锂云母提锂工艺及脱氟技术研究进展

杨佩东; 董树豪; 郭慧; 韩桂洪; 曹亦俊

doi:10.13779/j.cnki.issn1001-0076.2022.03.003

锂云母提锂工艺及脱氟技术研究进展

郑州大学化工学院, 河南郑州 450001

基金项目:
国家自然科学基金(52104271);河南省自然科学基金(212300410278);河南省科技攻关(212102310371);中国博士后基金(2020M682353);河南省博士后启动经费(202002020)

详细信息

作者简介: 杨佩东(1998-)男，陕西宝鸡人，硕士研究生，主要从事矿产资源综合利用

通讯作者: 郭慧(1989-)女，河南林州人，讲师，主要从事锂资源的高效提取，E-mail：hnhguo89@zzu.edu.cn

中图分类号: TD983;TF826⁺.3

收稿日期: 2022-05-11

刊出日期: 2022-06-25

A Review of Lithium Extraction from Lepidolite and Current Research Development of Fluorine Removal

School of Chemical Engineering, Zhengzhou University, Zhengzhou 450001, China

More Information

Corresponding author: GUO Hui, hnhguo89@zzu.edu.cn

Received Date: 11 May 2022

Publish Date: 25 June 2022

摘要

摘要:
锂云母是我国重要的锂矿资源, 开发高效的提锂工艺对于保障锂行业可持续发展具有重要的研究意义。氟具有极强的电负性, 可以取代表界面羟基, 从而进入锂云母晶格, 在锂云母中含量可达5%~10%, 如何实现提锂过程中氟的深度脱除对于锂云母的清洁、高效提取具有重要意义。通过对典型的硫酸法、石灰石法、硫酸盐法、氯化焙烧法、压煮法和氟化学法等锂云母提锂工艺研究现状进行阐述, 充分探讨各主流提锂工艺的反应原理、工艺条件等, 客观分析总结工艺的优缺点, 并对目前脱氟技术的研究现状进行分析, 总结现有脱氟工艺的反应机理及脱氟装置改进方向。最后, 对锂云母整体提锂工艺的深度脱氟, 凝练出液相氟脱除的新思路, 旨在为锂云母清洁、高效提取提供重要的理论基础。
- 锂云母 /
- 焙烧 /
- 脱氟 /
- 提锂 /
- 综合利用
Abstract:
Lepidolite is an important lithium resource in China. The development of efficient lithium extraction process is of great significance to ensuring the sustainable development of lithium industry. Due to the strong electronegativity of fluorine(F), about 5%~10% of F attacks the lepdolite lattice by taking interfacial hydroxyl groups. It is critical for the clean and effective utilisation lepidolite to accomplish the deep removal of fluorine during the lithium extraction process. Firstly, the typical methods to extract lithium from lepidolite were discussed such as sulfuric acid and limestone, sulfate, chloride roasting, pressure autoclave method and the fluorine chemical method. The reaction principle and technological conditions including the advantages and disadvantages of different methods were systematically discussed. Moreover, the current research development of defluorination was summarized such as the reaction mechanism and development of defluorination device. Finally, the deep fluorine removal, especially for fluorine in lithium containing liquid phase, was proposed as a new research direction, aiming at providing an important theoretical basis for clean and efficient lithium extraction of lepidolite.
- lepidolite /
- roasting /
- fluorine removal /
- lithium extraction /
- comprehensive utilization

HTML全文

图 1 我国近年锂资源供应结构^[3]

Figure 1.

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图 2 硫酸法工艺流程示意图^[20]

Figure 2.

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图 3 硫酸盐法工艺流程^[58]

Figure 3.

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图 4 氟化学法反应机理示意图^[50]

Figure 4.

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图 5 不同温度下LiF与水蒸气反应平衡组成^[57]

Figure 5.

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表 1 几种典型锂矿的化学组成^[12-14]

Table 1. Chemical composition of typical lithium ores

矿物种类	化学式	晶体结构	矿物的化学成分/%
矿物种类	化学式	晶体结构	Li₂O	Na₂O	K₂O	SiO₂	F	FeO	Al₂O₃
锂辉石	LiAl(SiO₃)₂	链状	8.03	0.55	0.48	63.6	_	_	28.7
透锂长石	LiAlSi₄O₁₀	架片状	4.73	0.17	0.02	77.7	_	_	17.1
锂云母	K(Li, Al)₃(Al, Si, Rb)₄O₁₀(F, OH)₂	层状	4.19	0.56	8.55	52.3	5.9	_	28.8
锂霞石	KLiFeAl(AlSi₃) O₁₀(F, OH)₂	粒、块状	2-5	0.19	10.1	42.8	6.1	11	21.7
锂磷铝石	LiAl(F, OH)PO₄	短柱状	7.40	5.12	_	_	9.4	_	33.6

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表 2 锂云母主流提锂工艺现状及优缺点

Table 2. Advantages and disadvantages of the current lithium extraction methods from lepidolite

工艺方法	应用现状	锂浸出率	优点	缺点
硫酸法^[18-25]	工艺成熟、应用广泛，主要用于锂辉石矿提锂	92%~96%	生产效率高，固液相混合均匀，回收率高^[21]	浸出液杂质含量高、工艺流程长、酸浸中和渣量大^[23]、对设备防腐蚀性能要求高
硫酸盐法^[26-33]	适用于处理江西宜春锂云母矿	90%~95%	能耗低，焙烧、浸出时间短^[26]	钾盐用量大，铷铯浸出率低^[28]，易导致窑内结圈
石灰石法^[34-38]	已被逐渐淘汰	85%~90%	工艺简单，原料成本低^[34]	锂回收率低^[35]，能耗高
氯化焙烧法^[39-44]	有一定应用	90%~95%	焙烧时间短、有价金属回收率高	浸出液含钙高，腐蚀设备严重^[39]
压煮法^[45-46]	江西赣锋锂业应用	75%~94%	工艺简单^[45]，浸出率高	对工艺条件及矿物种类要求苛刻^[46]
氟化学法^[47-54]	尚未工业化应用	93%~96%	流程较短、成本低，锂云母综合利用率高^[47]	面临含氟溶液的净化和氟元素循环利用问题^[54]

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