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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2022 · IF 3.119

Measurements of Solid–Liquid Equilibria in Quaternary System LiBr–MgBr2–KBr–H2O and Its Two Ternary Systems (LiBr–MgBr2–H2O and MgBr2–KBr–H2O) at 288.15 and 308.15 K

Guopeng Chen,Junsheng Yuan,Zilong Liu,Ming Lei,Bin Li

The solid–liquid equilibria in the LiBr–MgBr2–KBr–H2O system was measured, along with its two subsystems, LiBr–MgBr2–H2O and MgBr2–KBr–H2O, at 308.15 and 288.15 K using the isothermal dissolution equilibrium method. The stable phase diagrams of the three systems at 308.15 and 288.15 K were plotted. For the ternary LiBr–MgBr2–H2O system, two univariant curves, one ternary invariant point, and two crystallization fields, the fields being MgBr2·6H2O and LiBr·2H2O, were identified. The ternary system MgBr2–KBr–H2O contained three univariant curves, two ternary invariant points, and three crystallization fields corresponding to KBr, KBr·MgBr2·6H2O, and MgBr2·6H2O. From the stable phase diagram of the quaternary system, five univariant curves, four crystallization fields, and two invariant points were observed. The corresponding solids of the four crystallization fields were KBr, LiBr·2H2O, KBr·MgBr2·6H2O, and MgBr2·6H2O. The quaternary phase diagrams at 288.15 and 308.15 K had similar shapes, and the shapes of each crystallization field were identical. The crystallization field of KBr was larger than the other crystallization fields. With an increase in temperature, the crystallization field of KBr became smaller and that of LiBr became larger.

研究领域: 化学热力学 · 无机化学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2023 · IF 2.6

Study on Stable Phase Equilibria of Quinary System LiBr–NaBr–KBr–MgBr2–H2O at 298.15 K

Chang-Wei Peng,Rui-Zhi Cui,Shi-Hua Sang,Hong-Bao Ren

According to the composition characteristics of mineral elements in underground brine in the Sichuan basin of China, the complete phase equilibria and phase diagram of the quinary system LiBr–NaBr–KBr–MgBr2–H2O were studied at 298.15 K. Using the experimentally determined solubilities and equilibrium solids, the spatial stereo phase diagram of the quinary system, the dry base projection phase diagrams of the saturated surfaces of the four salts MgBr2·6H2O, KBr, LiBr·2H2O, and NaBr·2H2O, and the corresponding water content diagrams were plotted, respectively. The experimental results show that at 298.15 K, in addition to the four original components, the anhydrous salt NaBr and the double salt KBr·MgBr2·6H2O are formed. The phase diagram of the quinary system at 298.15 K contains 10 univariate curves, three invariant points, and six equilibrium solid-phase crystallization regions (KBr crystallization region, NaBr crystallization region, NaBr·2H2O crystallization region, MgBr2·6H2O crystallization region, LiBr·2H2O crystallization region, KBr·MgBr2·6H2O crystallization region). When MgBr2·6H2O or KBr is saturated, LiBr has a strong salting-out effect on KBr, NaBr, or MgBr2 and NaBr, while when LiBr·2H2O is saturated, MgBr2 has a salting-out effect on KBr and NaBr. All four saturated projection surfaces have MgBr2·6H2O, and NaBr is generated. These phase equilibrium data can provide a theoretical basis to guide underground brine mining and extract useful components.

研究领域: 化学 · 材料科学
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CHEMICAL RESEARCH IN CHINESE UNIVERSITIES · 2020 ·Vol. 36 ·期 6 ·1234-1240 · IF 1.063

Measured and Predicted Solubility Phase Diagrams of Quaternary Systems LiBr-NaBr-MgBr2-H2O and LiBr-KBr-MgBr2-H2O at 298.15 K

Cui Ruizhi,Li Wu,Dong Yaping,Li Jun

The stable phase equilibria of quaternary systems LiBr-NaBr-MgBr 2 -H 2 O and LiBr-KBr-MgBr 2 -H 2 O at 298.15 K were studied by both experimental measurement(isothermal solution saturation method) and theoretical prediction(Pitzer model). The solubilities of the saturated solution have been determined experimentally and two stable phase diagrams and relevant water diagrams of the two quaternary systems were obtained. Results show that quaternary system LiBr-NaBr-MgBr 2 -H 2 O is hydrate II type as NaBr and NaBr·2H 2 O coexistence. Its phase diagram consists of only one invariant point, four univariant curves, and five crystallization fields. The quaternary system LiBr-KBr-MgBr 2 -H 2 O is a complex type as the double salt KBr·MgBr 2 ·6H 2 O formed. In addition to this double salt, the three single salts LiBr·2H 2 O, KBr and MgBr 2 ·6H 2 O also crystallize. In this paper, the solubilities of phase equilibria in above quaternary systems were also calculated by the Pitzer’s electrolyte solution model. All the needed parameters can be obtained from the literature or be fitted by experimental data. On the Basis of the experimental and calculated results, the phase diagram of the quaternary system was plotted for comparison. It shows that the calculation results are consistent with the experimental ones.

CAS / MDL: 7758-02-3
研究领域: 化学热力学 · 无机化学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2023 · IF 2.6

Experiments and Prediction of Solid–Liquid Phase Equilibria in the Quinary System NaBr–KBr–MgBr2–SrBr2–H2O and Its Quaternary Subsystem NaBr–MgBr2–SrBr2–H2O at 308.2 K

Chun-Tao Hu,Yun-Yun Gao,Shi-Hua Sang,Yu-Qiu Cen,Xiao-Feng Guo,Cheng Li

To efficiently exploit and utilize bromine-rich brine resources of China, solid–liquid phase equilibria of the quinary system NaBr–KBr–MgBr2–SrBr2–H2O (saturated with KBr) and the quaternary system NaBr–MgBr2–SrBr2–H2O at 308.2 K were studied in detail by the isothermal dissolution equilibrium method. The dry salt phase diagram of the quinary system NaBr–KBr–MgBr2–SrBr2–H2O (saturated with KBr) includes one invariant point, three isothermal dissolution curves, and three crystallization regions (NaBr·2H2O, KBr·MgBr2·6H2O, and SrBr2·6H2O) under the condition of KBr saturation. And the crystallization region of KBr·MgBr2·6H2O is the smallest, so KBr·MgBr2·6H2O is difficult to crystallize and precipitate. Similarly, The dry salt phase diagram of the quaternary system NaBr–MgBr2–SrBr2–H2O is composed of two invariant points, five isothermal solubility curves, and four crystallization fields, which are hydrate salts NaBr·2H2O, MgBr2·6H2O, and SrBr2·6H2O and anhydrous simple salt NaBr. The crystallization region of MgBr2·6H2O is the smallest, the solubility of magnesium bromide is the largest, and it is difficult to crystallize and precipitate in this saturated solution. Furthermore, the mixing ion-interaction parameter ΨNa, Sr, Br of Pitzer’s model is fitted, which can be used for the subsequent prediction of phase equilibria containing strontium system. In addition, the solubilities of salts in the quinary system and the quaternary subsystem were theoretically predicted, and the experimental value was compared with the calculated value. The calculated value was in good agreement with the experimental value.

CAS / MDL: 10294-41-4 7789-53-9
研究领域: 化学工程 · 无机化学
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Frontiers in Chemistry · 2023 · IF 5.5

Solid-liquid equilibria in relevant subsystems of LiBr-NaBr-KBr-MgBr2-CaBr2-H2O system at 298.15 K

Cui Ruizhi,Peng Changwei,Nie Guoliang,Sang Shihua,Ren Hongbao,Li Wu

In view of the composition characteristics of lithium, calcium and bromine rich in Nanyishan oil and gas field brine of western Qaidam Basin, Qinghai Province, as well as based on the results reported in relevant literature, the phase equilibrium relationship of ternary system LiBr-CaBr2-H2O at 298.15 K was studied by isothermal dissolution equilibrium method. The equilibrium solid phase crystallization regions, as well as the compositions of invariant point, in phase diagram of this ternary system were clarified. On basis of the above ternary system research, the stable phase equilibria of quaternary systems (LiBr-NaBr-CaBr2-H2O, LiBr-KBr-CaBr2-H2O and LiBr-MgBr2-CaBr2-H2O), as well as quinary systems (LiBr-NaBr-KBr-CaBr2-H2O, LiBr-NaBr-MgBr2-CaBr2-H2O and LiBr-KBr-MgBr2-CaBr2-H2O) were further carried out at 298.15 K. According to the above experimental results, the corresponding phase diagrams at 298.15 K were drawn, which revealed the phase relationship of each component in solution and the law of crystallization and dissolution, and meanwhile summarized changing trends. The research results of this paper lay a foundation for further research on the multitemperature phase equilibria and thermodynamic properties of lithium and bromine containing high-component brine system in later stage, and also provide basic thermodynamic data for guiding the comprehensive development and utilization of this oil and gas field brine resource.

研究领域: 化学 · 热力学
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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2021 · IF 2.694

Measurements and Predictions of the Solubilities in the Ternary System MgBr2 + SrBr2 + H2O at 288 and 308 K

Yun-Yun Gao,Xiao-Feng Guo,Lan-Rong Zhao,Shi-Hua Sang

The stable phase equilibria of the ternary system MgBr2 + SrBr2 + H2O at 288 and 308 K were studied with the isothermal dissolution equilibrium method. The compositions of solutions and solid phases have been determined and the equilibrium solid phases at the invariant points were identified with the aid of the X-ray diffraction method. The phase diagrams of this system at 288 and 308 K were both constructed in terms of experimental results. Two stable phase diagrams show that this system is hydrate type I at two temperatures without formation of a solid solution or complex salt. Both the phase diagrams are composed of one invariant point, two univariate curves, and two crystallization regions (SrBr2·6H2O and MgBr2·6H2O). The equilibrium solid phases of the invariant point at 288 and 308 K are both SrBr2·6H2O and MgBr2·6H2O, respectively. Combining the Pitzer single-salt parameters of MgBr2 and SrBr2 reported in the literatures, the unreported mixing ion-interaction parameters θMg,Sr and ΨMg,Sr,Br at 288 and 308 K were fitted with the measured values in this study using the Pitzer equations. The agreement between the experimental values and calculated results in the ternary system MgBr2 + SrBr2 + H2O at 288 and 308 K shows that the parameters fitted with solubilities are reliable.

研究领域: 化学 · 物理化学
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