Advances in Basic Research on Solution Chemistry for Zr-Hf Extraction and Separation System AITranslate

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Basic Information:

DOI：10.13373/j.cnki.cjrm.XY23080010

Chinese Library Classification Number:O652.62

Citation Information:

Nuclear-grade zirconium （Zr）and hafnium （Hf）are important basic materials for securing the development of the nuclear industry. Solvent extraction separation is the key to the preparation of nuclear-grade Zr and Hf. Zr（Ⅳ）and Hf（Ⅳ）ions are in an extremely tendency to hydrolyze and polymerize in aqueous solution. In order to inhibit the hydrolysis of Zr（Ⅳ）and Hf（Ⅳ）and to increase their extraction reaction activity，acidic aqueous phase media are commonly used. The traditional MIBK-HSCN （methyl isobutyl ketone-thiocyanate）extraction system has many shortcomings，such as considerable loss of extractant dissolution and serious environmental pollution. To overcome those shortcomings，developing of alternative extractants has been continuously considered as a research hotspot. Depending on the active functional group，the extractants developed in recent years can be mainly categorized into O-，N-，P- and S-containing types. According to the theory of hard and soft acids and bases （HSAB）， Zr（Ⅳ）and Hf（Ⅳ）ions are classified as a hard Lewis acids，while O is classified as a hard base. Therefore，among the extractants that have been developed so far，O-containing extractants are the most abundant. Among them，acidic phosphorus-oxygen extractants such as P204 have shown excellent performance. Meanwhile，research on "green" and "designable" N-or P-containing ionic liquid extractants has become quite popular. However，the research on the above extractants is still in the laboratory stage. It is difficult to replace MIBK extractant and realize industrial application. In the selection of organic solvents，the influence of factors such as density and viscosity are usually taken into account. In addition，it is recommended that due attention should be paid to the structural characteristics of the extractant and the organic solvent. For example，the phosphonic acid extractant is usually in the form of a dimer. Therefore，the selection of organic solvents with electron-donor characteristics as diluents will facilitate the depolymerization of the extractant and expose its active functional groups. Moreover，from the perspective of interfacial chemical reaction equilibrium，the selected organic solvent with suitable solubility is also necessary to improve the separation efficiency. Among the commonly used co-extractants，thiocyanic acid has a special structure and strong coordination ability. However，it has poor thermal stability，and decomposes easily. In recent years，the applied research of Hoffmeister series in the field of solvent extraction and separation has been gradually expanded，which provides a useful reference for the selection of co-extractants. Furtherly，both HSAB theory and the Hofmeister series are important principles in the selection of salting-out agents and reverse-extraction agents. In general，the following factors should be taken into account：1）microstructure and acid-base differences of Zr（Ⅳ）and Hf（Ⅳ）ions；2）The strength of complexation stability of Zr（Ⅳ）and Hf（Ⅳ）ions with different anions；3）The magnitude of the affinity of the different anions towards O （organic）/A （aqueous）phases.