偕胺肟基材料海水提铀技术研究评述及展望

Review and Perspective on Technology for Uranium Extraction from Seawater Using Amidoxime-based Materials

  • 摘要: 从材料筛选研发和实施方式演变两个方面简要回顾了海水提铀技术的发展过程。针对性地介绍了两种实用前景较好的偕胺肟基材料接枝制备方法,详细综述了近年来与偕胺肟基材料相关的小分子配体与铀酰离子及其他共存金属离子的配位化学研究,特别强调了不同条件下金属离子诱导偕胺肟官能团的转化反应。对海水提铀技术研发的限制性因素进行了分析,并试探性地从宏观实施方案和微观机理研究两个方面预测了海水提铀材料和技术的研发方向。

     

    Abstract: The development of technology for uranium extraction from seawater is briefly described with regard to the aspects of material screening and evolution of deployment methods. By evaluating the developed materials of possibly practicable in last seventy years, grafted polymers of amidoxime functionality are uniquely addressed in a broader perspective of economic interests. Two representative grafting methods for preparing absorbents bearing amidoxime groups with good practical prospects are summarized. The philosophy of approaching more grafting degree and more functional group intensity is scrutinized, finding that the amount and intensity of amidoxime group on the adsorbents are not proportionally related to the extraction capability of uranium from seawater. The contribution made in recent years to the coordination chemistry of some related small molecule ligands with uranyl ion and other coexisting metal ions is reviewed in detail. Especially the complexation of uranyl ion with two small molecules, succinimidedioxime and succindiamodoxime which represent the minor structures from less favorable ‘head-to-head’ connection of polymerization of acrylonitrile, is comparatively compiled with that of glutarimidedioxime and glutardiamidoxime which represent the major structures from the favorable ‘heat-to-end’ connection. With similar structure and same functional group, the two cyclic compounds, succinimidedioxime and glutarimidedioxime present clear difference in complexation with uranyl ion under seawater conditions. The six-member ring glutarimidedioxime favorably forms mononuclear 1∶2 uranyl complex, while the five-member ring succinimidedioxime tends to give di-nuclear 2∶2 uranyl complex. The conversion reactions of the amidoxime functional groups induced by metal ions under different conditions are tapped to emphasize the variety of functional groups of the absorbents, which might provide additional approaches to optimize the adsorbents with more favorable functional groups for economically catching uranium from seawater. The cyclic glutarimidedioxime functional group can be easily prepared from the open chain glutardiamidoxime through the reaction induced with proton and nickel ions together at room temperature instead of the reaction of heating to over 120 ℃ in traditionally used methods. The unreached functional groups of hydroxamic acids derived from the hydrolysis of the major functional groups in previous studies are proposed for examining. The restrictive factors for the uranium extraction from seawater are analyzed in regard with the open environment of the ocean and the very low concentration of uranium. The possible focusing points of the research and development on the technology for uranium extraction is tentatively predicted in respect to the practical employment method and the exact extraction mechanisms. In contract with the philosophy of emphasizing the selectivity of the adsorbents for uranium in previous research, it is suggested that a comprehensive approach of economically extracting uranium might be to take the co-extraction of other valuable metal ions, such as lithium and gold, from seawater into account.

     

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