四元体系Li~+,Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O 273K相平衡研究
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摘要
针对含锂相关水盐体系相平衡研究不够完善的问题,采用等温溶解平衡法研究四元体系Li~+,Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O在273 K相平衡关系,并根据溶解度数据绘制相图。结果表明该体系属于简单交互四元体系,无复盐和固溶体生成。其相图包含2个共饱点,5条单变量曲线和4个结晶相区(分别是Li_2B_4O_7·3H_2O、Li_2SO_4·H_2O、MgB_4O_7·9H_2O和MgSO_4·7H_2O)。从相图中可以看出,MgB_4O_7所对应的相区最大,溶解度最小。对比该体系在不同温度下相图发现,随着温度升高MgSO_4和MgB_4O_7的结晶区明显减小,而Li_2B_4O_7和Li_2SO_4的结晶区明显增大,说明MgSO_4和MgB_4O_7的溶解度相较于Li_2B_4O_7和Li_2SO_4对温度变化更敏感。
Phase equilibrium of water-salt systems containing lithium is not well studied. An isothermal dissolution equilibrium method was used to study phase equilibrium of Li~+, Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O quaternary system at 273 K, and phase diagram was obtained. The results show that this quaternary system is a simple interactive quaternary system without double salt or solid solution formation. The phase diagram contains two invariant points, five univariant curves and four crystallization areas(corresponding to Li_2B_4O_7·3H_2O, Li_2SO_4·H_2O, MgB_4O_7·9 H_2O and MgSO_4·7H_2O). The phase diagram shows that MgB_4O_7 has the largest phase region and the lowest solubility. Phase diagrams at different temperatures were compared and the results show that with the increase of temperature, the crystallization regions of MgSO_4 and MgB_4O_7 decrease significantly, while the crystallization regions of Li_2B_4O_7 and Li_2SO_4 increase significantly. The results show that the solubility of MgSO_4 and MgB_4O_7 is more sensitive to temperature than that of Li_2B_4O_7 and Li_2SO_4.
Phase equilibrium of water-salt systems containing lithium is not well studied. An isothermal dissolution equilibrium method was used to study phase equilibrium of Li~+, Mg~(2+)//SO_4~(2-),B_4O_7~(2-)-H_2O quaternary system at 273 K, and phase diagram was obtained. The results show that this quaternary system is a simple interactive quaternary system without double salt or solid solution formation. The phase diagram contains two invariant points, five univariant curves and four crystallization areas(corresponding to Li_2B_4O_7·3H_2O, Li_2SO_4·H_2O, MgB_4O_7·9 H_2O and MgSO_4·7H_2O). The phase diagram shows that MgB_4O_7 has the largest phase region and the lowest solubility. Phase diagrams at different temperatures were compared and the results show that with the increase of temperature, the crystallization regions of MgSO_4 and MgB_4O_7 decrease significantly, while the crystallization regions of Li_2B_4O_7 and Li_2SO_4 increase significantly. The results show that the solubility of MgSO_4 and MgB_4O_7 is more sensitive to temperature than that of Li_2B_4O_7 and Li_2SO_4.
引文
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[2]LIU Zhen-min(刘振敏),YANG Geng-sheng(杨更生).The utilization and sustainable development of salt lake resources in China(我国盐湖资源的开发利用与可持续发展)[J].Bulletin of Mineralogy,Petrology and Geochemistry(矿物岩石地球化学通报),1999,2(18):59-61.
[3]YAN Jun(严军),HUANG Xiao-liang(黄小良).Studies on utilize of potassium,magnesium and lithium in Saline Lakes of Qinghai province(青海省盐湖钾、镁、锂盐资源开发利用探讨)[J].Journal of Salt Lake Research(盐湖研究),2002,10(4):63-69.
[4]Teeple J E.The Industrial Development of Searles Lake Brines with Equilibrium Data[M].New York:The Chemical Catalog Company,1929.
[5]SONG Peng-sheng(宋彭生),DONG Ya-ping(董亚萍),LI Wu(李武).Phase diagram of Li+,Na+,K+//Cl-,SO2-4-H2O system at 25℃and its utilization(Li+,Na+,K+//Cl-,SO42--H2O五元体系25℃相图及其应用)[J].Journal of Salt Lake Research(盐湖研究),2017,25(3):9-17.
[6]SUN Bo(孙柏),SONG Peng-sheng(宋彭生),LI Wu(李武),et al.Thermodynamics and phase equilibria of the oil field brine with Sr system at 25℃I.Sr,Na,K,Li//Cl-H2O system(含锶油田水体系热力学和相平衡研究I.Sr,Na,K,Li//Cl-H2O体系)[J].Journal of Salt Lake Research(盐湖研究),2015,23(4):50-58.
[7]MENG Ling-zong(孟令宗),DENG Tian-long(邓天龙),SUN Bo(孙柏).Metastable equilibria of the ternary system Na+//Cl-,B4O72--H2O at 28℃and 35℃(Na+//Cl-,B4O72--H2O体系在28℃与35℃时介稳相平衡研究)[J].Journal of Salt Lake Research(盐湖研究),2007,15(1):34-38.
[8]MENG Ling-zong,GUO Ya-fei,DENG Tian-long,et al.Solid and liquid metastable phase equilibria in the aqueous quaternary system Li+,Mg2+//SO42-,borate-H2O at 273.15 K[J].Chemical Research in Chinese Universities,2017,33(4),655-659.
[9]ZENG Ying,CAO Fu-jia,LI Long-guang,et al.Metastable phase equilibrium in the aqueous quaternary system(Li2SO4+Na2SO4+Li2B4O7+Na2B4O7+H2O)at 273.15 K[J].Journal of Chemical and Engineering Data,2011,56(5),2569-2573.
[10]LI Ming(李明).Study on equilibria in quinary system Li+,Mg2+//Cl-,SO42-,B4O72--H2O at 288 K(五元体系Li+,Mg2+//Cl-,SO42-,B4O72--H2O 288 K稳定相平衡研究)[D].Chengdu(成都):Chengdu University of Technology(成都理工大学),2009.
[11]SANG Shi-hua(桑世华),LI Ming(李明),LI Heng(李恒),et al.A study on phase equilibria of the quaternary system Li+,Mg2+//SO42-,B4O72--H2O at 288 K(交互四元体系Li+,Mg2+//SO42-,B4O72--H2O 288 K相平衡研究)[J].Acta Geologica Sinica(地质学报),2010,11(84):1704-1707.
[12]REN Xiao-jing(任效京),HUANG Xue-li(黄雪莉).Phase equilibria in the quaternary system of Li+,Mg2+//Cl-,SO42--H2O at273.15 K(273.15 K下四元体系Li+,Mg2+//Cl-,SO42--H2O相平衡研究)[J].Inorganic Chemicals Industry(无机盐工业),2018,48(7):13-15.
[13]WANG Shi-qiang(王士强),GAO Jie(高洁),YU Xue(余学),et al.Study on the interference of coexisting lithium ion on the measurement of magnesium ion(大量Li+存在对Mg2+分析测定中的影响研究)[J].Journal of Salt Lake Research(盐湖研究),2007,15(1):44-48.
[14]Qinghai Institute of Salt Lakes,Chinese Academy of Sciences(中国科学院青海盐湖研究所).Analysis Method of Brine and Salt(卤水和盐的分析方法)[M].Beijng(北京):Science and Technology Press(科学技术出版社),1984.
[15]JING Yan(景燕).A new method for synthesis of Hungtsaoite(合成章氏硼镁石的新方法)[J].Sea-Lake Salt and Chemical Industry(海湖盐与化工),2000,29(2):24-25.