锂资源提取技术研究进展

doi:10.19964/j.issn.1006-4990.2023-0299

Abstract

Abstract:

Lithium is considered as one of the most important energy metals in the 21st century.Under the common goal of global carbon reduction，the rapid development of new energy industry has promoted the continuous growth of lithium consumption in the past three years，and triggered a research boom on lithium extraction technology at home and abroad.According to the occurrence state of lithium resources，the technology of extracting lithium from mineral and brine was summarized，and the advantages and disadvantages of various methods were systematically summarized and compared.The main methods of extracting lithium from mineral mainly included limestone roasting，sulfuric acid，sulfate roasting，pressure boiling，chlorination roasting and direct acid leaching.The technologies that had received widespread attention in extracting lithium from brine mainly included precipitation，adsorption，solvent extraction，membrane separation and electrochemistry.The high price of lithium carbonate was fallen，and the international situation of lithium salt acquisition became increasingly severe.It was imperative to continuously develop and improve the lithium extraction technology，enhance the self-sufficiency of lithium resources，and achieve cost reduction and efficiency improvement of lithium extraction technology.

Key words: lithium extraction, lithium mineral, salt-lake brine, separation

CLC Number:

TQ131.11

CHEN Haixia, YAN Hong, SUN Yunlong, MA Guoqiang. Research progress of lithium resource extraction technology[J]. Inorganic Chemicals Industry, 2024, 56(1): 9-22.

Figures/Tables 7

Fig.1

Fig.2

Fig.3

Fig.4

Table 1

Comparison of lithium extraction processes from minerals"

方法	原理	适用范围	优点	缺点
石灰石烧结法	与石灰石按比例混合焙烧，破坏矿物结构，使锂转化为可溶性LiOH	无具体限制	实用性强；生产成本低；原料易获取	蒸发能耗高；锂回收率低；浸出的矿泥及滤渣易凝聚，设备维护困难；废渣量大，难以再利用；面临淘汰
硫酸法	浓硫酸酸化焙烧将矿石中的锂转变为硫酸锂	矿石（锂辉石）提锂主流方法，矿石品位要求低	工艺简单；锂及其他有价金属提取率高；废渣少	硫酸腐蚀设备；硫酸和纯碱消耗量大；高温焙烧能耗高；提取锂云母时浸出液杂质含量高，纯化困难
硫酸盐法	以硫酸盐作为焙烧助剂，转化为可溶性硫酸锂浸出以实现锂溶出	锂云母提锂主流方法，主要用于含锂硅酸盐类和磷酸盐矿物	工艺简单；较硫酸法延长设备寿命；产物杂质少；产率高	能耗较高；会生成含氟、硫有害气体，污染环境；金属铷和铯的回收率低
压煮法	在高压条件下用Na⁺或Ca²⁺取代锂矿石中的Li⁺以得到含锂浸出液	主要用于处理锂云母矿	工艺流程简单；锂浸出率高；物料流通量小；设备腐蚀程度小	高温高压，反应条件苛刻；设备要求高；需脱氟焙烧，污染环境
氯化焙烧法	利用氯化剂将碱金属离子和其他有价金属离子转化为氯化物提取到浸出液中	主要用于处理锂云母矿	工艺流程简单；氯化剂廉价；能耗低；锂回收率高	工艺引入氯，腐蚀设备；高温氯化LiCl 气体难以收集；生产成本高；产生影响环境的废气、废渣
全湿法	利用氟离子对铝硅酸盐的强腐蚀性，省却焙烧工艺，以硫酸为浸出剂，氟化物为助浸剂提取锂	含锂硅酸盐矿物	无需高温焙烧，能耗低；成本低	存在副产品回收、废水处理、分离工艺优化问题

Table 1

Fig.5

Table 2

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方法	原理	适用范围	优点	缺点
沉淀法	利用太阳能蒸发浓缩、逐级除杂富集锂，通过化学沉淀分离锂产品	高锂含量和低镁锂比的卤水	工艺成熟，碳酸盐沉淀法已实现工业应用；操作简易；成本较低；能耗低	工艺流程长；回收率低；产生大量废渣，环境不友好
吸附法	使用高选择性吸附剂来吸附卤水中Li⁺以实现从高镁锂比卤水中分离锂离子	无具体限制	铝盐吸附剂工艺成熟，已产业化；对卤水镁锂比无要求；高洗脱率；工艺流程简单；绿色环保	粉状吸附剂难以回收；流动性差；循环稳定性差；溶损严重；杂质含量高；吸附容量低
溶剂萃取法	利用锂离子在水相和有机相的溶解度差异，转相富集，再通过反萃提取	无具体限制	高镁锂比卤水中提锂最有效方法；工艺简单；成本较低；有机相循环使用，绿色经济	TBP萃取剂在水中溶损严重；氯化铁易乳化；高浓度盐酸造成设备腐蚀；萃取剂易挥发
膜分离法	通过外在驱动力的作用对溶质进行分离，为离子选择性迁移过程，主要分为纳滤法和电渗析法	无具体限制	镁锂分离效率高；可操作性强；生产稳定性佳；淡水消耗量小；清洁无污染	进口膜材料成本较高；膜易堵塞或损坏
电化学法	锂电池正极材料充放电过程中伴随Li⁺在电极与电解液间转移，实现吸附、脱附效果	无具体限制	适用低品位、复杂盐湖卤水体系；装置可模块化；提锂效率高；环境友好	锂吸附容量较低；电极循环性能较差；能耗高；副反应较多

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