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

doi:10.11949/0438-1157.20250643

摘要/Abstract

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需进行资源化处置，其所含的锂具有较高开发潜力，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约3200-3350元·t^-1 Li₂CO₃。研究结果为油气田采出水中低含量锂的提取/回收提供了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

Abstract:

As the associated wastewater produced by the exploitation of oil, natural gas, and shale gas, oil and gas field produced water is in urgent need of resource disposal. The lithium contained in it has high development potential, but its composition is complex, the lithium content is low, and the development is difficult. 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 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

中图分类号:

TQ 150.9

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, DOI: 10.11949/0438-1157.20250643.

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, DOI: 10.11949/0438-1157.20250643.

图/表 16

图1 油气田采出水电化学吸附-选择性电渗析耦合锂提取回收工艺示意图

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

表1 油气田采出水组成成分

Table 1 Composition of produced water in oil and gas fields

采出水组成	Li⁺	Mg²⁺	Na⁺	Ca²⁺	Sr²⁺	Ba²⁺
离子浓度（mg/L）	50	121.7	72510	1273.8	928.3	1135.3

图2 流动型电化学提锂装置的设备图(a)和原理图(b)

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

图3 选择性电渗析装置的设备图(a)和原理图(b)

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

图4 不同杂质离子体系的提锂容量(a)、电压随时间变化趋势(b)、电流效率和单位能耗(c)、分离系数(d)及离子半径与离子水合自由能(e)

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

图5 不同Ba2+含量的提锂容量(a)、电压随时间变化趋势(b)、电流效率和单位能耗(c)和分离系数(d)

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

图6 不同流速下5个循环的提锂容量均值(a)和500 mL·min-1条件下10个循环的Li+浓度(b)

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)

表2 各阶段溶液离子组成

Table 2 Ionic composition of the solution at each stage

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

图7 不同浓度梯度下的提锂容量(a)和电流效率与单位能耗(b)

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

图8 操作电压对淡室电导率(a)、电流(b)、Li+浓度(c)、锂回收率(d)、电流效率(e)和单位能耗(f)的影响

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)

图9 连续电渗析过程中的电流(a)、锂回收率(b)、浓室Li+浓度(c)、电流效率和单位能耗(d)的变化趋势

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

表3 除杂后溶液组成

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）

图10 (a-b)为产品Li2CO3的SEM图

Fig.10 (a-b) SEM images of product Li2CO3

图11 产品Li2CO3的XRD图

Fig.11 XRD pattern of the product Li2CO3

表4 产品Li2CO3中各离子浓度

Table 4 Concentration of each ion in the product Li2CO3

	Li⁺	Na⁺	Mg²⁺	Ca²⁺	Sr²⁺	Ba²⁺
离子浓度（mg·L^-1）	947	1.086	0.094	4.999	1.949	0.879

表5 实验相关参数

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（W h·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（元·kWh^-1）	0.7
除杂过程药剂消耗（元·t^-1 Li₂CO₃）	14.39
沉淀过程药剂消耗（元·t^-1 Li₂CO₃）	2363.52

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