二(叔丁基苯)二硫代次膦酸从硝酸-硝酸钠介质中萃取Th(Ⅳ)

    Extraction of Th(Ⅳ) From Nitric Acid-Sodium Nitrate Media With Bis(p-Tert-Butylphenyl)Dithiophosphinic Acid

    • 摘要: 研究了二(叔丁基苯)二硫代次膦酸(bis(p-tert-butylphenyl)dithiophosphinic acid,HL)从硝酸-硝酸钠介质中萃取Th(Ⅳ)的行为和机制。以其二甲苯溶液作为有机相,考察了萃取时间、萃取剂浓度、水相NaNO3浓度、平衡水相pH值及温度等因素对萃取的影响。结果表明,该萃取剂萃取Th(Ⅳ)的分配比随萃取剂浓度、平衡水相pH值以及温度的增大而增大,随水相NaNO3浓度的增大而减小。斜率法分析结果表明,该萃取剂萃取Th(Ⅳ)符合阳离子交换机制,萃合物组成为ThL4,萃取反应式为 \mathrmT\mathrmh^4++4\mathrmH\mathrmL_\left(\mathrmo\right) \mathop\rightleftharpoons\limits^K_\mathrme\mathrmx \mathrmT\mathrmh\mathrmL_4_\left(\mathrmo\right)+4\mathrmH^+ ,25 ℃时的萃取平衡常数(Kex)为10−7.84,ΔHϴ为25.8 kJ/mol,ΔSϴ为−66.4 J/(mol•K)。实验平衡水相pH值范围内,Th(Ⅳ)、U(Ⅵ)和Ln(Ⅲ)(以Eu(Ⅲ)和Nd(Ⅲ)为代表)的相互分离因子(SF)随pH值增大而增大。当平衡水相pH值为3.11时,SFTh(Ⅳ)/Eu(Ⅲ)、SFTh(Ⅳ)/Nd(Ⅲ)和SFU(Ⅵ)/Th(Ⅳ)分别为4.2×104、1.1×104和1.0×102

       

      Abstract: Thorium, a crucial and prospective nuclear material, whether enriched and extracted from ores or recovered from the complex composition of nuclear waste, is imperative for alleviating pressure on energy resources and sustaining ecological balance. A variety of methods are currently applied within the domain of thorium isolation and purification, among which solvent extraction has the distinction of being the most commonly used and recognized extraction method in the nuclear field. Nevertheless, identifying a suitable extractant continues to pose a significant challenge. Dithiophosphinic acid has been the subject of considerable research interest due to its exceptional ability to selectively separate trivalent actinide ions, An(Ⅲ), from lanthanide ions, Ln(Ⅲ). However, the extraction of tetravalent actinide ions has received comparatively less attention. In order to further evaluate the potential application of those extractants, the extraction behavior of Th(Ⅳ) from nitric acid-sodium nitrate media was investigated using bis(p-tert-butylphenyl)dithiophosphinic acid(HL) in xylene as the organic phase. The effects of HL concentration in the organic phase on the extraction of Th(Ⅳ) were studied, as well as the NaNO3 concentration in the aqueous phase, the pH of the equilibrated aqueous phase, and the temperature, to determine the composition of the extracted complex and further to reveal the extraction mechanism. In addition, the selectivity for Th(Ⅳ) in coexistence with U(Ⅵ) and Ln(Ⅲ) was analyzed to evaluate its potential application in the advanced nuclear fuel cycle. The extraction is governed by the cation exchange mechanism, described by the equation of \mathrmT\mathrmh^4++4\mathrmH\mathrmL_\left(\mathrmo\right) \mathop\rightleftharpoons\limits^K_\mathrme\mathrmx \mathrmT\mathrmh\mathrmL_4_\left(\mathrmo\right)+4\mathrmH^+ , with the extracted complex species of ThL4. At 25 ℃, the extraction equilibrium constant(Kex) is measured as 10−7.84, while ΔHϴ is 25.8 kJ/mol and ΔSϴ is −66.4 J/( mol•K). Moreover, the determined mutual separation factors of Th(Ⅳ), U(Ⅵ) and Ln(Ⅲ) increase with the increasing pH within the experimental pH range. When the pH of the equilibrium aqueous phase is 3.11, the determined SFTh(Ⅳ)/Eu(Ⅲ), SFTh(Ⅳ)/Nd(Ⅲ), and SFU(Ⅵ)/Th(Ⅳ) are 4.2×104, 1.1×104, and 1.0×102, respectively. The high selectivity for U(Ⅵ), Th(Ⅳ) and Ln(Ⅲ) demonstrates its potential application in the separation of uranium, thorium and rare earths, providing new insights for the development and exploitation of nuclear energy resources.

       

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