马朝辉,闫国庆,闫潇,吴刚,陈伟东,王力军

• 1:有研资源环境技术研究院(北京)有限公司
• 2:中原关键金属实验室

摘要(Abstract)：

熔盐精馏作为一种高效环保的锆铪火法分离技术，相比湿法分离工艺，其具有流程短、成本低等显著优势。氯铝酸钾（KAlCl＿4）是典型的精馏熔盐体系，锆铪氯化物（ZrCl＿4,HfCl＿4）在该体系中的热力学参数是开展熔盐精馏技术研究的重要基础。本文利用现有0.165～0.300(ZrCl＿4/HfCl＿4摩尔分数)范围和463～621 K温度区间的蒸气压实验数据，对精馏条件下锆铪氯化物在KAlCl＿4熔盐中的热力学特性进行了分析与评估。结果表明，锆铪氯化物在熔盐中的蒸气压和温度的关系符合Antonie方程，不同摩尔分数下的Antonie拟合方程相关系数均大于0.9883，可以准确预测不同温度下蒸气压。KAlCl＿4熔盐在623～673 K,ZrCl＿4/HfCl＿4摩尔分数为0.165～0.300条件下表现为非理想溶液，采用Margules,Van Laar和Redlich-Kister等热力学模型，对锆铪氯化物在KAlCl＿4熔盐中的活度系数和摩尔分数进行了拟合分析，结果表明，Redlich-Kister三阶展开结合选择性引入高阶项的方法能获得较优拟合效果，拟合方程相关系数达到0.8731～0.9067，平均相对误差为10.15%～13.31%，计算得到的活度与蒸气压的线性拟合方程相比使用摩尔分数的拟合结果相关系数由0.5426～0.7202增大到0.9395～0.9598，平均相对误差为6.99%～8.29%，显著提升了预测数据的准确性。本文从理论层面实现了不同精馏条件下锆铪氯化物在KAlCl＿4熔盐中蒸气压的预测与计算，为锆铪熔盐精馏分离的工艺的优化与设计、关键装备研发及熔盐体系热力学性质研究提供了重要基础数据支撑与理论参考。

关键词(KeyWords)： 锆铪分离;熔盐精馏;热力学;蒸气压;活度系数

Abstract:

Keywords:

基金项目(Foundation): 国家重点研发计划项目（2023YFC2908103）;; 中原关键金属实验室开放基金项目（GJJSKFZD202406）资助

作者(Author): 马朝辉,闫国庆,闫潇,吴刚,陈伟东,王力军

DOI: 10.13373/j.cnki.cjrm.XY25080017

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