1.成都理工大学材料与化学化工学院,四川 成都 610059
2.四川省攀西战略矿产资源综合利用协同创新中心, 四川 成都 610059
郑秋风(1996—),男,硕士研究生,zhengqiufengc413@126.com
于旭东(1985—),男,博士,副教授,xwdlyxd@126.com
收稿:2020-04-22,
修回:2020-06-30,
网络首发:2020-12-17,
纸质出版:2020-12-05
移动端阅览
郑秋风, 罗军, 陈帅, 陈念粗, 于旭东, 曾英. 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, 71(12): 5443-5451 DOI: 10.11949/0438-1157.20200420.
ZHENG Qiufeng, LUO Jun, CHEN Shuai, CHEN Niancu, YU Xudong, ZENG Ying. Measurements and simulation for aqueous quaternary system MgCl2-SrCl2-AlCl3-H2O at 298.2 K[J]. CIESC Journal, 2020, 71(12): 5443-5451 DOI: 10.11949/0438-1157.20200420.
郑秋风, 罗军, 陈帅, 陈念粗, 于旭东, 曾英. 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, 71(12): 5443-5451 DOI: 10.11949/0438-1157.20200420. DOI:
ZHENG Qiufeng, LUO Jun, CHEN Shuai, CHEN Niancu, YU Xudong, ZENG Ying. Measurements and simulation for aqueous quaternary system MgCl2-SrCl2-AlCl3-H2O at 298.2 K[J]. CIESC Journal, 2020, 71(12): 5443-5451 DOI: 10.11949/0438-1157.20200420. DOI:
采用等温溶解平衡法研究了298.2 K四元体系MgCl
2
-SrCl
2
-AlCl
3
-H
2
O的相平衡关系,测定了该体系的溶解度和平衡溶液的密度、折射率。根据实验数据,分别绘制了298.2 K该四元体系的空间立体图、相图、水图、密度-组成图和折射率-组成图。研究发现:298.2 K下,四元体系MgCl
2
-SrCl
2
-AlCl
3
-H
2
O无复盐或固溶体生成,稳定相图由2个共饱点、5条单变量曲线和4个结晶区组成。四个结晶区分别为MgCl
2
·6H
2
O、SrCl
2
·6H
2
O、SrCl
2
·2H
2
O和AlCl
3
·6H
2
O,其中SrCl
2
·6H
2
O结晶区最大,SrCl
2
·2H
2
O结晶区最小,说明SrCl
2
·6H
2
O更容易结晶析出。平衡液相的密度和折射率随着
J
(MgCl
2
)的变化呈规律性变化。采用Pitzer模型进行了298.2 K四元体系MgCl
2
-SrCl
2
-AlCl
3
-H
2
O溶解度计算,对比发现,计算结果与实验结果基本吻合。
Solid-liquid equilibria of the aqueous quaternary system MgCl
2
-SrCl
2
-AlCl
3
-H
2
O at 298.2 K was studied by using the isothermal dissolution equilibrium method. The solubility
density
and refractive index of the aqueous quaternary system were measured. The corresponding space diagram
stable phase diagram
water content diagram
and the diagrams of density
vs
composition
refractive index
vs
composition were constructed based on the experimental data. The results show that there is no double that salt or solid solution was formed in the quaternary system. The stable phase diagram of the quaternary system MgCl
2
-SrCl
2
-AlCl
3
-H
2
O at 298.2 K consists of two invariant points
five isothermal dissolution curves
and four crystallization regions. The four crystallization regions correspond to four single hydrate salts magnesium chloride hexahydrate (MgCl
2
·6H
2
O)
strontium chloride hexahydrate (SrCl
2
·6H
2
O)
strontium chloride dihydrate (SrCl
2
·2H
2
O)
and aluminum chloride hexahydrate (AlCl
3
·6H
2
O). With a view to the crystallization regions
the crystallization region of salt SrCl
2
·2H
2
O is the smallest
while the crystallization region of salt SrCl
2
·6H
2
O is the largest
meaning SrCl
2
·6H
2
O can be more easily separated from solution than other coexisting salts in this system at 298.2 K. The densities and refractive indices of the solution at equilibrium change regularly with the change of
J
(MgCl
2
) of the solution. The Pitzer model is used to calculate the solubility of the 298.2 K quaternary system MgCl
2
-SrCl
2
-AlCl
3
-H
2
O. The comparison found that the calculated results are basically consistent with the experimental results.
韩松昊, 税鹏, 余超, 等. 中国锶资源现状及可持续发展建议[J ] . 科技通报, 2018, 34 (1): 1-5.
Han S H, Shui P, Yu C, et al. Present situation and sustainable development suggestion of Chinese strontium resource industry[J ] . Bull. Sci. Technol., 2018, 34 (1): 1-5.
李波, 段东平, 王树轩, 等. 以碳酸锶废渣为原料制备高纯氯化锶[J ] . 盐湖研究, 2013, 21 (2): 58-61.
Li B, Duan D P, Wang S X, et al. The preparation of high purity strontium chloride from strontium carbonate waste[J ] . J. Salt Lake Res., 2013, 21 (2): 58-61.
曾英, 陈佩君, 于旭东. 四元体系Rb+, Cs+, Mg2+ // SO42- - H2O 298.2 K相平衡研究[J ] . 化工学报, 2020, 71 (8): 3460-3468.
Zeng Y, Chen P J, Yu X D. Phase equilibria of quaternary system Rb+, Cs+, Mg2+ // SO42- - H2O at T =298.2 K[J ] . CIESC Journal, 2020, 71 (8): 3460-3468.
聂国亮, 桑世华, 崔瑞芝. 298 K 和323 K条件下五元体系NaBr-KBr-MgBr2-CaBr2-H2O相平衡研究[J ] . 化工学报, 2019, 70 (9): 3267-3274.
Nie G L, Sang S H, Cui R Z. Phase equilibria in quinary system NaBr-KBr-MgBr2-CaBr2-H2O at 298 K and 323 K[J ] . CIESC Journal, 2019, 70 (9): 3267-3274.
任永胜, 曹晶, 于冰洁. 313.15 K四元体系Na+ // SO42-, CO32-, NO3- - H2O固液相平衡研究[J ] . 化工学报, 2019, 70 (6): 2102-2109.
Ren Y S, Cao J, Yu B J. Solid-liquid equilibria of quaternary system Na+ // SO42-, CO32-, NO3- - H2O at 313.15 K[J ] . CIESC Journal, 2019, 70 (6): 2102-2109.
Yu X D, Zheng M P, Zeng Y, et al. Solid-liquid equilibrium of quinary aqueous solution composed of lithium, potassium, rubidium, magnesium, and borate at 323.15 K[J ] . J. Chem. Eng. Data, 2019, 64 (12): 5681-5687.
Wang L, Yu X D, Li M L, et al. Phase equilibrium for the aqueous ternary systems NH4+, Sr2+(Ca2+)//Cl- - H2O at T = 298 K[J ] . J. Chem. Eng. Jpn., 2018, 51 (7): 551-555.
Dong O Y, Zeng D W, Zhou H Y, et al. Phase change materials in the ternary system NH4Cl+CaCl2+H2O[J ] . Calphad: Comput. Coupling Phase Diagrams Thermochem., 2011, 35 (3): 269-275.
Zhang R Z, Yang J M, Zhang L, et al. The phase equilibriums in the NH4Cl-CaCl2-H2O system at 50 and 75℃ and their Pitzer model representations[J ] . Russ. J. Phys. Chem. A, 2014, 88 (13): 2325-2330.
Li X, Yuan J S, Ji Z Y, et al. Phase equilibrium of the ternary system of NH4Cl-CaCl2-H2O at 50℃[J ] . Front. Chem. Eng. China, 2010, 4 (1): 75-77.
Yu X D, Zeng Y, Zhang Z X. Solid-liquid metastable phase equilibria in the ternary systems KCl+NH4Cl+H2O and NH4Cl+MgCl2+H2O at 298.15 K[J ] . J. Chem. Eng. Data, 2012, 57 (6): 1759-1765.
Yu X D, Wang L, Chen J, et al. Salt-water phase equilibria in ternary systems K+(Mg2+), NH4+ // Cl- - H2O at T = 273 K[J ] . J. Chem. Eng. Data, 2017, 62 (4): 1427-1432.
Yuan M X, Qiao X C, Yu J G. Phase equilibria of AlCl3+FeCl3+H2O, AlCl3+CaCl2+H2O, and FeCl3+CaCl2+H2O at 298.15 K[J ] . J. Chem. Eng. Data, 2016, 61 (5): 1749-1755.
袁梦霞, 乔秀臣. 三元体系AlCl3+CaCl2+H2O, AlCl3+FeCl3+H2O, CaCl2+FeCl3+H2O在35℃的相平衡[J ] . 化工学报, 2017, 68 (7): 2653-2659.
Yuan M X, Qiao X C. Phase eq uilibria of AlCl3+CaCl2+H2O, AlCl3+FeCl3+H2O and CaCl2+FeCl3+H2O ternary systems at 35℃[J ] . CIESC Journal, 2017, 68 (7): 2653-2659.
Li D C, Zhang Z Y, Fan R, et al. Solid-liquid phase equilibria in the aqueous systems (CaCl2+SrCl2+H2O) and (NaCl+CaCl2+SrCl2+H2O) at 288.15 K[J ] . J. Chem. Eng. Data, 2019, 64 (6): 2767-2773.
Guo L J, Zeng D W, Yao Y, et al. Isopiestic measurement and solubility evaluation of the ternary system (CaCl2+SrCl2+H2O) at T =298.15 K[J ] . J. Chem. Thermodyn., 2013, 63 : 60-66.
Gao Y Y, Ye C, Zhang W Y, et al. Phase equilibria in the ternary system CaCl2-SrCl2-H2O and the quaternary system KCl-CaCl2-SrCl2-H2O at 373 K[J ] . J. Chem. Eng. Data, 2018, 63 (8): 2738-2742.
毕玉敬, 孙柏, 赵静, 等. 25℃时三元体系SrCl2-CaCl2-H2O相平衡研究[J ] . 无机化学学报, 2011, 27 (9): 1765-1771.
Bi Y J, Sun B, Zhao J, et al. Phase equilibrium in ternary system SrCl2-CaCl2-H2O at 25℃[J ] . Chin. J. Inorg. Chem., 2011, 27 (9): 1765-1771.
Zheng Q F, Wang L, Zheng H, et al. Solid-liquid equilibria and Pitzer model simulation of the SrCl2-NH4Cl-MgCl2-H2O quaternary system at T =298 K[J ] . J. Chem. Eng. Data, 2018, 63 (12): 4606-4613.
Gao W C, Li Z B. A practical approach to produce Mg-Al spinel based on the modeling of phase equilibria for NH4Cl-MgCl2-AlCl3-H2O system[J ] . AIChE J., 2013, 59 (6): 1855-1867.
Yu X D, Liu M, Zheng Q F, et al. Measurement and correlation of phase equilibria of ammonium, calcium, aluminum, and chloride in aqueous solution at 298.15 K[J ] . J. Chem. Eng. Data, 2019, 64 (8): 3514-3520.
王林, 郑秋风, 刘敏, 等. 三元体系SrCl2 + MgCl2 + H2O 298 K相平衡测定及计算[J ] . 高校化学工程学报, 2019, 33 (4): 800-807.
Wang L, Zheng Q F, Liu M, et al. Phase equilibrium measurements and simulation of the SrCl2 + MgCl2 + H2O ternary system at 298 K[J ] . J. Chem. Eng. Chin. Univ., 2019, 33 (4): 800-807.
Yu X D, Zheng Q F, Wang L, et al. Solid-liquid phase equilibrium determination and correlation of ternary systems NH4Cl + AlCl3 + H2O, MgCl2 + AlCl3 + H2O and SrCl2 + AlCl3 + H2O at 298 K[J ] . Fluid Phase Equilib., 2020, 507 : 112426.
中国科学院青海盐湖研究所. 卤水和盐的分析方法[M]. 2版. 北京: 科学出版社, 1988: 69-72.
Institute of Qinghai Salt-Lake of Chinese Academy of Sciences. Analytical Methods of Brines and Salts [M]. 2nd ed. Beijing: Chinese Science Press, 1988: 69-72.
袁艺, 罗维, 钟世华,等. 铝及铝合金化学分析方法第16部分: 镁含量的测定: GB/T 20975.16-2008[S]. 北京: 中国标准出版社, 2008.
Yuan Y, Luo W, Zhong S H, et al. Methods for chemical analysis of aluminium and aluminium alloys-part16: determination of magnesium: GB/T 20975.16—2008[S]. Beijing: China Standards Press, 2008.
冯颖新, 杨宇宏, 田光,等. 铝及铝合金化学分析方法第17部分: 锶含量的测定 火焰原子吸收光谱法: GB/T 20975.17—2008[S]. 北京: 中国标准出版社, 2008.
Feng Y Y, Yang Y H, Tian G, et al. Methods for chemical analysis of aluminium and aluminium alloys - part17: determination of strontium content — flame atomic absorption spectrometric method: GB/T 20975.17—2008[S]. Beijing: China Standards Press, 2008.
李跃平, 石磊, 张树朝,等. 铝及铝合金化学分析方法第25部分: 电感耦合等离子体原子发射光谱法: GB/T 20975.25—2008[S]. 北京: 中国标准出版社, 2008.
Li Y P, Shi L, Zhang S C, et al. Methods for chemical analysis of aluminium and aluminium alloys-part 25: inductively coupled plasma atomic emission spectrometric method: GB/T 20975.25—2008[S]. Beijing: China Standards Press, 2008.
牛自得, 程芳琴, 李宝存, 等. 水盐体系相图及其应用[M]. 天津: 天津大学出版社, 2002: 84-85.
Niu Z D, Cheng F Q, Li B C, et al. Salt-Water System Phase Diagrams and Applications[M]. Tianjin: Tianjin University Press, 2002: 84-85.
Assarsson G O, Balder A. Equilibria between 18 and 100° in the aqueous ternary system containing Sr2+, Mg2+ and Cl-[J ] . J. Phys. Chem., 1954, 58 (2): 416.
Nie G L, Sang S H, Cui R Z, et al. Measurements and calculations of solid-liquid equilibria in two quaternary systems: LiCl-NaCl-SrCl2-H2O and LiCl-KCl-SrCl2-H2O at 298 K[J ] . Fluid Phase Equilib., 2020, 509 : 112458.
崔瑞芝, 李武, 董亚萍, 等. 298 K四元体系LiCl-MgCl2-CaCl2-H2O相平衡实验及溶解度计算[J ] . 化工学报, 2018, 69 (10): 4148-4155.
Cui R Z, Li W, Dong Y P, et al. Measurements and calculations of solid-liquid equilibria in quaternary system LiCl-MgCl2-CaCl2-H2O at 298 K[J ] . CIESC Journal, 2018, 69 (10): 4148-4155.
宋彭生, 董亚萍, 李武. Li+, Na+, K+ // Cl-, SO42- - H2O五元体系25℃相图及应用[J ] . 盐湖研究, 2017, 25 (3): 9-17.
Song P S, Dong Y P, Li W. Phase diagram of Li+, Na+, K+ // Cl-, SO42- - H2O system and its utilization[J ] . J. Salt Lake Res., 2017, 25 (3): 9-17.
Pitzer K S. Thermodynamics of electrolytes(Ⅰ): Theoretical basis and general equations[J ] . J. Phys. Chem., 1973, 77 (2): 268-277.
Pitzer K S, Mayorga G. Thermodynamics of electrolytes(Ⅱ): Activity and osmotic coefficients for strong electrolytes with one or both ions univalent[J ] . J. Phys. Chem., 1973, 77 (19): 2300-2308.
Pitzer K S. Activity Coefficients in Electrolyte Solutions[M]. 2nd ed. London: CRC Press, 1992.
Greenberg J P, Møller N. The prediction of mineral solubilities in natural waters: a chemical equilibrium model for the Na-K-Ca-Cl-SO4-H2O system to high concentration from 0 to 250 °C[J ] . Geochim. Cosmochim. Acta, 1989, 53 (10): 2503-2518.
Christov C. Thermodynamics of formation of double salts and mixed crystals from aqueous solutions[J ] . J. Chem. Thermodyn., 2005, 37 (10): 1036-1060.
Christov C. Thermodynamic study of the K-Mg-Al-Cl-SO4-H2O system at the temperature 298.15 K[J ] . Calphad: Comput. Coupling Phase Diagrams Thermochem., 2001, 25 (3): 445-454.
Clegg S L, Rard J A, Miller D G. Isopiesti c determination of the osmotic and activity coefficients of NaCl+SrCl2+H2O at 298.15 K and representation with an extended ion-interaction model[J ] . J. Chem. Eng. Data, 2005, 50 (4): 1162-1170.
Michael S. Thermodynamic properties of SrCl2(aq) from 252 K to 524 K and phase equilibria in the SrCl2-H2O system: implications for thermochemical heat storage[J ] . J. Chem. Thermodyn., 2018, 120 : 106-115.
0
浏览量
1
下载量
2
CSCD
关联资源
相关文章
相关作者
相关机构
京公网安备11010102001995号