CIESC Journal ›› 2021, Vol. 72 ›› Issue (4): 2123-2131.DOI: 10.11949/0438-1157.20201243

• Separation engineering • Previous Articles     Next Articles

Exploration and optimization of extraction process of bromine from underground brine by electrooxidation

ZHANG Xiao1,2,3(),JI Zhiyong1,2,3(),WANG Jing1,2,3,GUO Xiaofu1,2,3,LIU Jie1,2,3,ZHAO Yingying1,2,3,YUAN Junsheng1,2,3   

  1. 1.National-Local Joint Engineering Laboratory of Chemical Energy Saving Process Integration and Resource Utilization, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
    2.Engineering Research Center of Seawater Utilization of Ministry of Education, School of Chemical Engineering and Technology, Hebei University of Technology, Tianjin 300130, China
    3.Hebei Collaborative Innovation Center of Modern Marine Chemical Technology, Tianjin 300130, China
  • Received:2020-08-31 Revised:2020-12-15 Online:2021-04-05 Published:2021-04-05
  • Contact: JI Zhiyong

电氧化法地下卤水提溴探究及条件优化

张晓1,2,3(),纪志永1,2,3(),汪婧1,2,3,郭小甫1,2,3,刘杰1,2,3,赵颖颖1,2,3,袁俊生1,2,3   

  1. 1.河北工业大学化工学院,化工节能过程集成与资源利用国家-地方联合工程实验室,天津 300130
    2.河北工业大学 化工学院,海水资源高效利用化工技术教育部工程研究中心,天津 300130
    3.河北省现代海洋化工技术协同创新中心,天津 300130
  • 通讯作者: 纪志永
  • 作者简介:张晓(1994—),男,硕士研究生,18322596502@163.com
  • 基金资助:
    国家自然科学基金项目(21978064);河北省自然科学基金项目(B2019202423);河北省创新战略资助项目(20180401)

Abstract:

By designing an electrolytic cell containing a three-electrode system and strictly controlling the potential of the working electrode, an electro-oxidation method is proposed for the selective extraction of bromine resources in underground brine. The technical feasibility, the reaction kinetic model, the influence of co-existing Cl- and the initial pH of the anolyte, and the optimal operating time has been discussed respectively. The results showed that the electro-oxidation was technically feasible for extracting bromine from underground brine, and the reaction of electro-oxidation for extracting bromine from underground brine followed the second-order reaction kinetic model. The bromide reaction rate constant increased first and then decreased with the increase of chloride concentration. The co-existing chloride had both promoting and inhibititing effects on the electro-oxidation of bromide. The promotion effect might result from the increase of total solution conductivity caused by the increase of chloride concentration. The inhibitition effect might be due to the adsorption competition between chloride and bromide on the graphite electrode surface. The energy consumption deceased with the increase of chloride concentration, and the current efficiency was changed little with the change of chloride concentration. In addition, the bromide reaction rate constant gradually increased as the initial pH of the anolyte decreased, and current efficiency and energy consumption were relatively unaffected by it. In the process of extracting bromine from underground brine by electro-oxidation, the extraction ratio of Br2 grew more and more slowly with the time prolong, the current efficiency continued to decrease, and the energy consumption continued to rise and its growth rate was also increasing. Therefore, the optimal operating time might be 6—10 h.

Key words: underground brine, bromine extraction, electrochemistry, graphite electrode, oxidation, reaction kinetics

摘要:

通过设计包含三电极体系的电解槽,并严格控制工作电极电位,提出以电氧化的方法进行地下卤水中溴资源的选择性提取。对电氧化法地下卤水提溴的技术可行性、反应动力学模型、共存Cl-和阳极液初始pH的影响以及最佳操作时间展开分析讨论。结果表明:电氧化法用于地下卤水提溴具备技术可行性,且反应遵循二级反应动力学模型。随共存Cl-浓度的增加,Br-的电氧化反应速率常数先增大后减小,Cl-对反应可产生促进与抑制的双重作用:促进作用来源于随Cl-浓度升高而增大的溶液总电导率,抑制作用来源于Cl-与Br-在石墨电极表面的竞争吸附;单位能耗随Cl-浓度的增大而减小,电流效率相对不受影响。随阳极液初始pH的减小,Br-的电氧化反应速率常数逐渐增大,电流效率与单位能耗相对不受影响。随电氧化操作时间的延长,Br2提取率的增长速率逐渐降低,电流效率不断降低,单位能耗不断升高的同时其增长速率也不断增大;6~10 h为推荐的最佳的操作时间。

关键词: 地下卤水, 提溴, 电化学, 石墨电极, 氧化, 反应动力学

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