化工学报 ›› 2022, Vol. 73 ›› Issue (10): 4335-4344.DOI: 10.11949/0438-1157.20220894

• 热力学 • 上一篇    下一篇

298.2 K四元体系Li+, K+NH4+ // Cl--H2O相平衡研究

任思颖(), 于旭东(), 罗军, 冯霞, 赵志星, 姚智豪   

  1. 成都理工大学材料与化学化工学院,四川 成都 610059
  • 收稿日期:2022-06-27 修回日期:2022-08-22 出版日期:2022-10-05 发布日期:2022-11-02
  • 通讯作者: 于旭东
  • 作者简介:任思颖(1997—),女,硕士研究生,rensiyingc413@126.com
  • 基金资助:
    国家自然科学基金项目(U1507111)

Phase equilibria of aqueous quaternary system Li+, K+, NH4+ // Cl- - H2O at 298.2 K

Siying REN(), Xudong YU(), Jun LUO, Xia FENG, Zhixing ZHAO, Zhihao YAO   

  1. College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, Sichuan, China
  • Received:2022-06-27 Revised:2022-08-22 Online:2022-10-05 Published:2022-11-02
  • Contact: Xudong YU

摘要:

采用等温溶解平衡法研究了298.2 K三元体系Li+NH4+ // Cl--H2O和四元体系Li+,K+NH4+ // Cl--H2O的相平衡。采用湿渣法和XRD测定了三元体系共饱点处平衡固相组成,发现固溶体(NH4Cl) x (LiCl·H2O)1-x 形成;采用XRD和SEM测定了四元体系共饱点处平衡固相组成,发现固溶体(NH4Cl) x (LiCl·H2O)1-x 、(NH4Cl) x (KCl)1-x 和 (KCl) x (NH4Cl)1-x 形成。研究发现:298.2 K下,三元体系相图由2个共饱点、3条单变量曲线和3个结晶相区组成,结晶区面积按照NH4Cl > (NH4Cl) x (LiCl·H2O)1-x > LiCl·H2O顺序依次减小;四元体系相图包含3个共饱点、8条单变量曲线和6个结晶相区,结晶区面积按 (KCl) x (NH4Cl)1-x > NH4Cl > KCl > (NH4Cl) x (KCl)1-x > (NH4Cl) x (LiCl·H2O)1-x > LiCl·H2O顺序依次减小。结果表明:298.2 K时,在氯化物体系中,锂铵和钾铵均可形成固溶体,且钾铵比锂铵更容易形成固溶体而大量析出,增加了锂钾铵氯化物的分离难度。

关键词: 相平衡, 溶解性, 热力学性质, 固溶体, 水合物

Abstract:

The equilibrium solid phase composition of the ternary system Li+, NH4+ // Cl- - H2O and the quaternary system Li+, K+, NH4+ // Cl- - H2O were determined by isothermal dissolution method at 298.2 K. The composition of the equilibrium solid phase at the invariant point of the ternary system Li+, NH4+ // Cl- - H2O was determined by wet residue method and X-ray diffraction method. It was found that a solid solution (NH4Cl) x (LiCl·H2O)1-x was formed. The composition of the equilibrium solid phase at the invariant point of the quaternary system Li+, K+, NH4+ // Cl--H2O was determined by X-ray diffraction and SEM. It was found that solid solutions (NH4Cl) x (LiCl·H2O)1-x, (NH4Cl) x (KCl)1-x and (KCl) x (NH4Cl)1-x were formed. The stable phase diagram of the ternary system Li+, NH4+ // Cl--H2O consists of two invariant points, three uninvariant curves and three crystallization regions, the area of crystallization region decreases in the order of NH4Cl > (NH4Cl) x (LiCl·H2O)1-x > LiCl·H2O. The stable phase diagram of the quaternary system Li+, K+, NH4+ // Cl--H2O consists of three invariant points, eight uninvariant curves and six crystallization regions, the area of the crystallization regions decreases in the order of (KCl) x (NH4Cl)1-x > NH4Cl > KCl > (NH4Cl) x (KCl)1-x >(NH4Cl) x (LiCl·H2O)1-x > LiCl·H2O. The results show that in the chloride system at 298.2 K, both lithium ammonium and potassium ammonium can form solid solution, and potassium ammonium is easier to form solid solution than lithium ammonium and precipitate in large quantities, which increases the difficulty of separation of lithium potassium ammonium chloride.

Key words: phase equilibria, solubility, thermodynamics properties, solid solution, hydrate

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