低品位含锂气田采出水提锂技术研究与现场试验

doi:10.19965/j.cnki.iwt.2024-0951

摘要/Abstract

摘要：

近年来，随着新能源汽车市场对碳酸锂产品需求量的增加，气田采出水中锂资源开发引起社会各界广泛关注。气田采出水因化学组分复杂、Li⁺浓度相对盐湖卤水低，提锂工艺一直是制约气田采出水中锂资源化利用的关键问题。基于长庆靖边气田采出水低品位含锂特征（质量浓度50 mg/L以下），分别从预处理工艺及参数优选、提锂关键技术（吸附法和电化学法）评价及参数优化、现场提锂效果及成本分析等方面开展了研究。结果表明，气田采出水经絮凝沉淀-臭氧催化氧化预处理后，浊度去除率在90%以上，COD去除率可达43%。电化学提锂工艺锂回收率低，且存在副反应和不稳定性；而锰系吸附剂对气田采出水中Li⁺的吸附量在0.98~4.57 mg/g区间内，处理低品位含锂采出水更有优势。采用处理规模200 L/h的一体化橇装装置开展了现场试验，经过两级吸附塔后，锂离子吸附回收率最高达87%，进一步对富锂脱附液分离、浓缩、沉淀，得到碳酸锂成品，碳酸锂质量分数达99.2%，产品符合《碳酸锂》（GB 11075—2013）中0级标准。研究打通了低品位含锂气田采出水提锂关键工艺技术路线，为后续气田采出水规模化提锂奠定了基础。

关键词: 低品位含锂气田采出水, 预处理, 吸附法提锂, 锰系吸附剂, 铝系吸附剂, 电化学提锂, 现场试验

Abstract:

In recent years, with the increasing demand for lithium carbonate products in the new energy vehicle market, the development of lithium resources in gas field produced water has attracted widespread attention from all sectors of society. Due to the complex chemical composition of gas field produced water and the relatively lower concentration of Li⁺ compared with salt lake brine, lithium extraction technology has always been a key issue restricting the resource utilization of lithium in gas field produced water. Based on the low-grade lithium-containing characteristics of produced water from Changqing Jingbian Gas Field (with mass concentration below 50 mg/L), research was carried out from aspects such as pretreatment processes and parameter optimization, evaluation and parameter optimization of key lithium extraction technologies (adsorption and electrochemical methods), on-site lithium extraction effect, and cost analysis. The results showed that after the gas field produced water was pretreated by flocculation precipitation-ozone catalytic oxidation, the turbidity removal rate exceeded 90%, and the COD removal rate reached 43%. The electrochemical lithium extraction process had a low lithium recovery rate, accompanied by side reactions and instability. Manganese-based adsorbents, with an adsorption capacity for Li⁺ in gas field produced water ranging from 0.98 mg/g to 4.57 mg/g, had more advantages in treating low-grade lithium-containing produced water. Field test was conducted using an integrated skid-mounted device with treatment capacity of 200 L/h. After passing through two-stage adsorption towers, the lithium ion adsorption recovery rate could reach up to 87%. Further separation, concentration, and precipitation of the lithium-rich desorption solution were conducted to obtain lithium carbonate product with a mass fraction of 99.2%, which met the Grade 0 standard specified in Lithium Carbonate (GB 11075—2013). This research has established the key technological route for lithium extraction from low-grade lithium-containing gas field produced water, laying a foundation for the subsequent large-scale lithium extraction from gas field produced water.

Key words: low-grade lithium-containing gas field produced water, pretreatment, lithium extraction by adsorption, manganese-based adsorbents, aluminum-based adsorbents, electrochemical lithium extraction, field test

中图分类号:

X703

姬伟, 徐文龙, 何战友, 范婧, 何党联, 张建海, 谷言贺. 低品位含锂气田采出水提锂技术研究与现场试验[J]. 工业水处理, 2025, 45(11): 174-182.

Wei JI, Wenlong XU, Zhanyou HE, Jing FAN, Danglian HE, Jianhai ZHANG, Yanhe GU. Research and field test of lithium extraction technology for low-grade lithium-containing gas field produced water[J]. Industrial Water Treatment, 2025, 45(11): 174-182.

https://www.iwt.cn/CN/Y2025/V45/I11/174

图/表 16

图1 锰系吸附剂（a）和铝系吸附剂（b）的外观

Fig.1 Appearance of manganese-based adsorbent（a） and aluminum-based adsorbent（b）

表1 靖边气田不同气井采出水水质

Table 1 Produced water quality from different gas wells in Jingbian gas field

项目	1号水样	2号水样	3号水样	4号水样	5号水样
pH	5.55	5.84	5.46	5.31	5.55
电导率/（mS·cm^-1）	310	111.7	126	685	280
氯离子/（mg·L^-1）	75 980.7	19 712.0	103 935.9	108 953.4	41 574.3
总硬（以碳酸钙计）/（mg·L^-1）	63 554.8	18 562.0	103 402.7	97 854.2	43 378.7
硫酸根/（mg·L^-1）	ND	ND	ND	ND	ND
碳酸氢根/（mg·L^-1）	72.9	138.3	312.5	407.6	389.0
碳酸根/（mg·L^-1）	ND	ND	ND	ND	ND
COD/（mg·L^-1）	1 660	1 040	2 350	1 870	3 250
Li/（mg·L^-1）	41.8	5.2	77.5	48.4	19.4
B/（mg·L^-1）	16.78	8.10	44.33	45.13	19.28
Ba/（mg·L^-1）	50.23	116.40	879.08	515.05	37.20
Mg/（mg·L^-1）	3 138	643.83	3 023.3	3 468.03	1 561.88
Sr/（mg·L^-1）	748.00	487.60	896.10	895.33	879.88
Ca/（mg·L^-1）	19 343	5 568	31 021	29 356	13 014

图2 臭氧氧化工艺流程示意 1—反应器；2—取样阀；3—多孔布气板；4—气体流量计；5—臭氧浓度检测仪；6—氧气发生器；7—臭氧发生器；8—三通转接阀；9—尾气洗瓶。

Fig.2 Schematic diagram of ozone oxidation process flow

图3 现场试验工艺流程

Fig.3 Process flow chart of field test

图4 不同预处理工艺对吸附剂吸附提锂性能的影响

Fig.4 Effect of different pretreatment processes on lithium adsorption performance of the adsorbents

图5 不同pH下絮凝剂对气田采出水浊度、石油类物质去除效果的影响

Fig.5 Effects of pH on gas field produced water turbidity and petroleum substance removal by coagulants

图6 不同臭氧浓度、停留时间下臭氧催化氧化对COD的去除效果

Fig.6 COD removal efficiency by ozone catalytic oxidation under different ozone concentrations and residence times

图7 锰系吸附剂、铝系吸附剂对不同气田采出水中Li⁺的吸附效果

Fig.7 Li⁺ adsorption performance of Mn-based and Al-based adsorbents in gas field produced water

图8 低锂浓度、中等锂浓度气田采出水电化学提锂的锂回收率及pH变化

Fig.8 Lithium recovery rate and pH variation during electrochemical lithium extraction from gas field produced water with low and medium Li⁺ concentrations

图9 不同pH下锰系吸附剂对Li⁺吸附性能锰系吸附剂

Fig.9 Adsorption performance of manganese-based adsorbents for Li⁺ under different pH

图10 锰系吸附剂的循环利用性能

Fig.10 Recyclability performance of manganese-based adsorbents

图11 现场吸附提锂的试验效果

Fig.11 Field test results of lithium adsorption and extraction

表2 现场试验的锂脱附液离子成分

Table 2 Ion composition of lithium desorption solution in field test

脱附液中离子	Li⁺	Mn²⁺	Ca²⁺	Mg²⁺	Ba²⁺	Sr²⁺	Na⁺
质量浓度/（mg·L^-1）	849.7	214.5	526.6	35.0	295.1	13.1	30.1

图12 锂脱附液资源化处理的各工段离子质量浓度

Fig.12 Ionic mass concentration in each stage during the resource utilization of lithium desorption solution

表3 碳酸锂产品化学成分

Table 3 Chemical composition of lithium carbonate product

指标	Ba（以干基计）/%	Mg（以干基计）/%	Mn（以干基计）/%	Sr（以干基计）/%	Na（以干基计）/%	Ca（以干基计）/%	Li₂CO₃（以干基计）/%
现场碳酸锂产品	ND	ND	ND	ND	0.015	0.009	99.20

表4 现场试验提锂运行成本

Table 4 Operating costs for lithium extraction in field test

项目类型	提锂运行成本（以单位质量碳酸锂计）/（万元·t^-1）
合计	8.51
动力成本	1.86
药剂成本	1.33
耗材成本（包括吸附剂、膜元件等）	4.64
公用工程成本	0.68

参考文献 18

[1]	吕帅轲，赵云良，陈立才，等. 锰系和铝系吸附剂对江汉盆地卤水中锂的吸附性能研究［J］. 金属矿山，2022（8）：94-100.
	Shuaike LÜ， ZHAO Yunliang， CHEN Licai，et al. Study on lithium adsorption properties of manganese-based and aluminum-based adsorbents for the brine from Jianghan basin［J］. Metal Mine，2022（8）：94-100.
[2]	叶燕，高立新. 对四川气田水处理的几点看法［J］. 石油与天然气化工，2001，30（5）：263-265.
	YE Yan， GAO Lixin. Views on the treatment of gas field water in Sichuan［J］. Chemical Engineering of Oil and Gas，2001，30（5）：263-265.
[3]	高娟琴，王登红，王伟，等. 国内外主要油（气）田水中锂提取现状及展望［J］. 地质学报，2019，93（6）：1489-1500.
	GAO Juanqin， WANG Denghong， WANG Wei，et al. Current status and prospects of lithium extraction in major domestic and foreign oil（gas） field waters［J］. Acta Geologica Sinica，2019，93（6）：1489-1500.
[4]	柯季. 气田水直接提锂研究成功［J］. 井矿盐技术，1982，13（6）：40.
	KE Ji. Successful research on direct extraction of lithium from gas field water［J］. China Well and Rock Salt，1982，13（6）：40.
[5]	钟辉. 偏钛酸型锂离子交换剂的交换性质及从气田卤水中提锂［J］. 应用化学，2000，17（3）：307-309.
	ZHONG Hui. Property of H₂TiO₃ type ion exchangers and extraction of lithium from brine of natural gas wells［J］. Chinese Journal of Applied Chemistry，2000，17（3）：307-309.
[6]	潘磊，许飞龙，李建楠，等. 油田水制备电池级碳酸锂研究［J］. 无机盐工业，2019，51（6）：41-44.
	PAN Lei， XU Feilong， LI Jiannan，et al. Research of battery grade Li₂CO₃ preparation by oilfield water［J］. Inorganic Chemicals Industry，2019，51（6）：41-44.
[7]	CHAGNES A， SWIATOWSKA J. Lithium process chemistry：Resources，extraction，batteries，and recycling［M］. Amsterdam，The Netherlands，2015：233-267.
[8]	ZHANG Junxiang， CHENG Zeyu， QIN Xinbo，et al. Recent advances in lithium extraction from salt lake brine using coupled and tandem technologies［J］. Desalination，2023，547：116225. doi:10.1016/j.desal.2022.116225
[9]	陈欣怡，夏开胜，高强，等. 锂离子选择性吸附材料的制备与提取应用［J］. 化学进展，2023，35（10）：1519-1533.
	CHEN Xinyi， XIA Kaisheng， GAO Qiang，et al. Preparation and extraction application of lithium ion selective adsorption materials［J］. Progress in Chemistry，2023，35（10）：1519-1533.
[10]	郝勇，马瑞瑞，田元立，等. 锂离子筛在盐湖卤水提锂中的研究进展［J］. 应用化工，2024，53（2）：494-498.
	HAO Yong， MA Ruirui， TIAN Yuanli，et al. Research progress of lithium ion sieve in extracting lithium from salt lake brine［J］. Applied Chemical Industry，2024，53（2）：494-498.
[11]	李彦乐，刘宜林，霍俊杰，等. 层状结构铝系吸附剂在盐湖提锂领域的研究［J］. 化工学报，2023，74（12）：4777-4791.
	LI Yanle， LIU Yilin， HUO Junjie，et al. Research progress of aluminum adsorbents in lithium extraction from salt lakes［J］. CIESC Journal，2023，74（12）：4777-4791.
[12]	黄敏，余亮良. 锰基锂离子筛研究进展［J］. 有色冶金设计与研究，2023，44（5）：14-17.
	HUANG Min， YU Liangliang. Research progress in manganese-based lithium-ion sieve［J］. Nonferrous Metals Engineering & Research，2023，44（5）：14-17.
[13]	付煜，邓觅，黄冬根，等. 盐湖卤水提锂技术研究进展［J］. 无机盐工业，2023，55（9）：9-16.
	FU Yu， DENG Mi， HUANG Donggen，et al. Research progress of lithium extraction technology from salt lake brine［J］. Inorganic Chemicals Industry，2023，55（9）：9-16.
[14]	张俊义，董生德，贺欣，等. 电化学法提锂技术的研究进展［J］. 化学通报，2023，86（9）：1044-1052.
	ZHANG Junyi， DONG Shengde， HE Xin，et al. Research progress in electrochemical lithium extraction technology［J］. Chemistry，2023，86（9）：1044-1052.
[15]	王伟，李海涛，罗军，等. 絮凝剂在废水处理中的应用［J］. 广州化工，2024，52（22）：120-122.
	WANG Wei， LI Haitao， LUO Jun，et al. Application of flocculant in wastewater treatment［J］. Guangzhou Chemical Industry，2024，52（22）：120-122.
[16]	钟振辉，刘晓珊，黄洁阳，等. 絮凝法处理原水的研究进展［J］. 广东化工，2016，43（7）：148-149.
	ZHONG Zhenhui， LIU Xiaoshan， HUANG Jieyang，et al. Research progress in the treatment of raw water by flocculation［J］. Guangdong Chemical Industry，2016，43（7）：148-149.
[17]	袁闯，李正宾. 臭氧催化氧化技术在化工废水处理中的应用［J］. 化学工程与装备，2024（7）：158-160.
	YUAN Chuang， LI Zhengbin. Application of ozone catalytic oxidation technology in chemical wastewater treatment［J］. Chemical Engineering & Equipment，2024（7）：158-160.
[18]	王冠颖，郭涵，刘馨瑶，等. 臭氧催化氧化深度处理焦化废水技术梳理［J］. 工业水处理，2025，45（5）：29-37．
	WANG Guanying， GUO Han， LIU Xinyao，et al. Technical carding of advanced treatment of coking wastewater by ozone catalytic oxidation［J］. Industrial Water Treatment，2025，45（5）：29-37．

选择文件类型/文献管理软件名称

选择包含的内容