电化学法油气田采出水同步提锂溴及制溴化锂

doi:10.11949/0438-1157.20250417

化工学报 ›› 2025, Vol. 76 ›› Issue (10): 5213-5224.DOI: 10.11949/0438-1157.20250417

电化学法油气田采出水同步提锂溴及制溴化锂

赵海霞¹^,⁴(), 刘洋², 王雷¹^,⁴, 高凤凤³, 郭志远¹^,⁴, 张盼盼¹^,⁴, 汪婧¹^,⁴, 纪志永¹^,⁴()

^1.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 300401
^2.中国石油长庆油田分公司油气工艺研究院，陕西西安 710018
^3.太原理工大学化学与化工学院，山西太原 030024
^4.河北省现代海洋化工技术协同创新中心，天津 300401

收稿日期:2025-04-20 修回日期:2025-05-29 出版日期:2025-10-25 发布日期:2025-11-25
通讯作者: 纪志永
作者简介:赵海霞（1998—），女，硕士研究生，3344046314@qq.com
基金资助:
国家自然科学基金项目(92475207);国家自然科学基金项目(U23A20119);国家自然科学基金项目(21978064);河北省自然科学基金项目(B2022202024);河北省自然科学基金项目(B2019202423)

Electrochemical method for synchronous extraction of lithium and bromine from oil and gas field produced water to lithium bromide

Haixia ZHAO¹^,⁴(), Yang LIU², Lei WANG¹^,⁴, Fengfeng GAO³, Zhiyuan GUO¹^,⁴, Panpan ZHANG¹^,⁴, Jing WANG¹^,⁴, Zhiyong JI¹^,⁴()

^1.Engineering Research Center of Seawater Utilization Technology of Ministry of Education, School of Chemical Engineering, Hebei University of Technology, Tianjin 300401, China
^2.PetroChina Changqing Oilfield Branch Oil and Gas Technology Research Institute, Xi'an 710018, Shaanxi，China
^3.College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi，China
^4.Hebei Collaborative Innovation Center of Modern Marine Chemical Technology, Tianjin 300401, China

Received:2025-04-20 Revised:2025-05-29 Online:2025-10-25 Published:2025-11-25
Contact: Zhiyong JI

摘要/Abstract

摘要：

油气田采出水是油气开采过程中产生的废水，含锂、溴等高附加值矿物资源。目前，溶存锂、溴提取需分步进行，效率较低、操作较为烦琐。因此，开发同步提取技术，对实现锂、溴的高效、绿色、低成本资源化提取与回收具有重要意义。本文分别采用高温固相法和水热法制备LiMn₂O₄（LMO）和BiOBr（BOB）电极活性材料，进而构建LMO/BOB电极体系；对无膜同步分极吸附和有膜同步分极脱附的操作电压进行调控，并对两电极间活性材料质量比进行优化匹配。优化条件下，3 h达到吸附平衡，Li⁺吸附容量24.13 mg/g、Br^-吸附容量88.13 mg/g；3 h脱附达到平衡，基于单位质量LMO电极，单次分极脱附可得到2.70 mmol LiBr溶液。研究结果为油气田采出水中锂和溴的同步提取与回收提供了方法和数据参考。

关键词: 同步提取, LMO/BOB电极体系, 电化学无膜吸附, LiBr

Abstract:

The produced water of oil and gas fields is the waste water produced in the process of oil and gas exploitation, which contains high value-added mineral resources such as lithium and bromine. Currently, the extraction of dissolved lithium and bromine needs to be carried out in steps, which is inefficient and cumbersome. Therefore, the development of synchronous extraction technology is of great significance for the efficient, green and low-cost resource extraction and recovery of lithium and bromine. LiMn₂O₄ (LMO) and BiOBr (BOB) electrode active materials are prepared by high temperature solid phase and hydrothermal methods, respectively, and then the LMO/BOB electrode system is constructed. The operating voltage of synchronous adsorption without membrane and synchronous desorption with membrane are regulated, and the mass ratio of active materials between the two electrodes is optimized. Under the optimized conditions, the adsorption equilibrium is reached in 3 h, the adsorption capacity of Li⁺ is 24.13 mg/g, and the adsorption capacity of Br^- is 88.13 mg/g. The desorption reaches equilibrium within 3 h, and based on the unit mass LMO electrode, the two-electrode adsorption can obtain 2.70 mmol LiBr solution at one time. The research results provide a method and data reference for the synchronous extraction and recovery of lithium and bromine in the produced water of oil and gas fields.

Key words: synchronous extraction, LMO/BOB electrode system, electrochemical membraneless adsorption, LiBr

中图分类号:

TQ 150.9

赵海霞, 刘洋, 王雷, 高凤凤, 郭志远, 张盼盼, 汪婧, 纪志永. 电化学法油气田采出水同步提锂溴及制溴化锂[J]. 化工学报, 2025, 76(10): 5213-5224.

Haixia ZHAO, Yang LIU, Lei WANG, Fengfeng GAO, Zhiyuan GUO, Panpan ZHANG, Jing WANG, Zhiyong JI. Electrochemical method for synchronous extraction of lithium and bromine from oil and gas field produced water to lithium bromide[J]. CIESC Journal, 2025, 76(10): 5213-5224.

图/表 15

表1 某高氯油气田采出水组成成分

Table 1 Composition in high-chlorine produced water of oil and gas field

共存离子	浓度/(mg/L)
Li⁺	47
Na⁺	62347
K⁺	2766
Mg²⁺	472
Ca²⁺	2816
Cl^-	107715
$S O 4 2 -$	1936
Br^-	543

表1 某高氯油气田采出水组成成分

Table 1 Composition in high-chlorine produced water of oil and gas field

共存离子	浓度/(mg/L)
Li⁺	47
Na⁺	62347
K⁺	2766
Mg²⁺	472
Ca²⁺	2816
Cl^-	107715
$S O 4 2 -$	1936
Br^-	543

图1 同步吸/脱附过程

Fig.1 Synchronous adsorption/desorption process

表2 不同电极体系的简称

Table 2 Abbreviations of different electrochemical systems

电极体系	全称	简称
单独提锂体系	LiMn₂O₄/Li_1-_x Mn₂O₄	LMO/L_1-_x MO
单独提溴体系	BiOBr/BiOBr_1-_x	BOB/BOB_1-_x
同步分极提锂、溴体系	Li_1-_x Mn₂O₄/BiOBr_1-_x	L_1-_x MO/BOB_1-_x

图2 LMO和BOB粉体的XRD谱图

Fig.2 XRD patterns of LMO and BOB powders

图3 LMO和BOB电极的CV曲线

Fig.3 CV curves of LMO and BOB electrode

图4 LMO/BOB电极体系中不同电压下Br-脱附容量

Fig.4 Br- desorption capacity at different voltages in LMO/BOB electrode system

图5 电极电位（a）；以BOB电极为工作电极的LSV曲线（b）

Fig.5 The OCV of the electrode (a); Linear sweep voltammogram with BOB electrode as working electrode (b)

图6 不同电极体系及电压下吸/脱附容量及电流随时间变化

Fig.6 Adsorption/desorption capacity and the current change with time under different electrode systems and voltages

图7 不同脱附电压下的锰溶损率

Fig.7 The dissolution loss rate of Mn under different desorption voltages

图8 LMO/BOB电极体系不同吸/脱附电压下电流随时间变化

Fig.8 The current changes with time under different adsorption and desorption voltages in the LMO/BOB electrode system

图9 LMO/BOB体系中Li+和Br-对应的吸附浓度变化量与活性材料质量的比值（a）和Li+和Br-的吸附容量（b）

Fig.9 The corresponding change in adsorption concentration of Li+ and Br-versus the mass of the active material (a) and the adsorption capacity of Li⁺ and Br- (b) in LMO/BOBsystem

图10 不同电极体系中阳离子和阴离子选择性

Fig.10 Cation and anion selectivity in different electrode systems

图11 在LMO/BOB电极体系5次循环中电极的XRD谱图和吸/脱附容量及脱附效率变化

Fig.11 XRD patterns of the electrodes and adsorption/desorption capacity and desorption efficiency change during the 5 cycles in the LMO/BOB electrode system

图12 某高氯油气田采出水中离子吸附容量和选择性

Fig.12 Ion adsorption capacity and selectivity in high-chlorine produced water of oil and gas field

表3 不同电极体系对Li+和Br-的吸附性能比较

Table 3 Comparison of Li+ and Br- adsorption performance in different electrochemical systems

电极体系	Li⁺吸附容量/ (mg/g)	Br^-吸附容量/ (mg/g)	时间/min	文献
B-LMO//Ag	20.60	—	60	[31]
H-LMOE	11.93	—	10	[14]
CNTS/QCS/BiOBr	—	78.71	120	[30]
BiOBr/PVDF/CB	—	67.10	240	[21]
BiOBr	9.52(Cs⁺)	53.28	240	[15]
LMO/L_1-_x MO	18.11	—	180	本工作
BOB/BOB_1-_x	—	105.02	180	本工作
LMO/BOB	24.13	88.13	180	本工作

参考文献 31

[1]	Vera M L, Torres W R, Galli C I, et al. Environmental impact of direct lithium extraction from brines[J]. Nature Reviews Earth & Environment, 2023, 4: 149-165.
[2]	蒋晨啸, 陈秉伦, 张东钰, 等. 我国盐湖锂资源分离提取进展[J]. 化工学报, 2022, 73(2): 481-503.
	Jiang C X, Chen B L, Zhang D Y, et al. Progress in isolating lithium resources from China salt lake brine[J]. CIESC Journal, 2022, 73(2): 481-503.
[3]	杨婷, 张红梅, 张帆, 等. CNT-GO掺杂LiMn₂O₄膜电极的制备及其提锂性能[J]. 高校化学工程学报, 2023, 37(5): 832-839.
	Yang T, Zhang H M, Zhang F, et al. Preparation and lithium extraction performance of CNT-GO doped LiMn₂O₄ film electrode[J]. Journal of Chemical Engineering of Chinese Universities, 2023, 37(5): 832-839.
[4]	张晓, 纪志永, 汪婧, 等. 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 X, Ji Z Y, Wang J, et al. Exploration and optimization of extraction process of bromine from underground brine by electrooxidation[J]. CIESC Journal, 2021, 72(4): 2123-2131.
[5]	Marín P E, Milian Y, Ushak S, et al. Lithium compounds for thermochemical energy storage: a state-of-the-art review and future trends[J]. Renewable and Sustainable Energy Reviews, 2021, 149: 111381.
[6]	Cabeza L F, Gutierrez A, Barreneche C, et al. Lithium in thermal energy storage: a state-of-the-art review[J]. Renewable and Sustainable Energy Reviews, 2015, 42: 1106-1112.
[7]	Tang L Y, Lu W J, Li X F. Electrolytes for bromine-based flow batteries: challenges, strategies, and prospects[J]. Energy Storage Materials, 2024, 70: 103532.
[8]	Shakoor N, Adeel M, Ahmad M A, et al. Reimagining safe lithium applications in the living environment and its impacts on human, animal, and plant system[J]. Environmental Science and Ecotechnology, 2023, 15: 100252.
[9]	Shtangeeva I, Niemelä M, Perämäki P, et al. Phytoextration of bromine from contaminated soil[J]. Journal of Geochemical Exploration, 2017, 174: 21-28.
[10]	Yang C H, Zhu B, Zhan M J, et al. Lithium in cancer therapy: friend or foe?[J]. Cancers, 2023, 15(4): 1095.
[11]	Villegas-Vázquez E Y, Quintas-Granados L I, Cortés H, et al. Lithium: a promising anticancer agent[J]. Life, 2023, 13(2): 537.
[12]	Pei W, Cheng Q, Jiao S, et al. Performance evaluation of the electrodialysis regenerator for the lithium bromide solution with high concentration in the liquid desiccant air-conditioning system[J]. Energy, 2019, 187: 115928.
[13]	Baudino L, Santos C, Pirri C F, et al. Recent advances in the lithium recovery from water resources: from passive to electrochemical methods[J]. Advanced Science, 2022, 9(27): 2201380.
[14]	Wang J, Fang J W, Ji Z Y, et al. Preparation of a novel hollow porous LiMn₂O₄ film electrode (H-LMOE) and its improved performance for lithium extraction[J]. Journal of Environmental Chemical Engineering, 2023, 11(5): 110878.
[15]	Wang T Y, An X W, Wang P F, et al. Simultaneous selective separation and enrichment of bromine and cesium ions by electrochemically switched amphoteric ion membrane[J]. Desalination, 2024, 581: 117594.
[16]	Li M C, Zhao J Y, Li Y R, et al. Enhanced adsorption of cesium ions by electrochemically switched ion exchange method: based on surface-synthetic Na₂Ti₃O₇ nanotubes[J]. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2019, 579: 123712.
[17]	Zhang B L, Du X, Hao X G, et al. A novel potential-triggered SBA-15/PANI/PSS composite film for selective removal of lead ions from wastewater[J]. Journal of Solid State Electrochemistry, 2018, 22(8): 2473-2483.
[18]	Wang Z D, Feng Y T, Hao X G, et al. An intelligent displacement pumping film system: a new concept for enhancing heavy metal ion removal efficiency from liquid waste[J]. Journal of Hazardous Materials, 2014, 274: 436-442.
[19]	Ji W W, Niu J J, Zhang W, et al. An electroactive ion exchange hybrid film with collaboratively-driven ability for electrochemically-mediated selective extraction of chloride ions[J]. Chemical Engineering Journal, 2022, 427: 130807.
[20]	Cheng Y J, Wang J, Luo J H, et al. BiOI with inherent photo/electric biactivity recovery I^- by novel photoassisted electrochemically switched ion exchange technology[J]. Industrial & Engineering Chemistry Research, 2022, 61(26): 9394-9404.
[21]	Ye D N, Gao F F, Zeng G L, et al. An electroactive BiOBr/PVDF/CB film electrode for electrochemical extraction of bromine ions from brines[J]. Industrial & Engineering Chemistry Research, 2023, 62(22): 8882-8892.
[22]	Song X Y, Niu J J, Yan W J, et al. An electroactive BiOBr@PPy hybrid film with synergistic effect for electrochemically switched capture of bromine ions from aqueous solutions[J]. Separation and Purification Technology, 2022, 290: 120845.
[23]	Zhou G L, Chen L L, Li X W, et al. Construction of truncated-octahedral LiMn₂O₄ for battery-like electrochemical lithium recovery from brine[J]. Green Energy & Environment, 2023, 8(4): 1081-1090.
[24]	Zeng J S, Li M S, Li X F, et al. A novel coating onto LiMn₂O₄ cathode with increased lithium ion battery performance[J]. Applied Surface Science, 2014, 317: 884-891.
[25]	郭志远, 张帆, 纪志永, 等. 选择性电渗析提锂技术的研究进展[J]. 河北工业大学学报, 2022, 51(6): 1-9.
	Guo Z Y, Zhang F, Ji Z Y, et al. Research and prospect of lithium extraction by selective electrodialysis[J]. Journal of Hebei University of Technology, 2022, 51(6): 1-9.
[26]	Jin W, Hu M Q, Sun Z, et al. Simultaneous and precise recovery of lithium and boron from salt lake brine by capacitive deionization with oxygen vacancy-rich CoP/Co₃O₄-graphene aerogel[J]. Chemical Engineering Journal, 2021, 420: 127661.
[27]	Zhao M Y, Ji Z Y, Zhang Y G, et al. Study on lithium extraction from brines based on LiMn₂O₄/Li_1- _x Mn₂O₄ by electrochemical method[J]. Electrochimica Acta, 2017, 252: 350-361.
[28]	Wu Y, Cao C B, Zhang J T, et al. Hierarchical LiMn₂O₄ hollow cubes with exposed{111}planes as high-power cathodes for lithium-ion batteries[J]. ACS Applied Materials & Interfaces, 2016, 8(30): 19567-19572.
[29]	Guo Z Y, Ji Z Y, Chen Q B, et al. Prefractionation of LiCl from concentrated seawater/salt lake brines by electrodialysis with monovalent selective ion exchange membranes[J]. Journal of Cleaner Production, 2018, 193: 338-350.
[30]	Zhang L, Ma Z, Sun H D, et al. A novel CNTs/QCS/BiOBr composite membrane with electron-ion transfer channel for Br^- recovery in ESIX process[J]. Journal of Colloid and Interface Science, 2023, 646: 784-793.
[31]	Gu J, Zhou G L, Chen L L, et al. Particle size control and electrochemical lithium extraction performance of LiMn₂O₄ [J]. Journal of Electroanalytical Chemistry, 2023, 940: 117487.

电化学法油气田采出水同步提锂溴及制溴化锂

Electrochemical method for synchronous extraction of lithium and bromine from oil and gas field produced water to lithium bromide

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