壳聚糖锂离子筛复合材料用于页岩气废水提锂的研究  

Lithium extraction from shale gas wastewater using chitosan lithium-ion sieve composites

作　　者：任玉春 赵丹丹 龚韬 付辰 周飞 吴征莲 付永胜[1] 黄涛[1] REN Yuchun;ZHAO Dandan;GONG Tao;FU Chen;ZHOU Fei;WU Zhenglian;FU Yongsheng;HUANG Tao(School of Environmental Science and Engineering,Southwest Jiaotong University,Chengdu 611756,China;Leshan Environmental Monitoring Center Station of Sichuan Province,Department of Ecology and Environment of Sichuan Province,Leshan 614000,Sichuan,China;Chengdu Pollution Source Monitoring Centre,Chengdu 610066,China)

机构地区：[1]西南交通大学环境科学与工程学院,成都611756 [2]四川省乐山生态环境监测中心站,四川乐山614000 [3]成都市污染源监测中心,成都610066

出　　处：《安全与环境学报》2025年第4期1544-1552,共9页Journal of Safety and Environment

基　　金：中央高校基本科研业务费-科技创新项目(2682024CX106)。

摘　　要：为了开发一种高效的锂吸附材料,从四川盆地页岩气废水(Shale Gas Wastewater, SGW)中回收锂资源,以应对电动汽车和储能行业对锂电池需求的急剧上升,研究通过固相反应合成H1.33Mn1.67O4(HMO),并将壳聚糖(Chitosan, CTS)作为造粒剂,制备复合材料CTS/HMO。在SGW中,CTS/HMO对锂的吸附质量比达到7.83 mg/g,经5次吸附-解吸循环后吸附质量比仅下降1.25%,表现出较高的稳定性。动力学研究显示,准二级动力学模型更符合试验结果,表明吸附过程主要由化学吸附控制。等温吸附试验结果显示,CTS/HMO的吸附行为符合Langmuir模型,表明其为单层吸附。选择性试验进一步验证了CTS/HMO对锂的良好选择性,这归因于HMO尖晶石结构的离子筛效应。在固定床过滤试验中,流速为0.104 mL/min,床层总容积为7.7 cm3时,该材料约在2 950 min后达到饱和,显示出良好的吸附寿命;对不同流速下的固定床吸附进行Thomas模型拟合,结果显示较低流速下的吸附质量比较大。研究表明,CTS/HMO是一种具有良好前景的工业级锂吸附剂,适用于从SGW中提取锂资源,可为实现资源的可持续利用和环境保护提供新技术。This study aims to develop an efficient lithium adsorption material tailored for the recovery of lithium from Shale Gas Wastewater(SGW)in the Sichuan Basin.As the demand for lithium surges due to the growth of electric vehicles and energy storage solutions,there is an urgent need for sustainable lithium recovery methods.In this research,H 1.33 Mn 1.67 O 4(HMO)was synthesized through a solid-phase reaction,and a novel composite material,CTS/HMO,was created using chitosan(CTS)as a granulating agent.This composite material was optimized to enhance lithium adsorption capacity,stability,and reusability.In SGW adsorption tests,the CTS/HMO composite demonstrated a notable lithium adsorption mass ratio of 7.83 mg/g.Remarkably,after five adsorption-desorption cycles,the material s adsorption capacity decreased by only 1.25%,highlighting its excellent durability and reusability,which makes it suitable for multiple lithium extraction applications.Kinetic studies on the CTS/HMO composite indicated that its adsorption process adheres to a pseudo-second-order model,which is primarily driven by chemisorption and enhances both selectivity and efficiency.Additionally,isothermal studies demonstrated that lithium adsorption on CTS/HMO aligns with the Langmuir model,suggesting monolayer adsorption.This characteristic facilitates a uniform distribution of lithium ions and improves extraction efficiency.Selectivity experiments further demonstrated the strong affinity of CTS/HMO for lithium ions,a property attributed to the spinel structure of HMO.This structure provides an ion-sieving effect that preferentially adsorbs lithium ions over other competing ions present in wastewater.In laboratory fixed-bed filtration experiments,a flow rate of 0.104 mL/min and a bed volume of approximately 4.92 g of CTS/HMO adsorbent resulted in saturation after around 2950 minutes.Fitting the Thomas model to the fixed-bed adsorption data at various flow rates revealed that the adsorption capacity was higher at lower flow rates.The exceptional durability

关 键 词：环境工程学 锂资源回收 页岩气废水 壳聚糖 锰系锂离子筛 

分 类 号：X703[环境科学与工程—环境工程]