bn-C[4]C-6)(NO₃)(H₂O) were investigated. The results confirmed that Cs⁺ coordinates with 6 oxygen donor atoms of the crown ether moiety and interacts with two rotated phenyl rings via cation-π interaction. Nitrate anion takes part in the coordination either in a bidentate mode or in a mono dentate mode along with a water molecule, which ensures a coordination number of 8 for Cs⁺. This study implies that benzyl and its derivatives are alternative options of the substituent groups to the 1,3-alternate calix[4]arene-2,4-crown-6 ligands besides traditional alkyls with variant lengths, regarding to Cs⁺ separation from HLLW.

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来源期刊

Separation and Purification Technology 工程技术-工程：化工

CiteScore

14.00

自引率

12.80%

发文量

2347

审稿时长

43 days

期刊介绍： Separation and Purification Technology is a premier journal committed to sharing innovative methods for separation and purification in chemical and environmental engineering, encompassing both homogeneous solutions and heterogeneous mixtures. Our scope includes the separation and/or purification of liquids, vapors, and gases, as well as carbon capture and separation techniques. However, it's important to note that methods solely intended for analytical purposes are not within the scope of the journal. Additionally, disciplines such as soil science, polymer science, and metallurgy fall outside the purview of Separation and Purification Technology. Join us in advancing the field of separation and purification methods for sustainable solutions in chemical and environmental engineering.