Study on phase equilibrium of system Na+, K+, Mg2+//Cl-, NO3-, SO42--H2O at -15℃

WANG Xueying; HUANG Xueli; HUANG He; LUO Qinglong; ZOU Xuejing

doi:10.11949/0438-1157.20200059

您当前的位置：

首页 >

文章列表页 >

Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃

Thermodynamics | 更新时间：2026-07-24

- Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃
- CIESC Journal Vol. 71, Issue 11, Pages: 5059-5066(2020)
- 作者机构：
  
  新疆大学化学化工学院，新疆煤炭清洁转化与化工过程自治区重点实验室，新疆乌鲁木齐 830046
- 作者简介：
- 基金信息：
- DOI：10.11949/0438-1157.20200059
  CLC： O 642
- Received：15 January 2020，
  
  Revised：2020-06-30，
  
  Online First：03 November 2020，
  
  Published：05 November 2020
- 稿件说明：
移动端阅览
王雪莹, 黄雪莉, 黄河, 罗清龙, 邹雪净. -15℃下Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O体系相平衡研究[J]. 化工学报, 2020, 71(11): 5059-5066 DOI: 10.11949/0438-1157.20200059.

WANG Xueying, HUANG Xueli, HUANG He, LUO Qinglong, ZOU Xuejing. Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃[J]. CIESC Journal, 2020, 71(11): 5059-5066 DOI: 10.11949/0438-1157.20200059.
王雪莹, 黄雪莉, 黄河, 罗清龙, 邹雪净. -15℃下Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O体系相平衡研究[J]. 化工学报, 2020, 71(11): 5059-5066 DOI: 10.11949/0438-1157.20200059. DOI：

WANG Xueying, HUANG Xueli, HUANG He, LUO Qinglong, ZOU Xuejing. Study on phase equilibrium of system Na⁺, K⁺, Mg²⁺//Cl^-, NO₃^-, SO₄^2--H₂O at -15℃[J]. CIESC Journal, 2020, 71(11): 5059-5066 DOI: 10.11949/0438-1157.20200059. DOI：

摘要

新疆卤水硝酸盐矿主要含有Na

、K

、Mg

、Cl

、NO

、SO

六种离子，属于高元复杂体系，其合理利用和开发需要不同温度下的相平衡研究作为理论支撑。采用等温溶解平衡法，对Na

， K

， Mg

//Cl

， NO

， SO

-H

O体系在-15℃、NaCl·2H

O饱和条件下的相平衡进行了研究，并构建了相图。相图中有六个零变量点和八个两盐结晶区，只存在一种复盐KCl·MgCl

·6H

O。八个两盐结晶区，分别对应于NaCl·2H

O+Na

·10H

O、NaCl·2H

O+NaNO

、Na

Cl·2H

O+KCl、NaCl·2H

O+KNO

、NaCl·2H

O+MgSO

·7H

O、NaCl·2H

O+MgCl

·8H

O、NaCl·2H

O+Mg(NO

)

·6H

O和NaCl·2H

O+KCl·MgCl

·6H

O，其中NaCl·2H

O+Na

·10H

O共晶区最大，在低温时，硫酸钠的溶解度最小，降温过程中较易结晶析出。与该体系在25℃下的相图相比，复盐种类减少5种，零变量点减少19个，相关系得以极大简化。

Abstract

Xinjiang brine nitrate mine mainly contains six kinds of ions: Na

and SO

belonging to a high-element complex system

and its rational utilization and development require phase equilibrium studies at different temperatures as theoretical support. The phase equilibrium of the system Na

//Cl

-H

O saturated with NaCl·2H

O at -15℃ was investigated using the isothermal solution equilibrium method. According to the measured data

the phase diagrams were constructed. Only one double salt KCl·MgCl

·6H

O was found in the system. There are six invariant points and eight two-salt crystallization fields corresponding to NaCl·2H

O+Na

·10H

NaCl·2H

O+NaNO

NaCl·2H

O+KCl

NaCl·2H

O+KNO

NaCl·2H

O+MgSO

·7H

NaCl·2H

O+MgCl

·8H

NaCl·2H

O + Mg(NO

)

·6H

O and NaCl·2H

O+KCl·MgCl

·6H

O. The crystallization area of NaCl·2H

O+Na

·10H

O occupies the largest part because of its low solubility

and they will crystallize out easily from the mixed solution in the cooling process

. Compared with the phase diagram of the system at 25℃

there are 5 types of double salts reduced

19 zero variable points reduced

and the phase relationship is greatly simplified.

关键词

Keywords

references

张明刚 . 新疆盐湖卤水水化学特征研究 [J ] . 盐湖研究 , 1993 , 1 ( 1 ): 17 - 32 .

Zhang M G . Study on the chemical characteristics of brine in Xinjiang salt lake [J ] . Journal of Salt Lake Research , 1993 , 1 ( 1 ): 17 - 32 .

郑喜玉 . 新疆盐湖的形成演化环境 [J ] . 盐湖研究 , 1993 , 1 ( 1 ): 1 - 10 .

Zheng X Y . Formation and evolution environment of salt lake in Xinjiang [J ] . Journal of Salt Lake Research , 1993 , 1 ( 1 ): 1 - 10 .

黄雪莉 . 298. 16 K下 , Na + , K + , Mg 2+ //Cl - , NO 3 - , SO 4 2- -H 2 O体系液固相平衡及应用基础研究 [D ] . 大连: 大连理工大学 , 2007 .

Huang X L . Study on liquid-solid equilibrium and application of the Na + , K + , Mg 2+ //Cl - , NO 3 - , SO 4 2- -H 2 O system at 298 . 16 K [D ] . Dalian : Dalian University of Technology , 2007 .

刘福云 , 黄雪莉 , 黄文婷 , 等 . 三元水盐体系冰点和共晶点的测定、相图表达及计算 [J ] . 化工学报 , 2017 , 68 ( 9 ): 3336 - 3342 .

Liu F Y , Huang X L , Huang W L , et al . Determination, graphics expression and calculation of freezing point and eutectic point in ternary salt-water system [J ] . CIESC Journal , 2017 , 68 ( 9 ): 3336 - 3342 .

廖玲 , 黄雪莉 , 宋欢 . 258 . 15 K下五元体系Na + , K + //Cl - , NO 3 - , SO 4 2- -H 2 O相平衡研究 [J ] . 高校化学工程学报, 2016 , 30 ( 1 ): 7 - 12 .

Liao L , Huang X L , Song H . Phase equilibria of quinary system Na + , K + //Cl - , NO 3 - , SO 4 2- -H 2 O at 258.15 K [J ] . Journal of Chemical Engineering of Chinese Universities , 2016 , 30 ( 1 ): 7 - 12 .

朱巧丽 , 黄雪莉 . -15℃下Na + , K + , Mg 2+ //Cl - , SO 4 2- -H 2 O体系相平衡 [J ] . 化工学报 , 2015 , 66 ( 4 ): 1252 - 1257 .

Zhu Q L , Huang X L . Liquid-solid phase equilibrium of Na + , K + , Mg 2+ //Cl - , SO 4 2- -H 2 O system at -15℃ [J ] . CIESC Journal , 2015 , 66 ( 4 ): 1252 - 1257 .

Shestov A S , Marchenko A V . The consolidation of saline ice blocks in water of varying freezing points: laboratory experiments and computer simulations [J ] . Cold Regions Science & Technology , 2015 , 122 : 71 - 79 .

Karamoddin M , Varaminian F . Water purification by freezing and gas hydrate processes and removal of dissolved minerals (Na + , K + , Mg 2+ , Ca 2+ ) [J ] . Journal of Molecular Liquids , 2016 , 223 : 1021 - 1031 .

Hasan M , Rotich N , John M , et al . Salt recovery from wastewater by air-cooled eutectic freeze crystallization [J ] . Chemical Engineering Journal , 2017 , 326 : 192 - 200 .

John M , Häkkinen A , Louhi-Kultanen M . Purification efficiency of natural freeze crystallization for urban wastewaters [J ] . Cold Regions Science and Technology , 2020 , 170 : 102953 .

Bian S J , Li D D , Gao D D , et al . Hydrometallurgical processing of lithium, potassium, and boron for the comprehensive utilization of da Qaidam lake brine via natural evaporation and freezing [J ] . Hydrometallurgy , 2017 , 173 : 80 - 83 .

于旭东 , 黄琴 , 王林 , 等 . KCl-PEG4000-H 2 O三元体系288、298、308 K相平衡测定及计算 [J ] . 化工学报 , 2019 , 70 ( 3 ): 830 - 839 .

Yu X D , Huang Q , Wang L , et al . Measurements and simulation for ternary system KCl-PEG4000-H 2 O at 288, 298 and 308 K [J ] . CIESC Journal , 2019 , 70 ( 3 ): 830 - 839 .

Spenser R , Moller N , Weare J . The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Mg-Cl-SO 4 -H 2 O system at temperatures below 25℃ [J ] . Geochim. Cosmochim. Acta , 1990 , 54 : 575 – 590 .

Marion G M , Farren R E . Mineral solubilities in the Na-K-Mg-Ca-Cl-SO 4 -H 2 O system: a re-evaluation of the sulfate chemistry in the Spencer-Moller-Weare model [J ] . Geochimica Et Cosmochimica Acta , 1999 , 63 ( 9 ): 1305 - 1318 .

Fu C , Sang S H , Zhou M F , et al . Phase equilibria in the ternary systems Li 2 B 4 O 7 -MgB 4 O 7 -H 2 O and K 2 B 4 O 7 -MgB 4 O 7 -H 2 O at 273 K [J ] . Journal of Chemical & Engineering Data , 2016 , 61 ( 3 ): 1071 - 1077 .

桑世华 , 张婷婷 , 傅超 , 等 . 四元体系Li + , K + , Mg 2+ //B 4 O 7 2- -H 2 O 273 K相平衡 [J ] . 化工学报 , 2017 , 68 ( 9 ): 3343 - 3349 .

Sang S H , Zhang T T , Fu C , et al . Phase equilibrium of the quaternary system Li + , K + , Mg 2+ //B 4 O 7 2- -H 2 O at 273 K [J ] . CIESC Journal , 2017 , 68 ( 9 ): 3343 - 3349 .

Zhao X P , Zhang X P , Yang Y Y , et al . Phase equilibria in the quaternary systems KCl-K 2 B 4 O 7 -K 2 SO 4 -H 2 O and MgCl 2 -MgB 4 O 7 -MgSO 4 -H 2 O at 273 K [J ] . Journal of Chemical & Engineering Data , 2017 , 62 ( 4 ): 1377 - 1383 .

曾英 , 林晓峰 , 郑志远 . Li + , K + //SO 4 2- , B 4 O 7 2- -H 2 O交互四元体系273 K介稳相平衡研究 [J ] . 高校化学工程学报 , 2009 , 23 ( 1 ): 7 - 11 .

Zeng Y , Lin X F , Zheng Z Y . Study on metastable phase equilibrium of the reciprocal quaternary system Li + , K + //SO 4 2- , B 4 O 7 2- -H 2 O at 273 K [J ] . J. Chem. Eng. Chin. Univ. , 2009 , 23 ( 1 ): 7 - 11 .

Li D , Meng L Z , Deng T L , et al . Thermodynamic study of solid–liquid equilibrium in NaCl-NaBr-H 2 O system at 288.15 K [J ] . Russian Journal of Physical Chemistry A , 2018 , 92 ( 6 ): 1213 - 1218 .

Dou S Y , Zhao B , Li L , et al . Phase diagram of Mg 2+ , NH 4 + //Cl - , SO 4 2- -H 2 O system at 0℃ and their application [J ] . Fluid Phase Equilibria , 2016 , 409 : 264 - 270 .

Zhang J , Guo H F , Cao J L , et al . Phase equilibrium of the quaternary system Na 2 SO 4 -MgSO 4 -(NH 4 ) 2 SO 4 -H 2 O at 0℃ [J ] . Journal of Chemical & Engineering Data , 2013 , 58 ( 9 ): 2622 - 2628 .

牛自得 , 程芳琴 . 水盐体系相图及其应用 [M ] . 天津 : 天津大学出版社 , 2002 .

Niu Z D , Cheng F Q . Phase Diagram of Salt-water System and Its Applications [M ] . Tianjin : Tianjin University Press , 2002 .

中国科学院青海盐湖所 . 卤水和盐的分析方法 [M ] . 北京 : 科学与技术出版社 , 1984 .

Institute of Qinghai Salt-Lake of Chinese Academy of Sciences . Analytical Methods of Brines and Salts [M ] . Beijing : Chinese Science Press , 1984 .

王明 . 分析化学手册 [M ] . 3版 . 北京 : 化学工业出版社 , 2016 .

Wang M . Handbook of Analytical Chemistry [M ] . 3rd ed . Beijing : Chemical Industry Press , 2016 .

Howards S , Slicok H L . Solubililies of Inorganic and Organic CompoundsM] . 3rd ed . New York : Pergamon Press , 1979 .

Drebushchak V A , Ogienko A G , Yunoshev A S . Metastable eutectic melting in the NaCl-H 2 O system [J ] . Thermochim. Acta , 2017 , 647 : 94 - 100 .

Archer D G . Thermodynamic properties of the NaCl+H 2 O system(Ⅱ): Thermodynamic properties of NaCl(aq), NaCl·2H 2 O(cr) and phase equilibria [J ] . Journal of Physical and Chemical Reference Data , 1992 , 21 ( 4 ): 793 - 829 .

Wang X Y , Wang X F , Luo Q L , et al . Phase equilibria in the aqueous quinary system Na + , Mg 2+ //Cl - , NO 3 - , SO 4 2- -H 2 O and its subsystem at 258 K [J ] . Journal of Chemical & Engineering Data , 2020 , 65 ( 1 ): 264 - 273 .

Christov C . Chemical equilibrium model of solution behavior and bishofite (MgCl 2 ·6H 2 O(cr)) and hydrogen-carnallite (HCl·MgCl 2 ·7H 2 O(cr)) solubility in the MgCl 2 +H 2 O and HCl·MgCl 2 +H 2 O systems to high acid concentration at (0 to 100)℃ [J ] . Journal of Chemical & Engineering Data , 2009 , 54 ( 9 ): 2599 - 2608 .

Pillay V , Gärtner R S , Himawan C , et al . MgSO 4 +H 2 O system at eutectic conditions and thermodynamic solubility products of MgSO 4 ·12H 2 O(s) and MgSO 4 ·7H 2 O(s) [J ] . Journal of Chemical & Engineering Data , 2009 , 50 ( 2 ): 551 - 555 .

Steiger M , Linnow K , Ehrhardt D , et al . Decom position reactions of magnesium sulfate hydrates and phase equilibria in the MgSO 4 -H 2 O and Na + -Mg 2+ -Cl - -SO 4 2- -H 2 O systems with implications for Mars [J ] . Geochimica Et Cosmochimica Acta , 2011 , 75 ( 12 ): 3600 - 3626 .

Li D D , Zeng D W , Yin X , et al . Phase diagrams and thermochemical modeling of salt lake brine systems(Ⅲ): Li 2 SO 4 +H 2 O, Na 2 SO 4 +H 2 O, K 2 SO 4 +H 2 O, MgSO 4 +H 2 O and CaSO 4 +H 2 O systems [J ] . Calphad , 2018 , 60 : 163 - 176 .

Views

下载量

CSCD

Alert me when the article has been cited

提交

Tools

Publicity Resources

Experiment and calculation of phase equilibrium in ternary systems NaBr-CaBr2-H2O and KBr-CaBr2-H2O at 273.15 K

Phase equilibria in quaternary system Li+, K+, Mg2+//B4O72--H2O at 273 K

Predicting thermodynamic properties of refrigerants using an equation of state for square-well chain fluid with variable range

Preparation of 3.5-valent vanadium electrolyte via ammonia gas-phase reduction

Vapor-liquid equilibrium study of R1150+R1234ze(E) binary system at 223.15—253.15 K

Related Author

ZHANG Xueping

CUI Ruizhi

SANG Shihua

ZHANG Tingting

FU Chao

YANG Lei

JIA Yuqian

Related Institution

College of Chemistry & Chemical Engineering, Chengdu University of Technology

College of Chemical & Chemical Engineering, Sichuan University of Arts and Science

Key Laboratory of Comprehensive and Highly Efficient Utilization of Salt Lake Resources, Qinghai Institute of Salt Lakes, Chinese Academy of Sciences

College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology

Mineral Resources Chemistry Key Laboratory of Sichuan Higher Education Institutions

⁰