ThO2在HNO3中的回流溶解
Reflux Dissolution of Thorium Dioxide in Nitric Acid
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摘要: 为了寻求一种替代目前依赖氟离子的溶解方法,从而避免对不锈钢溶解器造成腐蚀并影响后续处理的问题,探索研究了ThO2在HNO3中的回流溶解过程。通过使用回流溶解装置并采用HNO3作为溶解剂,研究了HNO3浓度、温度和初始Th4+浓度对ThO2溶解效果的影响。结果表明:ThO2在HNO3中的溶解过程的表观活化能为41.47 kJ/mol;在HNO3初始浓度为9~12 mol/L时,随着HNO3初始浓度的增加,ThO2的溶解速率也随之增加,表现出约为3的表观级数;然而,当HNO3初始浓度超过12 mol/L后,ThO2溶解速率开始下降。此外,实验还发现初始Th4+浓度对溶解速率的影响较小。进一步的动力学研究采用缩芯模型,揭示了ThO2的溶解过程可能主要受到界面化学反应的控制。通过数据拟合,得到了表观反应速率常数k=(0.132±0.007) min−1。这一发现为优化钍基燃料循环的溶解过程和改进后续处理工艺提供了重要的理论依据。通过系统地研究不同因素对ThO2溶解的影响,为钍基燃料循环的溶解过程提供了新的视角和解决方案。通过优化HNO3浓度和控制溶解温度,可以在不使用氟离子的情况下实现ThO2的有效溶解,这对于钍基核燃料的后续处理和利用具有重要意义。Abstract: This study aims to investigate the reflux dissolution process of thorium dioxide in nitric acid, seeking an alternative to the current fluoride ion-dependent dissolution methods to prevent corrosion of stainless steel dissolvers and subsequent processing issues. By employing a reflux dissolution apparatus and utilizing nitric acid as the solvent, the effects of initial nitric acid concentration, temperature, and initial thorium ion concentration on the dissolution efficiency of thorium dioxide were systematically studied. The experimental results reveal that the apparent activation energy for the dissolution process of thorium dioxide in nitric acid is 41.47 kJ/mol. An increase in initial nitric acid concentration from 9 mol/L to 12 mol/L corresponded with an increased dissolution rate of thorium dioxide, exhibiting an apparent order of about 3. However, a decline in the dissolution rate was observed when the initial nitric acid concentration surpassed 12 mol/L. Additionally, the initial thorium ion concentration was found to have a minimal impact on the dissolution rate. Further kinetic studies employing the shrinking core model indicate that the dissolution process of thorium dioxide is predominantly controlled by interfacial chemical reactions. Data fitting yield an apparent reaction rate constant k of (0.132±0.007) min−1. These findings provide significant theoretical support for optimizing the dissolution process in thorium-based fuel cycles and improving subsequent processing techniques. By systematically examining the impact of various factors on the dissolution of thorium dioxide, this research offers new insights and solutions for the dissolution process within thorium-based fuel cycles. Effective dissolution of thorium dioxide can be achieved without the use of fluoride ions by optimizing nitric acid concentration and controlling dissolution temperature, which is of considerable importance for the subsequent processing and application of thorium-based nuclear fuels.