无机盐工业 ›› 2021, Vol. 53 ›› Issue (8): 55-59.doi: 10.19964/j.issn.1006-4990.2020-0562
收稿日期:
2020-10-19
出版日期:
2021-08-10
发布日期:
2021-08-11
作者简介:
刘治国(1976—),男,博士,副教授,主要研究方向:化工热力学,金属材料环境适应性研究,电化学腐蚀特性分析;E-mail: Liu Zhiguo1(),Zhang Na1,Chen Chuan1,Xu Xianzhen2
Received:
2020-10-19
Online:
2021-08-10
Published:
2021-08-11
摘要:
水盐体系的相平衡性质是化工单元操作的基础,在化学化工、海洋、地质等领域有着重要的研究价值。国内外许多学者对水盐体系汽液平衡进行了实验和理论的研究,构筑了各具特色的经验和半经验的模型。针对水盐体系,在NRTL理论的基础上,基于水化作用和混合盐假设建立了能够预测混合体系汽液平衡的活度系数扩展模型。通过对21组二元水盐体系和14组混合体系的关联计算,验证了该模型的可行性;同时,该模型可以采用二元体系参数直接预测计算混合水盐体系汽液平衡。
中图分类号:
刘治国,张娜,陈川,徐显朕. 水盐体系汽液平衡的热力学模型研究[J]. 无机盐工业, 2021, 53(8): 55-59.
Liu Zhiguo,Zhang Na,Chen Chuan,Xu Xianzhen. Study on thermodynamic model of vapor-liquid equilibrium of electrolyte system[J]. Inorganic Chemicals Industry, 2021, 53(8): 55-59.
表1
二元水盐体系模型参数
体系 | h | τi,w(0) | τw,i(0) | τi,w(1) | τw,i(1) |
---|---|---|---|---|---|
BaBr2+H2O | 1.50 | -4.42 | 3.52 | -228.19 | 321.73 |
CaBr2+H2O | 2.55 | -0.40 | -33.92 | -1 649.09 | 12 785.70 |
CaCl2+H2O | 1.10 | 781.44 | -3 771.77 | -98.47 | -6 010.44 |
CsBr+H2O | 0.50 | -4.34 | 4.12 | 423.85 | -480.68 |
CsCl+H2O | 0.30 | -3.38 | 2.83 | -59.70 | -20.03 |
CsI+H2O | 0.10 | -3.78 | -1.40 | 9.67 | 642.89 |
K2SO4+H2O | 0.60 | -38.84 | 70.38 | 12 703.70 | -17 691.81 |
KBr+H2O | 2.10 | 1.20 | -50.38 | -1 340.62 | 15 952.42 |
KCl+H2O | 2.00 | -2.92 | 2.38 | -81.81 | 126.71 |
KI+H2O | 3.00 | -3.63 | 3.64 | 199.06 | -326.81 |
LiCl+H2O | 2.15 | -4.99 | 13.17 | -4.29 | 16.17 |
LiBr+H2O | 0.80 | -5.47 | 56.87 | 510.23 | -23 153.41 |
MgCl2+H2O | 3.47 | -6.26 | -58.68 | 453.19 | 19 585.20 |
MgSO4+H2O | 0.41 | -2.63 | 3.29 | -696.95 | 2 367.36 |
Na2SO4+H2O | 0.10 | 1.06 | -1.45 | -1 441.50 | 1 425.60 |
NaBr+H2O | 4.00 | -1.50 | -0.69 | -456.26 | 567.10 |
NaCl+H2O | 3.10 | -2.54 | 2.06 | 184.51 | -203.49 |
NaI+H2O | 1.90 | -3.50 | 2.74 | -75.40 | -137.38 |
RbCl+H2O | 2.70 | -0.94 | 0.66 | -607.71 | 993.37 |
SrCl2+H2O | 2.00 | -6.85 | 30.00 | 539.38 | -8 296.66 |
ZnCl2+H2O | 3.00 | -3.77 | 3.26 | -1.23 | 2.83 |
表2
二元水盐体系汽液平衡的关联结果
体系 | T/K | 数据 点 | 本实验 | |
---|---|---|---|---|
dY/kPa | dP/% | |||
LiCl+H2O[ | 298.15~394.40 | 47 | 0.018 | 1.250 |
LiBr+H2O[ | 298.15~377.85 | 182 | 0.070 | 0.860 |
MgCl2+H2O[ | 273.15~376.45 | 151 | 0.076 | 0.850 |
MgSO4+H2O[ | 273.15~298.15 | 30 | 0.012 | 0.530 |
Na2SO4+H2O[ | 298.15~343.15 | 49 | 0.048 | 0.750 |
NaBr+H2O[ | 298.15~373.15 | 69 | 0.040 | 0.650 |
NaCl+H2O[ | 298.15~343.15 | 58 | 0.090 | 0.929 |
NaI+H2O[ | 298.15~343.15 | 51 | 0.061 | 0.690 |
RbCl+H2O[ | 298.15~343.15 | 59 | 0.068 | 0.710 |
SrCl2+H2O[ | 298.15~379.80 | 30 | 0.030 | 0.750 |
ZnCl2+H2O[ | 298.15~379.80 | 30 | 0.030 | 0.910 |
BaBr2+H2O[ | 298.15~353.15 | 55 | 0.079 | 0.780 |
CaBr2+H2O[ | 298.15~353.15 | 63 | 0.049 | 1.100 |
CaCl2+H2O[ | 273.15~423.15 | 322 | 0.081 | 1.820 |
CsBr+H2O[ | 298.15~353.15 | 51 | 0.097 | 1.010 |
CsCl+H2O[ | 298.15~353.15 | 63 | 0.091 | 0.970 |
CsI+H2O[ | 298.15~353.15 | 42 | 0.039 | 0.420 |
K2SO4+H2O[ | 298.15~383.65 | 104 | 0.051 | 1.150 |
KBr+H2O[ | 298.15~343.15 | 51 | 0.077 | 0.870 |
KCl+H2O[ | 273.15~343.15 | 66 | 0.044 | 0.670 |
KI+H2O[ | 298.15~343.15 | 60 | 0.097 | 0.950 |
平均值 | 0.059 | 0.880 |
表3
混合水盐体系汽液平衡的关联结果
体系 | T/K | 数据点 | 本实验 | |
---|---|---|---|---|
dY/kPa | dP/% | |||
NaCl-Na2SO4-H2O[ | 298.15 | 25 | 0.036 | 1.58 |
MgSO4-Na2SO4-H2O[ | 298.15 | 30 | 0.024 | 0.82 |
MgCl2-Na2SO4-H2O[ | 298.15 | 22 | 0.030 | 1.60 |
NaCl-MgSO4-H2O[ | 298.15 | 30 | 0.044 | 1.55 |
KCl-K2SO4-H2O[ | 280.15~323.15 | 50 | 0.021 | 0.85 |
KCl-KBr-H2O[ | 279.55~323.35 | 48 | 0.075 | 0.95 |
KCl-KNO3-H2O[ | 279.05~324.75 | 46 | 0.086 | 1.17 |
K2SO4-MgSO4-H2O[ | 310~374.35 | 360 | 0.080 | 1.10 |
NaCl-KCl-H2O[ | 298.15~382.25 | 180 | 0.091 | 1.80 |
NaCl-CaCl2-H2O[ | 313.25~388.25 | 240 | 0.091 | 1.10 |
NaCl-KCl-MgCl2-H2O[ | 298.15 | 136 | 0.026 | 0.80 |
MgCl2-MgSO4-H2O[ | 298.15 | 20 | 0.100 | 1.70 |
NaCl-MgCl2-H2O[ | 298.15 | 20 | 0.080 | 1.70 |
NaCl-KCl-MgCl2-CaCl2- MgSO4[ | 306.75~373.25 | 60 | 0.070 | 1.07 |
平均值 | 0.061 | 1.27 |
表4
混合水盐体系汽液平衡的预测结果
体系 | T/K | 数据 点 | 本实验 | |
---|---|---|---|---|
dY/kPa | dP/% | |||
NaCl-Na2SO4-H2O[ | 298.15 | 25 | 0.072 | 2.58 |
MgSO4-Na2SO4-H2O[ | 298.15 | 30 | 0.037 | 1.22 |
MgCl2-Na2SO4-H2O[ | 298.15 | 22 | 0.080 | 2.60 |
NaCl-MgSO4-H2O[ | 298.15 | 30 | 0.074 | 2.55 |
KCl-K2SO4-H2O[ | 280.15~323.15 | 50 | 0.031 | 1.50 |
KCl-KBr-H2O[ | 279.55~323.35 | 48 | 0.150 | 2.50 |
KCl-KNO3-H2O[ | 279.05~324.75 | 46 | 0.160 | 2.71 |
K2SO4-MgSO4-H2O[ | 310~374.35 | 360 | 0.180 | 3.10 |
NaCl-KCl-H2O[ | 298.15~382.25 | 180 | 0.170 | 2.80 |
NaCl-CaCl2-H2O[ | 313.25~388.25 | 240 | 0.140 | 1.90 |
NaCl-KCl-MgCl2-H2O[ | 298.15 | 136 | 0.046 | 1.50 |
MgCl2-MgSO4-H2O[ | 298.15 | 20 | 0.160 | 2.70 |
NaCl-MgCl2-H2O[ | 298.15 | 20 | 0.180 | 2.75 |
NaCl-KCl-MgCl2-CaCl2- MgSO4[ | 306.75~373.25 | 60 | 0.070 | 1.07 |
平均值 | 0.117 | 2.36 |
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