298.2 K四元体系MgCl2+CaCl2+AlCl3+H2O 相平衡研究

何志意; 方滇东; 郑秋风; 任思颖; 罗军; 于旭东

doi:10.13779/j.cnki.issn1001-0076.2022.06.018

298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 相平衡研究

1.
四川省冶勘设计集团有限公司, 四川成都 610051

2.
成都理工大学材料与化学化工学院, 四川成都 610059

详细信息

作者简介: 何志意（1989—）,女,硕士,工程师,研究方向为分析检测；E-mail：2298049880@qq.com

通讯作者: 于旭东（1985—）,男,博士,副教授,研究方向为相平衡与相分离技术；E-mail：xwdlyxd@126.com。

中图分类号: TF111.3

收稿日期: 2022-10-16

刊出日期: 2022-12-26

Phase Equilibria of Aqueous Quaternary System MgCl₂+CaCl₂+AlCl₃+H₂O at 298.2 K

1.
Sichuan Metallurgical Geological Survey and Design Group Co., Ltd, Chengdu 610051, China

2.
College of Materials and Chemistry & Chemical Engineering, Chengdu University of Technology, Chengdu 610059, China

More Information

Corresponding author: YU Xudong, xwdlyxd@126.com

Received Date: 16 October 2022

Publish Date: 26 December 2022

摘要

摘要:
为获取粉煤灰含铝溶浸液中铝与共存钙、镁之间的作用规律，采用等温溶解平衡法开展了298.2 K时四元体系MgCl₂+CaCl₂+AlCl₃+H₂O相平衡研究，测定了平衡液相组成及平衡液相密度，同时，绘制了该四元体系的干基相图、水图、密度-组成图。研究发现：298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 稳定相图由2个共饱点、4个结晶区以及5条单变量曲线组成，有复盐溢晶石（2MgCl₂·CaCl₂·12H₂O）生成，为复杂四元体系。4个结晶区分别对应3个单盐结晶区MgCl₂·6H₂O、CaCl₂·6H₂O、AlCl₃·6H₂O和1个复盐结晶区2MgCl₂·CaCl₂·12H₂O，结晶区按照AlCl₃·6H₂O、MgCl₂·6H₂O、CaCl₂·6H₂O、2MgCl₂·CaCl₂·12H₂O顺序依次减小，对应AlCl₃·6H₂O溶解度最小，2MgCl₂·CaCl₂·12H₂O溶解度最大。
- 相平衡 /
- 四元体系MgCl₂+CaCl₂+AlCl₃+H₂O /
- 溶解度 /
- 溢晶石
Abstract:
In order to obtain the interaction law between aluminum and coexisting calcium and magnesium in leaching solution containing aluminum of fly ash, the phase equilibria of the quaternary system MgCl₂+CaCl₂+AlCl₃+H₂O was investigated by isothermal dissolution method at 298.2 K. The composition of liquid phase and density were determined. Meanwhile, the phase diagram, water diagram and density vs composition diagram of the quaternary system were drawn, respectively. It was found that the stable phase diagram of the quaternary system MgCl₂+CaCl₂+AlCl₃+H₂O consisted of two invariant points, four crystallization regions and five univariate curves, which belonged to a complex system with the double salt of tachyhydrite formed. These four crystallization regions corresponded to single salts MgCl₂·6H₂O, CaCl₂·6H₂O, AlCl₃·6H₂O and double salt 2MgCl₂·CaCl₂·12H₂O, respectively. The crystallization regions decreaseed in the order of AlCl₃·6H₂O, MgCl₂·6H₂O, CaCl₂·6H₂O and 2MgCl₂·CaCl₂·12H₂O, the solubility of AlCl₃·6H₂O was the smallest and the solubility of 2MgCl₂·CaCl₂·12H₂O is the highest.
- phase equilibria /
- quaternary system /
- solubility /
- tachyhydrite

HTML全文

图 1 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 稳定相图

Figure 1.

下载: 全尺寸图片幻灯片

图 2 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 共饱点F₁处平衡固相XRD谱图

Figure 2.

下载: 全尺寸图片幻灯片

图 3 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 共饱点F₂处平衡固相XRD谱图

Figure 3.

下载: 全尺寸图片幻灯片

图 4 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 水含量−组成图

Figure 4.

下载: 全尺寸图片幻灯片

图 5 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 密度−组成图

Figure 5.

下载: 全尺寸图片幻灯片

表 1 298.2 K四元体系MgCl₂+CaCl₂+AlCl₃+H₂O 平衡溶液的溶解度和密度

Table 1. The solubilities and densities of the quaternary system MgCl₂+CaCl₂+AlCl₃+H₂O at 298.2 K

编号	密度/(g·cm⁻³)	液相组成, w(B) /%					干盐指数 J(B) (g/100g S)				平衡固相
		液相组成, w(B) /%				J(MgCl₂)+J(CaCl₂)+J(AlCl₃)=100
		w(MgCl₂)	w(CaCl₂)	w(AlCl₃)	w(H₂O)		J(MgCl₂)	J(CaCl₂)	J(AlCl₃)	J(H₂O)
1, A	1.4415	10.20	35.03	0.00	54.77		22.55	77.45	0.00	121.09	CaCl₂·6H₂O+Tac
2	1.4419	8.99	36.00	0.22	54.78		19.89	79.62	0.50	121.15	CaCl₂·6H₂O+Tac
3	1.4435	8.39	36.39	0.40	54.82		18.58	80.54	0.89	121.33	CaCl₂·6H₂O+Tac
4	1.4439	7.42	37.16	0.53	54.89		16.45	82.37	1.18	121.67	CaCl₂·6H₂O+Tac
5	1.4442	6.65	37.85	0.59	54.91		14.75	83.94	1.31	121.77	CaCl₂·6H₂O+Tac
6	1.4462	5.61	38.82	0.68	54.90		12.43	86.07	1.50	121.73	CaCl₂·6H₂O+Tac
7, F₁	1.4477	4.03	39.59	1.42	54.96		8.95	87.90	3.15	121.99	CaCl₂·6H₂O+AlCl₃·6H₂O+Tac
8	1.4285	5.63	38.21	1.25	54.91		12.48	84.74	2.78	121.76	AlCl₃·6H₂O+Tac
9	1.4163	8.56	34.71	1.41	55.32		19.16	77.69	3.15	123.84	AlCl₃·6H₂O+Tac
10	1.4150	9.41	33.95	1.30	55.34		21.06	76.02	2.92	123.9	AlCl₃·6H₂O+Tac
11	1.4132	11.30	32.46	1.05	55.19		25.22	72.43	2.35	123.16	AlCl₃·6H₂O+Tac
12	1.4134	12.24	31.58	0.97	55.21		27.33	70.51	2.16	123.26	AlCl₃·6H₂O+Tac
13, F₂	1.4171	13.97	29.20	0.71	56.12		31.84	66.54	1.62	127.92	MgCl₂·6H₂O+AlCl₃·6H₂O+Tac
14	1.4172	13.39	29.81	0.65	56.15		30.54	67.98	1.48	128.02	MgCl₂·6H₂O+Tac
15	1.4170	14.44	28.84	0.54	56.18		32.95	65.81	1.24	128.20	MgCl₂·6H₂O+Tac
16	1.4167	14.96	28.43	0.40	56.22		34.17	64.93	0.90	128.41	MgCl₂·6H₂O+Tac
17	1.4162	16.08	27.60	0.10	56.22		36.72	63.04	0.23	128.44	MgCl₂·6H₂O+Tac
18	1.4158	16.65	27.08	0.04	56.24		38.04	61.88	0.09	128.50	MgCl₂·6H₂O+Tac
19, B	1.4163	17.27	26.48	0.00	56.25		39.47	60.53	0.00	128.57	MgCl₂·6H₂O+Tac
20, C	1.3403	30.45	0.00	5.65	63.90		84.35	0.00	15.65	177.01	MgCl₂·6H₂O+AlCl₃·6H₂O
21	1.3436	28.36	2.85	4.91	63.88		78.52	7.89	13.59	176.88	MgCl₂·6H₂O+AlCl₃·6H₂O
22	1.3450	27.03	6.05	3.97	62.95		72.96	16.32	10.72	169.92	MgCl₂·6H₂O+AlCl₃·6H₂O
23	1.3513	24.75	10.48	3.18	61.59		64.42	27.29	8.29	160.29	MgCl₂·6H₂O+AlCl₃·6H₂O
24	1.3679	23.42	13.81	2.42	60.35		59.07	34.82	6.11	152.17	MgCl₂·6H₂O+AlCl₃·6H₂O
25	1.3797	21.03	18.04	1.65	59.28		51.64	44.31	4.05	145.58	MgCl₂·6H₂O+AlCl₃·6H₂O
26	1.3911	18.25	22.03	1.16	58.56		44.04	53.16	2.80	141.32	MgCl₂·6H₂O+AlCl₃·6H₂O
27	1.4048	15.67	26.38	1.05	56.90		36.37	61.20	2.43	132.04	MgCl₂·6H₂O+AlCl₃·6H₂O
28, D	1.4436	0.00	42.32	2.37	55.31		0.00	94.70	5.30	123.76	CaCl₂·6H₂O+AlCl₃·6H₂O
29	1.4431	0.84	42.29	2.06	54.81		1.85	93.58	4.57	121.29	CaCl₂·6H₂O+AlCl₃·6H₂O
30	1.4446	1.58	42.20	1.74	54.48		3.46	92.71	3.82	119.68	CaCl₂·6H₂O+AlCl₃·6H₂O
31	1.4450	2.21	41.99	1.59	54.21		4.83	91.69	3.48	118.37	CaCl₂·6H₂O+AlCl₃·6H₂O
注：Tac为2MgCl₂·CaCl₂·12H₂O。温度、密度的标准不确定度分别为0.2 K、0.0002 g/cm³; w(MgCl₂)、w(CaCl₂)及w(AlCl₃)的相对不确定度分别为0.0021、 0.0030、0.0026。

下载: 导出CSV

参考文献(29)

[1]	徐硕, 杨金林, 马少健. 粉煤灰综合利用研究进展[J]. 矿产保护与利用, 2021, 41(3): 104−111. doi: 10.13779/j.cnki.issn1001-0076.2021.03.015 XU S, YANG J L, MA S J. Research progress in the comprehensive utilization of fly ash[J]. Conservation and utilization of mineral resources, 2021, 41(3): 104−111. doi: 10.13779/j.cnki.issn1001-0076.2021.03.015
[2]	梁慧婷. 中国煤炭产业现状分析[J]. 农村经济与科技, 2019, 30(14): 113−114. doi: 10.3969/j.issn.1007-7103.2019.14.075 LIANG H T. Analysis on the present situation of China's Coal Industry[J]. Rural Economy and Science, 2019, 30(14): 113−114. doi: 10.3969/j.issn.1007-7103.2019.14.075
[3]	王建新, 李晶, 赵仕宝, 等. 中国粉煤灰的资源化利用研究进展与前景[J]. 硅酸盐通报, 2018, 37(12): 3834−3841. doi: 10.16552/j.cnki.issn1001-1625.2018.12.020 WANG J X, LI J, ZHAO S B, et al. Research Progress and Prospect of Resource Utilization of Fly Ash in China[J]. Bulletin of the Chinese Ceramic Society, 2018, 37(12): 3834−3841. doi: 10.16552/j.cnki.issn1001-1625.2018.12.020
[4]	李博琦, 谢贤, 吕晋芳, 等. 粉煤灰资源化综合利用研究进展及展望[J]. 矿产保护与利用, 2020, 40(5): 153−160. LI B Q, XIE X, LV J F, et al. Progress and prospect of research on comprehensive utilization of fly ash[J]. Conservation and utilization of mineral resources, 2020, 40(5): 153−160.
[5]	马家玉. 一种用于循环流化床粉煤灰的处理方法: CN104445212B[P]. 2017-09-12. MA J Y. A treatment method of fly Ash in circulating Fluidized bed: CN104445212B[P]. 2017-09-12.
[6]	雷锦顺, 李东东, 庄子宇, 等. Li-Na-K-Mg-Ca-Sr-Cl-H₂O七元体系多温相平衡性质的热力学模拟研究[J]. 盐湖研究, 2021, 29(3): 17−37. LEI J S, LI D D, ZHUANG Z Y, et al. Thermodynamic Modeling of the Phase Equilibrium in the Li-Na-K-Mg-Ca-Sr-Cl-H₂O System[J]. Journal of salt lake Resesrch, 2021, 29(3): 17−37.
[7]	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, CHENG P J, YU X D. Phase equilibria for quaternary system Rb⁺, Cs⁺, Mg²⁺ // SO₄²⁻ - H₂O at 298.2 K[J]. CIESC Journal, 2020, 71(8): 3460−3468.
[8]	任永胜, 曹晶, 于冰洁. 313.15 K 四元体系Na⁺ // SO₄²⁻, CO₃^2-, NO₃⁻ - H₂O固液相平衡研究[J]. 化工学报, 2019, 70(6): 2102−2109. RENG Y S, CAO J, YU B J. Solid-liquid equilibria of quaternary system Na⁺ // SO₄^2-, CO₃²⁻, NO₃⁻ -H₂O at 313.15 K[J]. CIESC Journal, 2019, 70(6): 2102−2109.
[9]	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. doi: 10.1252/jcej.17we387
[10]	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. doi: 10.1021/acs.jced.6b00981
[11]	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. doi: 10.1021/je300124u
[12]	张志翔, 曾英, 于旭东. 三元体系MgCl₂+NH₄Cl+H₂O 298.15 K稳定相平衡[J]. 化学工程, 2012, 40(1): 38−42. doi: 10.3969/j.issn.1005-9954.2012.01.010 ZHANG Z X, ZENG Y, YU X D. Stable phase equilibrium in aqueous ternary system MgCl₂+NH₄Cl+H₂O at 298.15 K[J]. Chemical Engineering(China), 2012, 40(1): 38−42. doi: 10.3969/j.issn.1005-9954.2012.01.010
[13]	陈帅, 杨博, 陈念粗, 等. 三元体系NH₄Cl+MgCl₂+H₂O 323.2 K相平衡研究[J]. 无机盐工业, 2022, 54(4): 100−103. CHEN S, YANG B, CHEN N C, et al. Study on phase equilibria of ternary system NH₄Cl+MgCl₂+H₂O at 323.2 K[J]. Inorganic Chemicals Industry, 2022, 54(4): 100−103.
[14]	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 Thermochemics, 2011, 35(3): 269−275. doi: 10.1016/j.calphad.2011.04.002
[15]	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]. Russian Journal of Physical Chemistry A, 2014, 88(13): 2325−2330. doi: 10.1134/S0036024414130214
[16]	LI X, YUAN J S, JI Z Y, et al. Phase equilibrium of the ternary system of NH₄Cl-CaCl₂-H₂O at 50℃[J]. Frontiers of Chemical Engineering in China, 2010, 4(1): 75−77. doi: 10.1007/s11705-009-0296-0
[17]	ASSARSSON G O. Equilibria in Aqueous Systems Containing K⁺, Na⁺, Ca²⁺, Mg²⁺ and Cl^-. III. The Ternary System CaCl₂-MgCl₂-H₂O[J]. Journal of the American Chemical Society, 1950, 72(4): 1442−1444. doi: 10.1021/ja01160a004
[18]	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 Equilibria, 2020, 507: 112426. doi: 10.1016/j.fluid.2019.112426
[19]	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]. Journal of Chemical & Engineering Data, 2016, 61(5): 1749−1755.
[20]	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 equilibria of AlCl₃+CaCl₂+H₂O, AlCl₃+FeCl₃+H₂O and CaCl₂+FeCl₃+H₂O ternary systems at 35℃[J]. CIESC Journal, 2017, 68(7): 2653−2659.
[21]	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]. Journal of Chemical & Engineering Data, 2019, 64(8): 3514−3520.
[22]	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 Journal, 2013, 59(6): 1855−1867. doi: 10.1002/aic.13963
[23]	中国科学院青海盐湖研究所. 卤水和盐的分析方法(第二版)[M]. 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, (2nd ed)[M]. Chinese Science Press: Beijing, China, 1988: 69-72.
[24]	赵世卓, 张煦, 席欢, 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—2020 [S]. 北京: 中国标准出版社, 2020. ZHAO S Z, ZHANG X, XI H, et al. Methods for chemical analysis of aluminium and aluminium alloys—Part 16: Determination of magnesium content: GB/T 20975.16—2020 [S]. Beijing: Standards Press of China, 2020.
[25]	张晓, 谢辉, 席欢, 等. 铝及铝合金化学分析方法第21部分: 钙含量的测定: GB∕T 20975.21—2020 [S]. 北京: 中国标准出版社, 2020. ZHANG X, XIE H, XI H, et al. Methods for chemical analysis of aluminium and aluminium alloy—Part 21: Determination of calcium content: B∕T 20975.21—2020 [S]. Beijing: Standards Press of China, 2020.
[26]	李跃平, 石磊, 张数朝, 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: GB/T 20975.25—2008 [S]. 北京: 中国标准出版社, 2008. LI Y P, SHI T, 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: Standards Press of China, 2008.
[27]	成怀刚, 程芳琴. 水盐体系相分离[M]. 北京: 冶金工业出版社, 2022: 44-45. CHENG H G, CHENG F Q. Phase separation of salt-water system [M]. Beijing: Metallurgical Industry Press, 2022: 44-45.
[28]	ZENG D W, ZHOU H Y, VOIGT W, Thermodynamic consistency of solubility and vapor pressure of a binary saturated salt + water system: Ⅱ. CaCl₂+H₂O[J]. Fluid Phase Equilibria, 2007, 253: 1-11.
[29]	LI D D, ZENG D W, YIN X, et al. Phase diagrams and thermochemical modeling of salt lake brine systems. Ⅱ. NaCl+H₂O, KCl+H₂O, MgCl₂+H₂O and CaCl₂+H₂O systems[J]. Calphad, 2016, 53: 78−89. doi: 10.1016/j.calphad.2016.03.007