岩盐矿提钾老卤中溴离子选择性电氧化过程研究

doi:10.11949/0438-1157.20220412

摘要/Abstract

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

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

中图分类号:

TQ 110.3

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.

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.

图/表 11

图1 三电极体系装置示意图

Fig.1 Schematic of three-electrode system

图2 不同体系线性扫描伏安法伏安特性曲线

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

图3 模拟卤水在NaBr加入前后的电流变化

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

图4 （a）阳极室中溴离子浓度与电氧化时间的关系;（b）零级反应动力学模型拟合;（c）一级反应动力学模型拟合;（d）二级反应动力学模型拟合

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

图5 不同氯离子浓度下溴离子浓度（a）和溴转化率（b）随时间的变化

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

图6 不同氯离子浓度下电氧化溴离子的一级反应动力学拟合（a）和一级反应动力学反应速率常数（b）

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

图7 电氧化溴过程电流效率、单位能耗随氯离子浓度变化关系

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

图8 不同阳极石墨电极有效面积下电氧化溴离子浓度（a）和溴转化率（b）随时间的变化关系

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

图9 不同阳极石墨电极有效面积下电氧化溴离子的一级反应动力学拟合（a）和一级反应动力学反应速率常数（b）

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

图10 不同转速下电氧化溴离子浓度（a）和溴转化率（b）随时间的变化关系

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

图11 不同转子转速下电氧化溴离子的一级反应动力学拟合（a）和一级反应动力学反应速率常数（b）

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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