Research on lithium extraction and recovery from oil and gas field produced water coupled with electrochemical adsorption-selective electrodialysis

doi:10.11949/0438-1157.20250643

Abstract

Abstract:

Oil and gas field produced water, as a by-product of oil, natural gas, and shale gas extraction, urgently needs to be recycled. The lithium it contains has high development potential, but its complex composition, low lithium content, and high development difficulty are significant. Based on this, the purification and concentration process of electrochemical adsorption-selective electrodialysis was proposed to ultimately realize the acquisition of lithium carbonate products from oil and gas field produced water. The effects of characteristic impurity ions (Ca²⁺, Sr²⁺, Ba²⁺) on the performance of electrochemical adsorption for lithium extraction from oil and gas field produced water were investigated, and the operating conditions were optimized. Under the simulated oil and gas field produced water system, the purity of lithium increased from 0.066% to 44.991%, and the lithium content increased from 50 mg·L^-1 to 124.35 mg·L^-1. Coupled with selective electrodialysis, the Li⁺ concentration in the concentrate was enriched to 5.68 g·L^-1, and after impurity removal-precipitation-washing and drying, lithium carbonate (Li₂CO₃) products with a purity of 99.06% can be obtained. The total cost calculated from both energy consumption and raw material consumption for the coupling process was about 3200—3350 CNY·t^-1 Li₂CO₃. The results of the study provide theoretical guidance and technical references for the extraction/recovery of lithium with low content in oil and gas field produced water.

Key words: oil and gas field produced water, lithium extraction, electrochemical adsorption, selective electrodialysis, coupling

摘要：

油气田采出水作为开采石油、天然气及页岩气等产生的伴生废水，亟须进行资源化处置，其所含的锂具有较高的开发潜力，但其组成复杂、锂含量较低、开发难度大。基于此，提出电化学吸附-选择性电渗析纯化浓缩工艺，以最终实现从油气田采出水中获取碳酸锂产品。探究了油气田采出水中特征杂质离子（Ca²⁺、Sr²⁺、Ba²⁺）对电化学吸附提锂性能的影响，并优化了操作条件，在模拟油气田采出水体系下，锂纯度由0.066%提升至44.991%，锂含量由50 mg·L^-1富集至124.35 mg·L^-1。与选择性电渗析进行耦合，在优化条件下浓缩液中Li⁺浓度富集至5.68 g·L^-1，再经除杂、沉淀、洗涤及干燥可得纯度为99.06%的碳酸锂（Li₂CO₃）。耦合工艺的能耗和药剂消耗共计3200~3350 CNY·t^-1 Li₂CO₃。研究结果可为油气田采出水中低含量锂的提取/回收提供理论指导与技术参考。

关键词: 油气田采出水, 提锂, 电化学吸附, 选择性电渗析, 耦合

CLC Number:

TQ 150.9

Shichen ZHANG, Zhiyuan GUO, Yanmin WANG, Yachao HAO, Jing WANG, Panpan ZHANG, Zhiyong JI. Research on lithium extraction and recovery from oil and gas field produced water coupled with electrochemical adsorption-selective electrodialysis[J]. CIESC Journal, 2025, 76(12): 6601-6613.

张世晨, 郭志远, 王艳敏, 郝亚超, 汪婧, 张盼盼, 纪志永. 油气田采出水电化学吸附-选择性电渗析耦合锂提取回收研究[J]. 化工学报, 2025, 76(12): 6601-6613.

Figures/Tables 16

Fig.1 Schematic diagram of electrochemical adsorption-selective electrodialysis coupled with lithium extraction and recovery process for oil and gas field produced water

Table 1 Composition of produced water in oil and gas fields

采出水组成	离子浓度/(mg/L)
Li⁺	50.0
Mg²⁺	121.7
Na⁺	72510.0
Ca²⁺	1273.8
Sr²⁺	928.3
Ba²⁺	1135.3

Fig.2 Equipment diagram (a) and schematic diagram (b) of the flow-type electrochemical lithium extraction device

Fig.3 Equipment diagram (a) and schematic diagram (b) of selective electrodialysis device

Fig.4 Lithium extraction capacity(a), voltage trend with time(b), current efficiency and specific energy consumption(c), separation factor (d) and ionic radius and ionic hydration free energy(e) under different impurity ion systems

Fig.5 Lithium extraction capacity (a), voltage trend with time (b), current efficiency and specific energy consumption (c) and separation coefficient (d) with different Ba2+ content

Fig.6 Average lithium extraction capacity for 5 cycles at different flow rates (a) and Li+ concentration for 10 cycles at 500 ml·min-1(b)

Table 2 Ionic composition of the solution at each stage

溶液	浓度/(mg·L^-1)
溶液	Li⁺	Mg²⁺	Na⁺	Ca²⁺	Sr²⁺	Ba²⁺
模拟油气田采出水	50.0	121.7	72510	1273.8	928.3	1135.3
电化学富锂液	124.4	1.3	145.7	2.3	1.5	1.3
浓度外推-电化学富锂液	2049.3	16.9	2263.5	28	18.9	14.8
电渗析浓缩液	5680	27.2	6332	48.7	31.6	23.6

Fig.7 Lithium extraction capacity (a) and current efficiency and specific energy consumption (b) at different concentration gradients

Fig.8 Effect of operating voltage on desalination chamber conductivity (a), current (b), Li+ concentration (c), lithium recovery (d), current efficiency (e) and specific energy consumption (f)

Fig.9 Trends of current (a), lithium recovery (b), concentration of Li+ in the concentration chamber (c), current efficiency and specific energy consumption (d) during continuous electrodialysis process

Table 3 Composition of the solution after removal of impurities

[Li⁺]/(g·L^-1)	[Mg²⁺]/(mg·L^-1)	[Na⁺]/(g·L^-1)	[Ca²⁺]/(mg·L^-1)	[Sr²⁺]/(mg·L^-1)	[Ba²⁺]/(mg·L^-1)
3.74	0.01	7.35	6.16	2.26	1.03

Fig.10 SEM images of Li2CO3

Fig.11 XRD pattern of the product Li2CO3

Table 4 Concentration of each ion in the product Li2CO3

Li⁺	Na⁺	Mg²⁺	Ca²⁺	Sr²⁺	Ba²⁺
947	1.086	0.094	4.999	1.949	0.879

Table 5 Experimental-related parameters

参数	数值
电化学吸附原料液Li⁺浓度/(mg·L^-1)	50
电化学吸附处理能力/(ml·min^-1)	500
电化学吸附单位能耗/(Wh·mol^-1 (Li))	10~12
电渗析锂回收率/%	60
电渗析处理能力/(L·h^-1)	1.0
进料浓度/(mg·L^-1)	3971.4
进料LiCl浓度/(g·L^-1)	2
浓缩液Li⁺浓度/(g·L^-1)	5.68
电压/V	5
膜有效面积/m²	0.147
实验时间/h	24
电渗析提锂单位能耗/(kWh·mol^-1(Li))	0.028~0.032
工业电价/(CNY·kWh^-1)	0.7
除杂过程药剂消耗/(CNY·t^-1 (Li₂CO₃))	14.39
沉淀过程药剂消耗/(CNY·t^-1 (Li₂CO₃))	2363.52

References 32

[1]	Tarascon J M. Is lithium the new gold?[J]. Nature Chemistry, 2010, 2(6): 510.
[2]	Kanagasundaram T, Murphy O, Haji M N, et al. The recovery and separation of lithium by using solvent extraction methods[J]. Coordination Chemistry Reviews, 2024, 509: 215727.
[3]	赵紫伊, 周雪, 王铁夫, 等. 油气田采出水锂资源回收可行性、技术现状及展望[J]. 环境工程技术学报, 2023, 13(4): 1434-1443.
	Zhao Z Y, Zhou X, Wang T F, et al. Feasibility, technical status and prospects of lithium recovery from produced water in oil and gas fields[J]. Journal of Environmental Engineering Technology, 2023, 13(4): 1434-1443.
[4]	Nikkhah H, Ipekçi D, Xiang W J, et al. Challenges and opportunities of recovering lithium from seawater, produced water, geothermal brines, and salt lakes using conventional and emerging technologies[J]. Chemical Engineering Journal, 2024, 498: 155349.
[5]	Zhao Y Z, Xing H F, Rong M, et al. Quantum chemical calculation assisted efficient lithium extraction from unconventional oil and gas field brine by β-diketone synergic system[J]. Desalination, 2023, 565: 116890.
[6]	Wang X M, Numedahl N, Jiang C Q. Direct lithium extraction from Canadian oil and gas produced water using functional ionic liquids—A preliminary study[J]. Applied Geochemistry, 2024, 172: 106126.
[7]	Pan Y N, Zhan W Q, Zhang W C. Sustainable lithium extraction from produced water: integrating membrane pretreatment and next-generation adsorbents[J]. Journal of Environmental Management, 2025, 382: 125343.
[8]	王晓丽, 杨文胜. 电化学提锂体系及其电极材料的研究进展[J]. 化工学报, 2021, 72(6): 2957-2971.
	Wang X L, Yang W S. Research progress of electrochemical lithium extraction systems and electrode materials[J]. CIESC Journal, 2021, 72(6): 2957-2971.
[9]	Meng X R, Jing Y, Li J M, et al. Electrochemical recovery of lithium from brine by highly stable truncated octahedral LiNi_{0. 05}Mn_{1. 95}O₄ [J]. Chemical Engineering Science, 2024, 283: 119400.
[10]	朱兴驰, 郭志远, 纪志永, 等. 选择性电渗析镁锂分离过程模拟优化[J]. 化工学报, 2023, 74(6): 2477-2485.
	Zhu X C, Guo Z Y, Ji Z Y, et al. Simulation and optimization of selective electrodialysis magnesium and lithium separation process[J]. CIESC Journal, 2023, 74(6): 2477-2485.
[11]	Rögener F, Tetampel L. Electrodialysis for the concentration of lithium-containing brines: an investigation on the applicability[J]. Membranes, 2022, 12(11): 1142.
[12]	Zhou Y M, Yan H Y, Wang X L, et al. Electrodialytic concentrating lithium salt from primary resource[J]. Desalination, 2018, 425: 30-36.
[13]	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.
[14]	Gu J, Chen L L, Fan L J, et al. Multistage regulation of LiMn₂O₄ electrode for electrochemical lithium extraction from salt-lake[J]. Desalination, 2024, 586: 117828.
[15]	Pu Z Y, Zhu Z Q, Lv X J, et al. N, P-doped graphite/LiMn₂O₄ hybrid electrode for high-performance all-climate dual-ion batteries[J]. Journal of Colloid and Interface Science, 2025, 686: 408-419.
[16]	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.
[17]	Mubita T M, Porada S, Biesheuvel P M, et al. Strategies to increase ion selectivity in electrodialysis[J]. Separation and Purification Technology, 2022, 292: 120944.
[18]	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.
[19]	Yuan H F, Li M Z, Cui L, et al. Electrochemical extraction technologies of lithium: development and challenges[J]. Desalination, 2025, 598: 118419.
[20]	杨金花, 孙永耀, 赵霞. 基于选择性电渗析技术的盐湖卤水镁锂分离试验研究[J]. 化学与粘合, 2025, 47(2): 192-197.
	Yang J H, Sun Y Y, Zhao X. Experimental study on magnesium lithium separation in salt lake brine based on selective electrodialysis technology[J]. Chemistry and Adhesion, 2025, 47(2): 192-197.
[21]	Liu Q, Yang P, Tu W W, et al. Lithium recovery from oil and gas produced water: opportunities, challenges, and future outlook[J]. Journal of Water Process Engineering, 2023, 55: 104148.
[22]	Karuppasamy K, Mayyas A, Alhseinat E, et al. Exploring lithium extraction technologies in oil and gas field-produced waters: from waste to valuable resource[J]. Chemical Engineering Journal Advances, 2024, 20: 100680.
[23]	Khatoon R, Raksasat R, Ho Y C, et al. Reviewing advanced treatment of hydrocarbon-contaminated oilfield-produced water with recovery of lithium[J]. Sustainability, 2023, 15(22): 16016.
[24]	汤国军, 张宏军, 何化, 等. 油气田采出水提锂技术研究[J]. 天然气与石油, 2023, 41(6): 67-72.
	Tang G J, Zhang H J, He H, et al. Research on technology for lithium extraction from oil and gas field produced water[J]. Natural Gas and Oil, 2023, 41(6): 67-72.
[25]	Kumar A, Fukuda H, Hatton T A, et al. Lithium recovery from oil and gas produced water: a need for a growing energy industry[J]. ACS Energy Letters, 2019, 4(6): 1471-1474.
[26]	Guo Z Y, Ji Z Y, Wang J, et al. Electrochemical lithium extraction based on “rocking-chair” electrode system with high energy-efficient: the driving mode of constant current-constant voltage[J]. Desalination, 2022, 533: 115767.
[27]	李丽, 李宇, 金艳, 等. 高硫高硬气田采出水提锂过程关键技术及应用[J]. 无机盐工业, 2023, 55(1): 74-80.
	Li L, Li Y, Jin Y, et al. Key technology and application of lithium extraction from produced water in high sulfur and high hardness gas fields[J]. Inorganic Chemicals Industry, 2023, 55(1): 74-80.
[28]	蒋雨新. 尖晶石锰酸锂电极强化电容去离子脱盐研究[D]. 长沙: 中南大学, 2023.
	Jiang Y X. A study of capacitive deionization desalination strengthened by spinel LiMn₂O₄ electrode[D]. Changsha: Central South University, 2023.
[29]	Zhao Y, Mamrol N, Tarpeh W A, et al. Advanced ion transfer materials in electro-driven membrane processes for sustainable ion-resource extraction and recovery[J]. Progress in Materials Science, 2022, 128: 100958.
[30]	陶箴奇, 张志强, 毕秋艳, 等. 氯化锂与碳酸钠反应结晶制备碳酸锂的研究[J]. 无机盐工业, 2016, 48(11): 25-28.
	Tao Z Q, Zhang Z Q, Bi Q Y, et al. Study on preparation of lithium carbonate via reactive crystallization from lithium chloride and sodium carbonate[J]. Inorganic Chemicals Industry, 2016, 48(11): 25-28.
[31]	Xu Z G, Sun S Y. Preparation of battery-grade lithium carbonate with lithium-containing desorption solution [J]. Metals, 2021, 11(9): 1490.
[32]	郭苏丽, 杨海华. ICP-AES法测定废旧磷酸铁锂回收碳酸锂中锂和金属杂质元素含量[J]. 广东化工, 2020, 47(19): 144-145, 152.
	Guo S L, Yang H H. Determination of lithium and metal impurity elements in lithium carbonate recovered from waste lithium iron phosphate by ICP-AES method[J]. Guangdong Chemical Industry, 2020, 47(19): 144-145, 152.