电氧化法地下卤水提溴探究及条件优化

doi:10.11949/0438-1157.20201243

化工学报 ›› 2021, Vol. 72 ›› Issue (4): 2123-2131.DOI: 10.11949/0438-1157.20201243

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.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

收稿日期:2020-08-31 修回日期:2020-12-15 出版日期:2021-04-05 发布日期:2021-04-05
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)

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

ZHANG Xiao^1,^2,³(),JI Zhiyong^1,^2,³(),WANG Jing^1,^2,³,GUO Xiaofu^1,^2,³,LIU Jie^1,^2,³,ZHAO Yingying^1,^2,³,YUAN Junsheng^1,^2,³

^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

摘要/Abstract

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

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

中图分类号:

TQ 110.3

张晓, 纪志永, 汪婧, 郭小甫, 刘杰, 赵颖颖, 袁俊生. 电氧化法地下卤水提溴探究及条件优化[J]. 化工学报, 2021, 72(4): 2123-2131.

ZHANG Xiao, JI Zhiyong, WANG Jing, GUO Xiaofu, LIU Jie, ZHAO Yingying, YUAN Junsheng. Exploration and optimization of extraction process of bromine from underground brine by electrooxidation[J]. CIESC Journal, 2021, 72(4): 2123-2131.

图/表 10

图1 电氧化法地下卤水提溴实验装置

Fig.1 Schematic of the experimental setup for extraction of bromine from concentrated seawater by electro-oxidation method

图2 线性扫描伏安法实验装置

Fig.2 Schematic of the experimental setup for linear sweep voltammetry

表1 中国部分地区地下卤水基本化学组成[25-28]

Table 1 The basic chemical composition of underground brines in some parts of China[25-28]

地区	浓度/(g·L^-1)
地区	K⁺	Na⁺	Ca²⁺	Mg²⁺	Cl^-	SO₄^2-	Br^-
四川某地	26	102	10.88	1.26	201.97	0.38	1.70
潍坊某地	0.99	37.92	1.07	5.99	71.76	9.09	0.26
莱州某1号盐场	1.52	60.3	1.02	7.85	110.1	12.35	0.401
莱州某2号盐场	1.21	47.9	1.07	6.30	88.18	9.75	0.320
莱州某3号盐场	0.647	33.40	1.31	5.59	64.14	8.03	0.211
莱州某4号盐场	0.461	17.33	0.843	2.27	32.73	3.34	0.113

图3 110.1 g·L-1 Cl-溶液在0.401 g·L-1 Br-添加前后的电流变化

Fig.3 Current profile during electro-oxidation of 110.1 g·L-1 Cl- solution before and after the addition of 0.401 g·L-1 Br-

图4 c（a）、lnc（b）和 1/c（c）随反应时间t的变化

Fig.4 Changes of c(a), lnc(b) and 1/c(c)with reaction time t

图5 Cl-浓度对Br-反应速率常数、电流效率及单位能耗的影响

Fig.5 Effect of chloride concentration on bromide reaction rate constant, current efficiency and energy consumption

图6 不同初始阳极液pH下的Br-反应速率常数、电流效率和单位能耗的对比

Fig.6 The comparison of bromide reaction rate constant, current efficiency and energy consumption at different initial pH of anolyte

图7 地下卤水提溴过程中Br2提取率、电流效率和单位能耗随反应时间的变化

Fig.7 The change of extraction ratio of bromine, current efficiency and energy consumption with reaction time during the process of bromine extraction from underground brine

图8 地下卤水提溴过程中单位能耗倒数随Br2提取率的变化

Fig.8 The change of reciprocal of energy consumption with extraction ratio of bromine during the process of bromine extraction from underground brine

表2 地下卤水处理过程中不同处理时间的各项参考指标

Table 2 Indicators at different treating time during the treatment of concentrated seawater

处理时间/h	产量/kg	单位产量/(kg·h^-1)	能耗×10^-3/kJ	单位能耗/(kJ·g^-1)	提取率/%
6	181.65	30.28	470.30	2.59	45.3
8	210.12	26.27	551.58	2.63	52.4
10	231.78	23.18	616.07	2.66	57.8

参考文献 31

1	张慧峰, 王国强, 蔡荣华, 等. 提溴技术研究进展与展望[J]. 化学工业与工程, 2010, 27(5): 450-456.
	Zhang H F, Wang G Q, Cai R H, et al. Progress in bromine extracting technology[J]. Chemical Industry and Engineering, 2010, 27(5): 450-456.
2	陈向锋, 曹春燕. 中国工业溴现状及前景展望[J]. 化工科技市场, 2010, 33(7): 5-8.
	Chen X F, Cao C Y. Current status and prospect forecast of Chinese industrial bromine[J]. Chemical Technology Market, 2010, 33(7): 5-8.
3	柴子华, 李明明. 我国溴工业生产技术现状与展望[J]. 盐科学与化工, 2018, 47(6): 1-4.
	Chai Z H, Li M M. Domestic manufacturing process and expectation of bromine industry[J]. Journal of Salt Science and Chemical Industry, 2018, 47(6): 1-4.
4	陈向楠, 王海增. 溴素资源与产业发展分析[J]. 盐业与化工, 2013, 42(6): 4-7.
	Chen X N, Wang H Z. Bromine resource and analysis of the industry development[J]. Journal of Salt and Chemical Industry, 2013, 42(6): 4-7.
5	黄西平. 国内外盐湖(地下)卤水资源综合利用综述[J]. 海洋技术, 2002, 21(4): 66-72.
	Huang X P. Multipurpose utilization of bittern resource in salt lake[J]. Ocean Technology, 2002, 21(4): 66-72.
6	韩积斌, 许建新, 安朝, 等. 盐湖地下卤水的开采技术及其展望[J]. 盐湖研究, 2015, 23(1): 67-72.
	Han J B, Xu J X, An Z, et al. Research advance of the salt lake underground brine extraction technology[J]. Journal of Salt Lake Research, 2015, 23(1): 67-72.
7	李海民, 程怀德, 张全有. 卤水资源开发利用技术述评[J]. 盐湖研究, 2003, 11(3): 51-64.
	Li H M, Cheng H D, Zhang Q Y. Evaluation of the technologies of comprehensive utilization and exploitation salt resource[J]. Journal of Salt Lake Research, 2003, 11(3): 51-64.
8	李海民, 程怀德, 张全有. 卤水资源开发利用技术述评(续完)[J]. 盐湖研究, 2004, 12(1): 62-72, 56.
	Li H M, Cheng H D, Zhang Q Y. Evaluation of the technologies of comprehensive utilizationand exploitation brine resources[J]. Journal of Salt Lake Research, 2004, 12(1): 62-72, 56.
9	张琳娜, 刘有智, 焦纬洲, 等. 卤水提溴技术的发展与研究现状[J]. 盐湖研究, 2009, 17(1): 68-72.
	Zhang L N, Liu Y Z, Jiao W Z, et al. Development and research status of bromine extracting technology from the brine[J]. Journal of Salt Lake Research, 2009, 17(1): 68-72.
10	詹进先. 试论威远气田水提溴技术[J]. 石油与天然气化工, 1996, 25(4): 239-242.
	Zhan J X. Discussion on bromine recovery process for Weiyuan gas field formation water[J]. Chemical Engineering of Oil and Gas, 1996, 25(4): 239-242.
11	郭如新. 美国溴产品近况和前景[J]. 盐湖研究, 2006, 14(1): 66-72.
	Guo R X. Present situation and prospect of bromine and its derivatives in USA[J]. Journal of Salt Lake Research, 2006, 14(1): 66-72.
12	Fan M H, Xu S Y. Adsorption and desorption properties of macroreticular resins for salidroside from Rhodiola sachalinensis A. Bor[J]. Separation and Purification Technology, 2008, 61(2): 211-216.
13	朱昌洛, 寇建军. 树脂吸附法由卤水中提溴[J]. 矿产综合利用, 2003, (5): 13-16.
	Zhu C L, Kou J J. Extraction of bromine from brine by RIP method[J]. Multipurpose Utilization of Mineral Resources, 2003, (5): 13-16.
14	Ensafi A A, Eskandari H. Selective extraction of bromide with liquid organic membrane[J]. Separation Science and Technology, 2001, 36(1): 81-89.
15	王国强, 张淑芬, 王俐聪, 等. 气态膜法海水提溴影响因素的研究[J]. 海洋技术, 2004, 23(1): 77-80.
	Wang G Q, Zhang S F, Wang L C, et al. Study on extraction of bromine from seawater with gas membrane[J]. Ocean Technology, 2004, 23(1): 77-80.
16	Kosaka Y, Fujita T, Nanun N. Recovery of bromine: JP58-041703[P]. 1983.
17	孙志娟, 张心亚, 黄洪, 等. 乳状液膜分离技术的发展与应用[J]. 现代化工, 2006, 26(9): 63-66.
	Sun Z J, Zhang X Y, Huang H, et al. Development of emulsion liquid membrane separation and its application[J]. Modern Chemical Industry, 2006, 26(9): 63-66.
18	万印华, 王向德, 张秀娟. 乳状液膜用表面活性剂研究进展[J]. 化工进展, 1998, 17(5): 12-15, 28.
	Wan Y H, Wang X D, Zhang X J. Progress in the study of surfactant used for emulsion liquid membrane[J]. Chemical Industry and Engineering Progress, 1998, 17(5): 12-15, 28.
19	王红, 王巍杰, 李红霞. 乳状液膜法提取溴[J]. 河北理工学院学报, 2005, 27(3): 110-112.
	Wang H, Wang W J, Li H X. The extraction of bromine with liquid membrane[J]. Journal of Hebei Institute of Technology, 2005, 27(3): 110-112.
20	张良晓, 孔望清, 杨祥. 表面活性剂在化学分离中的应用[J]. 河北化工, 2005, 28(4): 20-21, 46.
	Zhang L X, Kong W Q, Yang X. Application of surfactant in chemical separation[J]. Hebei Chemical Engineering and Industry, 2005, 28(4): 20-21, 46.
21	Bard A J, Jordan J, Parsons R. Standard Potentials in Aqueous Solutions[M]. New York: Marcel Dekker, 1985.
22	Cohen I, Shapira B, Avraham E, et al. Bromide ions specific removal and recovery by electrochemical desalination[J]. Environmental Science & Technology, 2018, 52(11): 6275-6281.
23	Sun M, Lowry G V, Gregory K B. Selective oxidation of bromide in wastewater brines from hydraulic fracturing[J]. Water Research, 2013, 47(11): 3723-3731.
24	Zhang X, Ji Z Y, Liu F, et al. Investigation of electrochemical oxidation technology for selective bromine extraction in comprehensive utilization of concentrated seawater[J]. Separation and Purification Technology, 2020, 248: 117108.
25	杨能红, 孙成高, 彭建忠. 地下卤水综合利用新工艺研究[J]. 盐业与化工, 2016, 45(5): 24-27.
	Yang N H, Sun C G, Peng J Z. New technology for comprehensive utilization of underground brine[J]. Journal of Salt and Chemical Industry, 2016, 45(5): 24-27.
26	王振, 要璇. 地下卤水综合利用工艺探究[J]. 化工设计通讯, 2017, 43(5): 185.
	Wang Z, Yao X. Study on comprehensive utilization of underground brine[J]. Chemical Engineering Design Communications, 2017, 43(5): 185.
27	康兴伦, 程作联. 山东渤海沿岸地下卤水的成分研究[J]. 海洋通报, 1990, 9(6): 25-29.
	Kang X L, Cheng Z L. Composition research for underground brine along Shandong coastal flatlands on Bohai sea[J]. Marine Science Bulletin, 1990, 9(6): 25-29.
28	贾梦秋, 杨文胜. 应用电化学[M]. 北京: 高等教育出版社, 2004.
	Jia M Q, Yang W S. Applied Electrochemistry [M]. Beijing: Higher Education Press, 2004.
29	刘建兰, 李冀蜀, 郭会明, 等. 物理化学(上) [M]. 北京: 化学工业出版社, 2013.
	Liu J L, Li J S, Guo H M, et al. Physical Chemistry [M]. Beijing: Chemical Industry Press, 2013.
30	Xu P, Drewes J E, Heil D, et al. Treatment of brackish produced water using carbon aerogel-based capacitive deionization technology[J]. Water Research, 2008, 42(10/11): 2605-2617.
31	Wang L, Lin S H. Theoretical framework for designing a desalination plant based on membrane capacitive deionization[J]. Water Research, 2019, 158: 359-369.

[1]	张义飞, 刘舫辰, 张双星, 杜文静. 超临界二氧化碳用印刷电路板式换热器性能分析[J]. 化工学报, 2023, 74(S1): 183-190.
[2]	胡超, 董玉明, 张伟, 张红玲, 周鹏, 徐红彬. 浓硫酸活化五氧化二钒制备高浓度全钒液流电池正极电解液[J]. 化工学报, 2023, 74(S1): 338-345.
[3]	程成, 段钟弟, 孙浩然, 胡海涛, 薛鸿祥. 表面微结构对析晶沉积特性影响的格子Boltzmann模拟[J]. 化工学报, 2023, 74(S1): 74-86.
[4]	宋瑞涛, 王派, 王云鹏, 李敏霞, 党超镔, 陈振国, 童欢, 周佳琦. 二氧化碳直接蒸发冰场排管内流动沸腾换热数值模拟分析[J]. 化工学报, 2023, 74(S1): 96-103.
[5]	米泽豪, 花儿. 基于DFT和COSMO-RS理论研究多元胺型离子液体吸收SO₂气体[J]. 化工学报, 2023, 74(9): 3681-3696.
[6]	陈美思, 陈威达, 李鑫垚, 李尚予, 吴有庭, 张锋, 张志炳. 硅基离子液体微颗粒强化气体捕集与转化的研究进展[J]. 化工学报, 2023, 74(9): 3628-3639.
[7]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[8]	范孝雄, 郝丽芳, 范垂钢, 李松庚. LaMnO₃/生物炭催化剂低温NH₃-SCR催化脱硝性能研究[J]. 化工学报, 2023, 74(9): 3821-3830.
[9]	杨百玉, 寇悦, 姜峻韬, 詹亚力, 王庆宏, 陈春茂. 炼化碱渣湿式氧化预处理过程DOM的化学转化特征[J]. 化工学报, 2023, 74(9): 3912-3920.
[10]	陈哲文, 魏俊杰, 张玉明. 超临界水煤气化耦合SOFC发电系统集成及其能量转化机制[J]. 化工学报, 2023, 74(9): 3888-3902.
[11]	杨学金, 杨金涛, 宁平, 王访, 宋晓双, 贾丽娟, 冯嘉予. 剧毒气体PH₃的干法净化技术研究进展[J]. 化工学报, 2023, 74(9): 3742-3755.
[12]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[13]	孟令玎, 崇汝青, 孙菲雪, 孟子晖, 刘文芳. 改性聚乙烯膜和氧化硅固定化碳酸酐酶[J]. 化工学报, 2023, 74(8): 3472-3484.
[14]	汪林正, 陆俞冰, 张睿智, 罗永浩. 基于分子动力学模拟的VOCs热氧化特性分析[J]. 化工学报, 2023, 74(8): 3242-3255.
[15]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.

电氧化法地下卤水提溴探究及条件优化

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 10

参考文献 31

相关文章 15

编辑推荐

Metrics

本文评价