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

doi:10.11949/0438-1157.20201243

Abstract

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

CLC Number:

TQ 110.3

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.

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.

Figures/Tables 10

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

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

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

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-

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

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

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

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

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

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

References 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.

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