Citation: | CHENG Ziyi, WEI Zhuo, HE Zhiyan, XIAO Shuyun, WANG Yanxu, ZHOU Kun. Stable Phase Equilibrium of the Ternary System Li+, NH4+//SO42--H2O at 298 K[J]. Conservation and Utilization of Mineral Resources, 2021, 41(1): 141-145. doi: 10.13779/j.cnki.issn1001-0076.2021.01.020 |
Sichuan Jiajika, Lijiagou and other places have rich spodumene reserves, it provides an important source of raw materials for downstream lithium battery energy storage materials and other fields.In the traditional spodumene production process of lithium carbonate, sodium hydroxide neutralization method is used to remove impurities such as iron and aluminum. However, the added value of by-product sodium sulfate is low, resulting in high production costs. This paper studies the process of replacing strong sodium oxide with ammonia gas to neutralize impurities to prepare lithium carbonate, it was found that LiNH4SO4 double salt was produced during the precipitation and crystallization process of refined lithium solution, which affected the yield of lithium and the quality of lithium carbonate products.In order to solve the problem, the stable phase equilibrium relationship of the ternary system Li+, NH4+//SO42--H2O at 298 K was studied by the isothermal dissolved equilibrium method. The solubility, density and refractive index data of each component of the equilibrium liquid phase were measured, and the phase diagram, density-composition diagram and refractive index composition diagram of the system were drawn. The results show that this system is a complex ternary system, with the formation of LiNH4SO4 double salt; its stable phase diagram consists of 3 solid phase crystallization regions, 3 univariate curves, 2 invariant points, 3 crystallization regions corresponding to (NH4)2SO4, Li2SO4·H2O and LiNH4SO4, And double salt LiNH4SO4 crystallization area is the largest.The research results show that in order to avoid the production of LiNH4SO4 double salt, It is necessary to reduce the lithium-sulfur ratio (w(Li2SO4)·H2O/w(NH4)2SO4) in the lithium solution to less than 1 through the calcium ion precipitation method at the front end of the spodumene-made industrial-grade lithium carbonate process, the research results provide theoretical guidance for the use of ammonia neutralization and impurity removal in the Sichuan spodumene hydrometallurgical process.
[1] | 周平, 唐金荣, 张涛. 全球锂资源供需前景与对策建议[J]. 地质通报. 2014(10): 1532-1538. doi: 10.3969/j.issn.1671-2552.2014.10.009 |
[2] | 张念, 张逸航. 未来我国动力电池对锂需求的展望[J]. 中国有色金属, 2019(24): 42-43. |
[3] | 崔晓林. 中国锂矿资源需求预测及供需分析[D]. 中国地质大学(北京).. |
[4] | 胡萍, 刘明, 傅利华. 碳酸锂工艺技术分析[J]. 世界有色金属. 2016(20): 48-49. |
[5] | 吴秉东, 张姚. 四川省锂矿资源现状及开发利用前景[J]. 采矿技术. 2016(4): 16-19. |
[6] | 薛峰峰, 郭琬, 周苏, 等. 粗品碳酸锂制备高纯碳酸锂工艺研究[J]. 无机盐工业. 2018(1): 46-48. |
[7] | 苏慧, 朱兆武, 王丽娜, 等. 矿石资源中锂的提取与回收研究进展[J]. 化工学报, 2019, 70(1): 10-23. |
[8] | 牛自得. 水盐体系相图及其应用[M]. 天津: 天津大学出版社, 2002: 172-182. |
[9] | 郑秋风, 罗军, 陈帅, 等. 298.2 K四元体系MgCl2-SrCl2-AlCl3-H2O相平衡实验及溶解度计算[J]. 化工学报. 2020(12): 5443-5451. |
[10] | 孙玖, 王如燕, 侯向阳, 等. 三元体系Li+, Cs+//SO42--H2O 298K稳定相平衡研究[J]. 矿产保护与利用, 2019(2): 59-63. |
[11] | 曹吉林, 章永洁, 纪志永, 等. 25℃ K2SO4-(NH4)2SO4-H2O体系相平衡的研究[J]. 河北工业大学学报. 2002(3): 14-17. |
[12] | 张学平, 周小玲, 范绍奇, 等. 三元体系LiBr-Li2SO4-H2O 298 K相平衡[J]. 化学工程. 2020(7): 59-61. |
[13] | FOSBOL P L, THOMSEN K, STENBY E H. Reverse Schreinemakers Method for Experimental Analysis of Mixed-Solvent Electrolyte Systems[J]. Journal of Solution Chemistry, 2009, 38(1): 1-14. |
Phase diagram of ternary system Li+, NH4+//SO42--H2O at 298 K
XRD pattern of the invariant point C
XRD pattern of the invariant point D
The ternary system Li+, NH4+//SO42--H2O equilibrium liquid phase-density composition diagram at 298K
The ternary system Li+, NH4+//SO42--H2O equilibrium liquid phase-refractive index composition diagram at 298K