化工学报 ›› 2020, Vol. 71 ›› Issue (1): 209-215.DOI: 10.11949/0438-1157.20191148
收稿日期:
2019-10-09
修回日期:
2019-11-09
出版日期:
2020-01-05
发布日期:
2020-01-05
通讯作者:
邓天龙
作者简介:
袁菲(1994—),女,博士研究生,基金资助:
Fei YUAN(),Jiangtao SONG,Jiayin HU,Yafei GUO,Shiqiang WANG,Tianlong DENG()
Received:
2019-10-09
Revised:
2019-11-09
Online:
2020-01-05
Published:
2020-01-05
Contact:
Tianlong DENG
摘要:
采用等温溶解平衡法研究了四元体系CaCl2-CaSO4-CaB6O10-H2O在308.15 K下的稳定相平衡。测定了该体系的溶解度及平衡溶液的物化性质(包括折射率、密度和pH)。根据实验数据,分别绘制了该四元体系的干基图、水图以及相应的物化性质–组成图。研究结果表明:该体系在308.15 K时有1个共饱点(CaCl2·4H2O + CaSO4·2H2O + CaB6O10·5H2O),3条单变量溶解度曲线,3个单盐结晶区,分别对应于CaCl2·4H2O、硬石膏(CaSO4·2H2O)和高硼钙石(CaB6O10·5H2O)。其中,硬石膏CaSO4·2H2O结晶区最大、高硼钙石CaB6O10·5H2O结晶区次之,而CaCl2·4H2O结晶区最小,表明硬石膏最易于结晶析出。此外,该四元体系在308.15 K下没有复盐和固溶体生成,属于简单水合物I型。平衡液相的物化性质随着CaCl2浓度的增大呈规律性变化,并在共饱点处发生转折。其中,折射率和密度的变化规律相近,而pH的变化规律则与之相反。对该四元体系的稳定相平衡进行研究,将为综合开发利用油田卤水中的钙、硼等资源提供理论依据。
中图分类号:
袁菲, 宋江涛, 胡佳音, 郭亚飞, 王士强, 邓天龙. 四元体系CaCl2-CaSO4-CaB6O10-H2O 308.15 K相平衡研究[J]. 化工学报, 2020, 71(1): 209-215.
Fei YUAN, Jiangtao SONG, Jiayin HU, Yafei GUO, Shiqiang WANG, Tianlong DENG. Phase equilibria of quaternary system CaCl2-CaSO4-CaB6O10-H2O at 308.15 K[J]. CIESC Journal, 2020, 71(1): 209-215.
类型 | CaO, wb/% | B2O3, wb/% | H2O, wb/% | CaO∶B2O3∶H2O (摩尔比) |
---|---|---|---|---|
理论值 | 15.77 | 58.88 | 25.35 | 1∶3∶5 |
实验值 | 15.81 | 58.83 | 25.38 | 1∶3∶5 |
表1 CaB6O10·5H2O化学分析数据
Table 1 Chemical analysis data of CaB6O10·5H2O
类型 | CaO, wb/% | B2O3, wb/% | H2O, wb/% | CaO∶B2O3∶H2O (摩尔比) |
---|---|---|---|---|
理论值 | 15.77 | 58.88 | 25.35 | 1∶3∶5 |
实验值 | 15.81 | 58.83 | 25.38 | 1∶3∶5 |
No. | Liquid composition, wB/% | Dry-salt composition, ZB/[g·(100 g·S)-1] | Solid phase | ||||||
---|---|---|---|---|---|---|---|---|---|
CaCl2 | CaSO4 | CaB6O10 | H2O | CaCl2 | CaSO4 | CaB6O10 | H2O | ||
1, A | 51.98 | 0.23 | 0 | 51.56 | 99.56 | 0.44 | 0 | 91.51 | CaCl2·4H2O + Gyps |
2 | 51.65 | 0.19 | 0.15 | 48.01 | 99.35 | 0.37 | 0.29 | 92.34 | CaCl2·4H2O + Gyps |
3 | 51.74 | 0.16 | 0.45 | 47.65 | 98.83 | 0.31 | 0.86 | 91.02 | CaCl2·4H2O + Gyps |
4 | 51.70 | 0.15 | 0.62 | 47.53 | 98.53 | 0.29 | 1.18 | 90.59 | CaCl2·4H2O + Gyps |
5, E | 49.59 | 0.14 | 1.00 | 49.27 | 97.75 | 0.27 | 1.98 | 97.12 | CaCl2·4H2O+Gyps+Gowerite |
6, B | 50.01 | 0 | 0.04 | 49.95 | 99.92 | 0 | 0.08 | 99.80 | CaCl2·4H2O + Gowerite |
7, C | 0 | 0.63 | 1.55 | 97.82 | 0 | 29.04 | 70.96 | 4705.16 | Gyps + Gowerite |
8 | 0.50 | 0.85 | 1.97 | 96.68 | 15.08 | 25.50 | 59.42 | 2916.50 | Gyps + Gowerite |
9 | 1.40 | 0.71 | 1.47 | 96.42 | 39.11 | 19.83 | 41.06 | 2693.30 | Gyps + Gowerite |
10 | 3.00 | 0.40 | 0.79 | 95.81 | 71.60 | 9.55 | 18.85 | 2286.63 | Gyps + Gowerite |
11 | 7.02 | 0.11 | 0.77 | 92.09 | 88.86 | 1.41 | 9.73 | 1164.98 | Gyps + Gowerite |
12 | 10.82 | 0.11 | 0.95 | 88.12 | 91.08 | 0.93 | 7.99 | 741.72 | Gyps + Gowerite |
13 | 27.19 | 0.48 | 0.80 | 71.53 | 95.50 | 1.69 | 2.81 | 251.25 | Gyps + Gowerite |
14 | 42.41 | 0.32 | 1.83 | 55.44 | 95.18 | 0.72 | 4.10 | 124.43 | Gyps + Gowerite |
15 | 48.28 | 0.27 | 1.89 | 49.55 | 95.71 | 0.54 | 3.75 | 98.23 | Gyps + Gowerite |
表2 四元体系CaCl2-CaSO4-CaB6O10-H2O在308.15 K下溶解度数据
Table 2 Solubilities of quaternary system (CaCl2-CaSO4-CaB6O10-H2O) at 308.15 K
No. | Liquid composition, wB/% | Dry-salt composition, ZB/[g·(100 g·S)-1] | Solid phase | ||||||
---|---|---|---|---|---|---|---|---|---|
CaCl2 | CaSO4 | CaB6O10 | H2O | CaCl2 | CaSO4 | CaB6O10 | H2O | ||
1, A | 51.98 | 0.23 | 0 | 51.56 | 99.56 | 0.44 | 0 | 91.51 | CaCl2·4H2O + Gyps |
2 | 51.65 | 0.19 | 0.15 | 48.01 | 99.35 | 0.37 | 0.29 | 92.34 | CaCl2·4H2O + Gyps |
3 | 51.74 | 0.16 | 0.45 | 47.65 | 98.83 | 0.31 | 0.86 | 91.02 | CaCl2·4H2O + Gyps |
4 | 51.70 | 0.15 | 0.62 | 47.53 | 98.53 | 0.29 | 1.18 | 90.59 | CaCl2·4H2O + Gyps |
5, E | 49.59 | 0.14 | 1.00 | 49.27 | 97.75 | 0.27 | 1.98 | 97.12 | CaCl2·4H2O+Gyps+Gowerite |
6, B | 50.01 | 0 | 0.04 | 49.95 | 99.92 | 0 | 0.08 | 99.80 | CaCl2·4H2O + Gowerite |
7, C | 0 | 0.63 | 1.55 | 97.82 | 0 | 29.04 | 70.96 | 4705.16 | Gyps + Gowerite |
8 | 0.50 | 0.85 | 1.97 | 96.68 | 15.08 | 25.50 | 59.42 | 2916.50 | Gyps + Gowerite |
9 | 1.40 | 0.71 | 1.47 | 96.42 | 39.11 | 19.83 | 41.06 | 2693.30 | Gyps + Gowerite |
10 | 3.00 | 0.40 | 0.79 | 95.81 | 71.60 | 9.55 | 18.85 | 2286.63 | Gyps + Gowerite |
11 | 7.02 | 0.11 | 0.77 | 92.09 | 88.86 | 1.41 | 9.73 | 1164.98 | Gyps + Gowerite |
12 | 10.82 | 0.11 | 0.95 | 88.12 | 91.08 | 0.93 | 7.99 | 741.72 | Gyps + Gowerite |
13 | 27.19 | 0.48 | 0.80 | 71.53 | 95.50 | 1.69 | 2.81 | 251.25 | Gyps + Gowerite |
14 | 42.41 | 0.32 | 1.83 | 55.44 | 95.18 | 0.72 | 4.10 | 124.43 | Gyps + Gowerite |
15 | 48.28 | 0.27 | 1.89 | 49.55 | 95.71 | 0.54 | 3.75 | 98.23 | Gyps + Gowerite |
图2 四元体系CaCl2-CaSO4-CaB6O10-H2O在308.15 K下的干基图及局部放大图
Fig.2 Dry-salt phase diagram and part enlargement of phase diagram for quaternary system (CaCl2-CaSO4-CaB6O10-H2O) at 308.15 K
图3 四元体系CaCl2-CaSO4-CaB6O10-H2O在308.15 K下的水图及局部放大图
Fig.3 Water-phase diagram and part enlargement of water-phase diagram for quaternary system (CaCl2-CaSO4-CaB6O10-H2O) at 308.15 K
No. | Liquid phase composition CaCl2, wb/% | Physicochemical properties | ||
---|---|---|---|---|
Refractive index, nD | Density, ρ/(g·cm-3) | pH | ||
1, A | 51.98 | 1.466014 | 1.50209 | 4.87 |
2 | 51.65 | 1.466722 | 1.51007 | 4.69 |
3 | 51.74 | 1.467257 | 1.51089 | 3.84 |
4 | 51.70 | 1.467872 | 1.51525 | 3.34 |
5, E | 49.59 | 1.470097 | 1.51522 | 2.80 |
6, B | 50.01 | 1.473100 | 1.52760 | 2.01 |
7, C | 0 | 1.334924 | 1.00666 | 7.77 |
8 | 0.50 | 1.336978 | 1.01205 | 7.70 |
9 | 1.40 | 1.335609 | 1.00898 | 7.75 |
10 | 3.00 | 1.337875 | 1.01887 | 7.69 |
11 | 7.02 | 1.349667 | 1.05984 | 7.25 |
12 | 10.82 | 1.360155 | 1.09354 | 6.84 |
13 | 27.29 | 1.401389 | 1.26400 | 5.50 |
14 | 42.41 | 1.443401 | 1.40641 | 4.24 |
15 | 48.28 | 1.457317 | 1.48112 | 3.42 |
表3 四元体系CaCl2-CaSO4-CaB6O10-H2O在308.15 K的物化性质
Table 3 Physicochemical properties of quaternary system (CaCl2-CaSO4-CaB6O10-H2O) at 308.15 K
No. | Liquid phase composition CaCl2, wb/% | Physicochemical properties | ||
---|---|---|---|---|
Refractive index, nD | Density, ρ/(g·cm-3) | pH | ||
1, A | 51.98 | 1.466014 | 1.50209 | 4.87 |
2 | 51.65 | 1.466722 | 1.51007 | 4.69 |
3 | 51.74 | 1.467257 | 1.51089 | 3.84 |
4 | 51.70 | 1.467872 | 1.51525 | 3.34 |
5, E | 49.59 | 1.470097 | 1.51522 | 2.80 |
6, B | 50.01 | 1.473100 | 1.52760 | 2.01 |
7, C | 0 | 1.334924 | 1.00666 | 7.77 |
8 | 0.50 | 1.336978 | 1.01205 | 7.70 |
9 | 1.40 | 1.335609 | 1.00898 | 7.75 |
10 | 3.00 | 1.337875 | 1.01887 | 7.69 |
11 | 7.02 | 1.349667 | 1.05984 | 7.25 |
12 | 10.82 | 1.360155 | 1.09354 | 6.84 |
13 | 27.29 | 1.401389 | 1.26400 | 5.50 |
14 | 42.41 | 1.443401 | 1.40641 | 4.24 |
15 | 48.28 | 1.457317 | 1.48112 | 3.42 |
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