Solid–Liquid Phase Equilibria of Quaternary System Li+, NH4+, Ca2+//Cl––H2O at 323.2 and 348.2 K

IF 2.1 3区 工程技术 Q3 CHEMISTRY, MULTIDISCIPLINARY
Shuang Wang, Jinniu Chen, Jiubo Liu, Jiantuan Jia, Shuai Chen, Changhao Wu and Xudong Yu*, 
{"title":"Solid–Liquid Phase Equilibria of Quaternary System Li+, NH4+, Ca2+//Cl––H2O at 323.2 and 348.2 K","authors":"Shuang Wang,&nbsp;Jinniu Chen,&nbsp;Jiubo Liu,&nbsp;Jiantuan Jia,&nbsp;Shuai Chen,&nbsp;Changhao Wu and Xudong Yu*,&nbsp;","doi":"10.1021/acs.jced.5c00392","DOIUrl":null,"url":null,"abstract":"<p >The solid–liquid phase equilibria of the quaternary system Li<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, Ca<sup>2+</sup>//Cl<sup>–</sup>–H<sub>2</sub>O at 323.2 and 348.2 K was investigated using isothermal dissolution method, targeting deep brines rich in ammonium and calcium. Equilibrium liquid-phase composition and density were determined. The solid solution (NH<sub>4</sub>Cl)<sub><i>x</i></sub>(LiCl·H<sub>2</sub>O)<sub>1–<i>x</i></sub> was confirmed by XRD and TG-DSC. The results show that the quaternary system Li<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, Ca<sup>2+</sup>//Cl<sup>–</sup>–H<sub>2</sub>O at 323.2 and 348.2 K exhibits complex behavior involving the formation of solid solution (NH<sub>4</sub>Cl)<sub><i>x</i></sub>(LiCl·H<sub>2</sub>O)<sub>1–<i>x</i></sub> and double salt (2NH<sub>4</sub>Cl·CaCl<sub>2</sub>·3H<sub>2</sub>O). The phase diagram of the system at 323.2 K consists of three invariant points, seven univariate curves, and five crystalline phase regions (NH<sub>4</sub>Cl, LiCl·H<sub>2</sub>O, 2NH<sub>4</sub>Cl·CaCl<sub>2</sub>·3H<sub>2</sub>O, (NH<sub>4</sub>Cl)<sub><i>x</i></sub>(LiCl·H<sub>2</sub>O)<sub>1–<i>x</i></sub>, and CaCl<sub>2</sub>·2H<sub>2</sub>O). At 348.2 K, it has two invariant points, five univariant curves, and four crystalline regions (NH<sub>4</sub>Cl, 2NH<sub>4</sub>Cl·CaCl<sub>2</sub>·3H<sub>2</sub>O, (NH<sub>4</sub>Cl)<sub><i>x</i></sub>(LiCl·H<sub>2</sub>O)<sub>1–<i>x</i></sub>, and CaCl<sub>2</sub>·2H<sub>2</sub>O). Comparative analysis of multitemperature phase diagrams of the quaternary system Li<sup>+</sup>, NH<sub>4</sub><sup>+</sup>, Ca<sup>2+</sup>//Cl<sup>–</sup>–H<sub>2</sub>O at 298.2, 323.2, and 348.2 K demonstrates that the crystalline phase region of LiCl·H<sub>2</sub>O decreases with the increase of temperature. Notably, at 348.2 K, lithium chloride exclusively exists within the (NH<sub>4</sub>Cl)<sub><i>x</i></sub>(LiCl·H<sub>2</sub>O)<sub>1–<i>x</i></sub>. This thermal behavior suggests that cooling crystallization could be effectively employed for lithium extraction from such brines.</p>","PeriodicalId":42,"journal":{"name":"Journal of Chemical & Engineering Data","volume":"70 9","pages":"3880–3890"},"PeriodicalIF":2.1000,"publicationDate":"2025-08-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of Chemical & Engineering Data","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jced.5c00392","RegionNum":3,"RegionCategory":"工程技术","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0

Abstract

The solid–liquid phase equilibria of the quaternary system Li+, NH4+, Ca2+//Cl–H2O at 323.2 and 348.2 K was investigated using isothermal dissolution method, targeting deep brines rich in ammonium and calcium. Equilibrium liquid-phase composition and density were determined. The solid solution (NH4Cl)x(LiCl·H2O)1–x was confirmed by XRD and TG-DSC. The results show that the quaternary system Li+, NH4+, Ca2+//Cl–H2O at 323.2 and 348.2 K exhibits complex behavior involving the formation of solid solution (NH4Cl)x(LiCl·H2O)1–x and double salt (2NH4Cl·CaCl2·3H2O). The phase diagram of the system at 323.2 K consists of three invariant points, seven univariate curves, and five crystalline phase regions (NH4Cl, LiCl·H2O, 2NH4Cl·CaCl2·3H2O, (NH4Cl)x(LiCl·H2O)1–x, and CaCl2·2H2O). At 348.2 K, it has two invariant points, five univariant curves, and four crystalline regions (NH4Cl, 2NH4Cl·CaCl2·3H2O, (NH4Cl)x(LiCl·H2O)1–x, and CaCl2·2H2O). Comparative analysis of multitemperature phase diagrams of the quaternary system Li+, NH4+, Ca2+//Cl–H2O at 298.2, 323.2, and 348.2 K demonstrates that the crystalline phase region of LiCl·H2O decreases with the increase of temperature. Notably, at 348.2 K, lithium chloride exclusively exists within the (NH4Cl)x(LiCl·H2O)1–x. This thermal behavior suggests that cooling crystallization could be effectively employed for lithium extraction from such brines.

Abstract Image

Li+, NH4+, Ca2+//Cl—H2O在323.2和348.2 K下的固液相平衡
以富铵、富钙深盐水为研究对象,采用等温溶解法研究了Li+、NH4+、Ca2+//Cl—H2O四元体系在323.2 K和348.2 K下的固液平衡。测定平衡液相组成和密度。通过XRD和TG-DSC证实了固溶体(NH4Cl)x(LiCl·H2O) 1-x的存在。结果表明,在323.2和348.2 K下,Li+、NH4+、Ca2+//Cl—H2O四元体系表现出复杂的行为,包括形成固溶体(NH4Cl)x(LiCl·H2O) 1-x和双盐(2NH4Cl·CaCl2·3H2O)。在323.2 K下,体系的相图由3个不变点、7条单变量曲线和5个晶相区(NH4Cl、LiCl·H2O、2NH4Cl·CaCl2·3H2O、(NH4Cl)x(LiCl·H2O) 1-x和CaCl2·2H2O)组成。在348.2 K时,它具有2个不变点、5条不变曲线和4个结晶区(NH4Cl、2NH4Cl·CaCl2·3H2O、(NH4Cl)x(LiCl·H2O) 1-x和CaCl2·2H2O)。对比分析了298.2、323.2和348.2 K时Li+、NH4+、Ca2+//Cl—H2O四元体系的多温相图,发现LiCl·H2O的结晶相区随着温度的升高而减小。值得注意的是,在348.2 K时,氯化锂完全存在于(NH4Cl)x(LiCl·H2O) 1-x中。这种热行为表明,冷却结晶可以有效地用于从这种盐水中提取锂。
本文章由计算机程序翻译,如有差异,请以英文原文为准。
求助全文
约1分钟内获得全文 求助全文
来源期刊
Journal of Chemical & Engineering Data
Journal of Chemical & Engineering Data 工程技术-工程:化工
CiteScore
5.20
自引率
19.20%
发文量
324
审稿时长
2.2 months
期刊介绍: The Journal of Chemical & Engineering Data is a monthly journal devoted to the publication of data obtained from both experiment and computation, which are viewed as complementary. It is the only American Chemical Society journal primarily concerned with articles containing data on the phase behavior and the physical, thermodynamic, and transport properties of well-defined materials, including complex mixtures of known compositions. While environmental and biological samples are of interest, their compositions must be known and reproducible. As a result, adsorption on natural product materials does not generally fit within the scope of Journal of Chemical & Engineering Data.
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
确定
请完成安全验证×
copy
已复制链接
快去分享给好友吧!
我知道了
右上角分享
点击右上角分享
0
联系我们:info@booksci.cn Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。 Copyright © 2023 布克学术 All rights reserved.
京ICP备2023020795号-1
ghs 京公网安备 11010802042870号
Book学术文献互助
Book学术文献互助群
群 号:604180095
Book学术官方微信