Selective electro-oxidation of bromide ion in potassium-extracted brine from rock salt mines

doi:10.11949/0438-1157.20220412

Abstract

Abstract:

The bromide ion content in the potassium-extracted old brine from the Indo-China Peninsula rock salt mine is about 3000 mg/L, which is a valuable raw material for bromine production. The effective utilization of associated bromine resources in rock salt mines provides a number of significant economic, social, and environmental benefits, which will improve the comprehensive utilization value of rock salt mine resources and alleviate the shortage of bromine resources in our country. In this work, a three-electrode system was designed in which the anode was graphite electrode, the cathode was platinum sheet electrode, and the reference was Ag/AgCl electrode. Firstly, the suitable potential for selective electro-oxidation of Br^- in the potassium-extracted brine from rock salt mines was determined by linear sweep voltammetry (LSV) method. Then, the kinetic and the expression of the oxidation rate of the electro-oxidation of Br^- in bromine-containing simulated brine under this potential condition were explored through the electro-oxidation experiments in the three-electrode system. Finally, the influence of Cl^- concentration, effective electrode area and stirring rate on the oxidation rate of Br^- in bromine-containing simulated brine was investigated, and the optimal operating conditions were obtained. The results show that 1.150 V is a suitable electrode potential for the selective oxidation of bromide ions, and the reaction conforms to the first-order kinetic law. For the potassium-extracted brine from the rock salt mines with the Cl^- concentration of 280 g/L, when the effective area of the graphite electrode is 50.18 cm² and the stirring rate is 400 r/min, the fastest electro-oxidation rate of Br^- was observed, the corresponding reaction rate constant is 0.3042 h^-1, and about 91.9% of Br^- was converted after 8 h of electro-oxidation.These results validate the feasibility of the selective oxidation of bromine in potassium-extracted brine from the rock salt mines by electro-oxidation.

Key words: electrochemistry, oxidation, bromine extraction, selectivity, three-electrode system, kinetics

摘要：

中南半岛岩盐矿提钾老卤中溴离子含量约为3000 mg/L，是极具价值的制溴原料。岩盐矿伴生溴资源的有效利用，对提高岩盐矿资源综合利用价值，缓解我国溴资源短缺现状，具有经济、社会及环境多重意义。通过三电极体系线性扫描伏安法与电氧化实验，对含溴模拟卤水中溴离子的氧化速率以及氯离子浓度、电极的有效面积、搅拌速率对其的影响进行研究。结果表明1.150 V为合适的溴离子选择性氧化的电极电位，且反应符合一级反应动力学规律。针对氯离子浓度为280 g/L的岩盐矿提钾老卤，石墨电极的有效面积50.18 cm²，搅拌速率400 r/min时溴离子电氧化的速率最快，反应速率常数为0.3042 h^-1，电氧化8 h后溴转化率为91.9%。

关键词: 电化学, 氧化, 溴素提取, 选择性, 三电极体系, 动力学

CLC Number:

TQ 110.3

Chenyu SU, Ying YANG, Xingfu SONG. Selective electro-oxidation of bromide ion in potassium-extracted brine from rock salt mines[J]. CIESC Journal, 2022, 73(7): 3007-3017.

苏晨昱, 杨颖, 宋兴福. 岩盐矿提钾老卤中溴离子选择性电氧化过程研究[J]. 化工学报, 2022, 73(7): 3007-3017.

Figures/Tables 11

Fig.1 Schematic of three-electrode system

Fig.2 Voltammetric curves of linear sweep voltammetry for different solutions

Fig.3 Current profile of simulated brine before and after NaBr addition

Fig.4 (a) Changes of Br- concentration with reaction time in anode chamber;Changes of (b) c, (c) lnc and (d) 1/c with reaction time

Fig.5 Changes of Br- concentration (a) and bromine conversion (b) with reaction time under different Cl- concentrations

Fig.6 Kinetic fitting of first-order reaction (a) and change of -k (b) for electro-oxidation of Br- at different Cl- concentrations

Fig.7 Change of current efficiency and unit energy consumption with Cl- concentrations

Fig.8 Change of Br- concentration (a) and bromine conversion (b) with reaction time under different anode electrode effective area

Fig.9 Kinetic fitting of first-order reaction (a) and change of -k (b) for electro-oxidation of Br- at different anode electrode effective area

Fig.10 Change of Br- concentration (a) and bromine conversion (b) with reaction time under the different rotating speed

Fig.11 Kinetic fitting of first-order reaction (a) and change of -k (b) for electro-oxidation of Br- at different rotating speed

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