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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 · 2022 · IF 3.119

Stable Phase Equilibria of the Quaternary System LiBr-NaBr-KBr-H2O and the Ternary System LiBr-KBr-H2O at 323.15 K

Guo-Liang Nie,Rui-Zhi Cui,Wu Li

According to the composition characteristics of lithium, potassium, bromine, and other resources rich in the salt lake brine of the Qinghai–Tibet Plateau, the phase equilibria of the quaternary system LiBr-NaBr-KBr-H2O and its ternary subsystem LiBr-KBr-H2O at 323.15 K are studied by an isothermal dissolution equilibrium method. The solubility of each system in equilibrium solution at the corresponding temperature is measured, and the corresponding phase diagrams are drawn according to the phase equilibrium experimental data. The results show that there is no complex salt or solid solution in the ternary system LiBr-KBr-H2O at 323.15 K. The phase diagram contains one invariant point (E1), two univariate curves (AE1 and BE1), and two equilibrium solid crystallization regions (corresponding to LiBr·H2O and KBr), belonging to the simple cosaturated type. The quaternary system LiBr-NaBr-KBr-H2O also has no formation of complex salt and solid solution. The phase diagram contains two invariant points (F1 and F2), five univariate curves (E1F1, E3F1, F1F2, E2F2, and E4F2), and four equilibrium solid-phase crystallization regions (corresponding to LiBr·H2O, KBr, NaBr·2H2O, and NaBr). At the same time, to further explain the phase equilibrium relationship of each system at different temperatures and the change rule of each component, comparison and discussion are carried out.

研究领域: 化学工程 · 材料科学
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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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JOURNAL OF CHEMICAL AND ENGINEERING DATA · 2020 · IF 2.369

Solid–Liquid Phase Equilibria in the Ternary System CaBr2–SrBr2–H2O at 273, 298, and 323 K

Xue-ping Zhang,Wei Wang,Han-zhong Zhang,Shi-hua Sang

In this paper, the stable phase equilibrium data of the ternary system CaBr2-SrBr2-H2O at T = 273, 298, and 323 K and 101.3 kPa have been determined by isothermal the dissolution equilibrium method. The phase diagrams of them at the investigated temperatures have been drawn. It is found that the isothermal phase diagrams of the CaBr2–SrBr2–H2O system at T = 273, 298, and 323 K are classified as a simple co-saturation type consisting of an invariant point and two univariant curves. The equilibrium solid phases corresponding to an invariant point of the system were detected as CaBr2·6H2O + SrBr2·6H2O at 273 and 298 K and those identified as CaBr2·4H2O + SrBr2·6H2O at 323 K. In this system, calcium bromide exhibits a strong salting-out effect on strontium bromide. Furthermore, isothermal solubilities at three temperatures were compared and discussed.

CAS / MDL: 71626-99-8 7789-53-9
研究领域: 化学 · 材料科学
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Processes · 2022 ·Vol. 10 ·期 5 ·823 · IF 3.352

Phase Equilibrium of the Quaternary System LiBr-Li2SO4-KBr-K2SO4-H2O at 308.15 K

Bin Li,Xinjun Jing,Junsheng Yuan

The phase equilibria of the reciprocal quaternary system LiBr-Li2SO4-KBr-K2SO4-H2O and its ternary sub-systems LiBr-Li2SO4-H2O and KBr-K2SO4-H2O at 308.15 K were studied using the isothermal dissolution equilibrium method. Then, the solubility data of the equilibrium solutions were collected, and the phase diagrams were plotted. The phase diagrams of the ternary sub-systems at 308.15 K were compared with those at other temperatures. This study found that the phase diagram of the LiBr-Li2SO4-H2O system at 308.15 K consisted of an invariant point, two solid-phase crystallization regions of Li2SO4·H2O and LiBr·2H2O, and their corresponding solubility curves. The system generated two hydrated salts, which belonged to the hydrate type I phase diagram. The phase diagram of the KBr-K2SO4-H2O system at 308.15 K consisted of an invariant point, two univariant solubility curves, and two solid-phase crystallization regions of KBr and K2SO4, and no solid solution and double salts were formed. Thus, it belonged to a simple co-saturation type phase diagram. In the LiBr-Li2SO4-KBr-K2SO4-H2O system, K2SO4·Li2SO4double salt formed at 308.15 K, and the phase diagram consisted of three invariant points, five crystallization regions, and seven univariant solubility curves.Keywords:lithium bromide;potassium bromide;lithium sulfate;potassium sulfate;phase equilibrium

研究领域: 化学 · 材料科学
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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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Scientific Reports · 2016 ·Vol. 6 ·期 1 ·1-13 · IF 5.228

Mechanochemical conversion of brominated POPs into useful oxybromides: a greener approach

Cagnetta Giovanni,Liu Han,Zhang Kunlun,Huang Jun,Wang Bin,Deng Shubo,Wang Yujue,Yu Gang

Brominated organic pollutants are considered of great concern for their adverse effect on human health and the environment, so an increasing number of such compounds are being classified as persistent organic pollutants (POPs). Mechanochemical destruction is a promising technology for POPs safe disposal because it can achieve their complete carbonization by solvent-free high energy ball milling at room temperature. However, a large amount of co-milling reagent usually is necessary, so a considerable volume of residue is produced. In the present study a different approach to POPs mechanochemical destruction is proposed. Employing stoichiometric quantities of Bi 2 O 3 or La 2 O 3 as co-milling reagent, brominated POPs are selectively and completely converted into their corresponding oxybromides (i.e. BiOBr and LaOBr), which possess very peculiar properties and can be used for some actual and many more potential applications. In this way, bromine is beneficially reused in the final product, while POPs carbon skeleton is safely destroyed to amorphous carbon. Moreover, mechanochemical destruction is employed in a greener and more sustainable manner.

CAS / MDL: 79-94-7
研究领域: 环境科学 · 化学工程
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Environmental Chemistry Letters · 2021 ·Vol. 19 ·期 4 ·3517-3522 · IF 9.027

Higher photochemical production of bromophenol by quinone-like substances extracted from humic substances using a new emodin-imprinted polymer

Liu Hui,Qiu Xiaojun,Li Zhi,Zhu Xiaomei,Sun Bing,Zhang Xiaoxing

Dissolved organic matter (DOM) in waters, soils, sediments, and organic waste is considered to have major role in the photochemical generation of emerging organobromine contaminants, yet mechanisms are unclear. Here we fractionated soil humic acids into bound quinone-like substances and an effluent fraction, using a new emodin-imprinted polymer. We tested the effect of these fractions on the photobromination of phenol with bromide. Results show that quinone-like substances induce three times more bromophenols than the effluent fraction. Our findings reveal a new method to separate reactive compounds from DOM and imply that formation of organobromine contaminants may be controlled by the composition of organic matter.

研究领域: 环境化学 · 光化学 · 分析化学 · 环境科学
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ENVIRONMENTAL SCIENCE & TECHNOLOGY · 2024 · IF 10.8

Simultaneous Oxidation of Bromide and Dissolution of Manganese Oxide Induced by Freezing

Yaohua Wu,Huazhe Wang,Juanshan Du,Yi Hu,Qinglian Wu,Wanqian Guo,Wonyong Choi

This study demonstrates that the oxidation of bromide by birnessite (δ-MnO2) results in the concurrent production of soluble manganese (Mn(II)) and reactive bromine (RBr) species in frozen solutions, a process not observed in aqueous solutions. This enhanced oxidation in ice is attributed to the concentration of protons, birnessite, or bromide in the ice grain boundary region. Furthermore, different types of commercial manganese oxides can also oxidize bromide to RBr and release Mn(II) in ice. The presence of fulvic acid (FA) further increases the simultaneous production of RBr and Mn(II) in ice, accompanying the formation of organobromine compounds (OBCs). In frozen δ-MnO2/Br–/FA system, a significant increase in OBCs, mainly highly unsaturated and phenolic compounds, was detected using Fourier transform ion cyclotron resonance mass spectrometry. A marked contrast was observed in the number of OBCs formed in frozen solutions (853 and 415 OBCs at initial pH 3.0 and 5.8, respectively) compared to their aqueous counterparts (11 and 23 OBCs). These findings introduce a new pathway for the formation of RBr, Mn(II), and OBCs in ice, highlighting the need for further research on the environmental fate of bromide and manganese.

研究领域: 环境科学 · 化学
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Journal of Environmental Chemical Engineering · 2024 · IF 7.4

Carbon molecular sieve gas separation membranes derived from in-situ crosslinked polyimide containing bromine groups

Min Chen,Jiangzhou Luo,Jun Hu,Yuxuan Zhao,Honglei Ling,Xueping Zong,Song Xue

The network polyimide (PI) precursor is a promising candidate to fabricate the advanced carbon molecular sieve (CMS) membrane since its robust crosslinked structure could prevent pore structure collapse during CMS formation. Exploring the relationship between network PI precursor structure and CMS membrane is highly significant. Herein, a novel brominated network PI precursor was fabricated via in-situ cross-linking technique firstly, and then the thermally induced bromination/debromination process was applied to tune the microporosity and gas transport properties of network PI precursor and its derived CMS membranes. After the bromination/debromination and carbonization at 550 °C, the resultant CMS membrane exhibited both high gas permeability and gas selectivities compared to its un-brominated network PI precursor derived CMS membrane. This is due to the bromination/debromination and carbonization enable the CMS membrane possesses large d -spacing values (11.06 Å), high BET surface areas (538.57 m 2 /g), and high percentage (∼71 %) of ultra-micropores. For instance, 6F-TA/TA-Br-550/30 membrane exhibits great CO 2 /CH 4 separation ability, with a CO 2 permeability of 6300 Barrer and a CO 2 /CH 4 selectivity of 46.11, which is suppressed the latest 2019 trade-off curves. We anticipate that the present bromination/debromination and carbonization could provide a fresh perspective on the rational design of network PI precursor and its derived CMS membrane with excellent gas separation performance.

CAS / MDL: 128-08-5
研究领域: 材料科学 · 化学工程
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JOURNAL OF HAZARDOUS MATERIALS · 2019 · IF 7.65

Mechanochemical degradation of brominated flame retardants in waste printed circuit boards by Ball Milling

Rui Wang,Zhixin Zhu,Shufei Tan,Jie Guo,Zhenming Xu

Degradation of brominated flame retardants (BFRs) in waste printed circuit boards (WPCBs) occurred due to mechanical force during the crushing process. In this study, a planetary ball-milling simulation experiment was designed to explore the mechanochemical debromination process of BFRs in WPCBs. The results showed that CaO had a better debromination performance than MgO and the mixture of Fe + SiO 2 , and high revolution speed and low mass ratio of WPCBs to CaO promoted the degradation of BFRs. After milling for 1 h, the particle size distribution was stable while the debromination efficiency increased with the increase of milling time. Ball milling promoted the migration of bromine from the inside to the new surface of WPCBs powder, and submicron particles adhered to the micron size aggregates. The polybrominated diphenyl ethers (PBDEs) detection showed that the concentrations of most PBDE congeners decreased with the increase of milling time, and a possible degradation pathway was proposed according to the experimental results. All the results provided new data for the mechanism of degradation of BFRs in WPCBs during the mechanical crushing process.

CAS / MDL: 7439-89-6 7631-86-9
研究领域: 环境科学 · 化学工程
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CHEMICAL ENGINEERING JOURNAL · 2018 · IF 6.735

Influence of (photo)bromination on the transformation, aggregation and sedimentation of graphene oxide

Yao Li,Min Zhang,Rongjie Hao,Huihui Wang,Xizhen He,Tingting Du,Xin Yang,Yingying Wang

The rapidly increasing use of graphene oxide (GO) necessitates the immediate investigation of the environmental fate and effects of this unique material. To date, little is known about the transformation of GO in environmental media, especially in water and wastewater treatment systems. This study explored the changes in the physicochemical properties of GO that result from (photo)bromination by simulating the reactions experienced by GO during water and wastewater treatment. The surface oxygen functionalities of GO considerably changed upon treatment. Specifically, the C OH and COOH groups of GO were lost under bromination , and the reduction of GO was enhanced under photobromination. GO sheets wrinkled and fragmented under bromination, and GO decomposition was enhanced by photobromination. The decreases in O/C ratio and GO decomposition in the presence of bromine were mainly attributed to the relatively high oxidation potential of bromine, which can oxidize carbon nanosheets. The oxidation of carbon nanosheets, in turn, resulted in the decomposition and formation of brominated disinfection by-products. Irradiation, hypobromous acid/hypobromite (HOBr/OBr − ), and reactive radicals, such as OH, Br , BrO and Br 2 − , may all affect the physicochemical transformation of GO in the presence of bromine and simulated solar light. Bromination and photobromination drastically changed the aggregation and sedimentation behavior of GO. The findings of this study advance knowledge on the transformations of GO in water treatment systems and provide insight on the environmental fate of the transformation products of GO.

CAS / MDL: 7758-02-3
研究领域: 环境科学 · 化学
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