Thermodynamic modelling of the Li-Na-K-OH-SO4-H2O system for lithium hydroxide production simulation

IF 4.8 2区材料科学 Q1 METALLURGY & METALLURGICAL ENGINEERING

Hydrometallurgy Pub Date : 2025-06-15 DOI:10.1016/j.hydromet.2025.106517

Yanfei Fan , Dongdong Li , Ziyu Zhuang , Dandan Gao , Dewen Zeng

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引用次数: 0

Abstract

The caustic addition process to Li₂SO₄ leachate is a principal industrial process in producing lithium hydroxide. This process relies on the double-decomposition reaction between Li₂SO₄ and NaOH in an aqueous system, followed by cooling to separate Na₂SO₄∙10H₂O and evaporation to produce LiOH∙H₂O. Due to the presence of Na and K impurities in lithium minerals, the operation takes place in the complex aqueous system Li-Na-K-OH-SO₄-H₂O. This work describes: (i) the development of a thermodynamic model for the complex Li-Na-K-OH-SO₄-H₂O system, (ii) validation of its reliability and (iii) quantitative simulation of lithium-hydroxide production. The results led to four key conclusions: 1) A relatively low concentration (Li < 20 g/L) in the caustic solution prevents the formation of Li₂SO₄∙3Na₂SO₄∙12H₂O, the principal source of lithium loss. 2) The optimal cooling temperature for removing Na₂SO₄∙10H₂O is −10 to −15 °C. 3) A moderate evaporation temperature (50–60 °C) is critical for achieving the high recovery of LiOH∙H₂O in a single cycle. 4) The mother liquor remaining after the crystallisation of LiOH∙H₂O can be fully recycled. Theoretically, Na and K are completely removed as Na₂SO₄∙10H₂O and NaK₃(SO₄)₂ solids.

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用于氢氧化锂生产模拟的Li-Na-K-OH-SO4-H2O体系热力学建模

硫酸渗滤液的碱加成工艺是生产氢氧化锂的主要工业工艺。该工艺依赖于水溶液中Li2SO4与NaOH的双重分解反应，然后冷却分离Na2SO4∙10H2O，蒸发生成LiOH∙H2O。由于锂矿物中存在Na和K杂质，该操作在复杂的水体系Li-Na-K-OH-SO4-H2O中进行。这项工作描述了：(i)复杂的Li-Na-K-OH-SO4-H2O体系的热力学模型的发展，（ii）其可靠性的验证和（iii）氢氧化锂生产的定量模拟。结果得出了四个关键结论：1)相对较低的浓度(Li <；在苛性碱溶液中加入20 g/L)可阻止Li2SO4∙3Na2SO4∙12H2O的形成，而Li2SO4∙12H2O是锂损失的主要来源。2)脱除Na2SO4∙10H2O的最佳冷却温度为−10 ~−15℃。3)适度的蒸发温度（50-60℃）是实现LiOH∙H2O单循环高回收率的关键。4) LiOH∙H2O结晶后剩余的母液可充分回收。理论上，Na和K被完全脱除为Na2SO4∙10H2O和NaK3(SO4)2固体。

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来源期刊

Hydrometallurgy 工程技术-冶金工程

CiteScore

9.50

自引率

6.40%

发文量

144

审稿时长

3.4 months

期刊介绍： Hydrometallurgy aims to compile studies on novel processes, process design, chemistry, modelling, control, economics and interfaces between unit operations, and to provide a forum for discussions on case histories and operational difficulties. Topics covered include: leaching of metal values by chemical reagents or bacterial action at ambient or elevated pressures and temperatures; separation of solids from leach liquors; removal of impurities and recovery of metal values by precipitation, ion exchange, solvent extraction, gaseous reduction, cementation, electro-winning and electro-refining; pre-treatment of ores by roasting or chemical treatments such as halogenation or reduction; recycling of reagents and treatment of effluents.