钴铁酸浸液分离及电池级磷酸铁回收技术进展

doi:10.16085/j.issn.1000-6613.2024-1087

摘要/Abstract

摘要：

钴铁合金酸浸液作为工业中常见的废液，含有大量的铁元素以及高附加值的钴元素，经过适当的除杂、分离和提纯处理后，铁元素可作为电池级磷酸铁的铁源，具有较大的应用潜力。本文系统介绍了钴铁酸浸液中钴离子与铁离子分离的主要技术方法，重点讨论了溶剂萃取法和沉淀分离法，溶剂萃取法以其选择性高、分离效率好而广泛应用，而沉淀分离法则因其操作简便、经济成本低备受关注。同时，本文还讨论了利用含铁废料制备高品质电池级磷酸铁的相关技术进展。指出了目前研究面临的问题并探讨了矿产资源回收利用的发展趋势，为实现资源的循环利用和锂离子电池等相关领域的发展开拓新思路，对促进循环经济和推动可持续发展具有重要意义。

关键词: 钴铁酸浸液, 分离, 电池级磷酸铁, 废物处理, 回收

Abstract:

Cobalt-iron alloy acid leachate, a common industrial waste, contains abundant iron and valuable cobalt. After appropriate purification, separation and refinement processes, iron can serve as a source of iron for battery-grade iron phosphate, offering substantial application potential. This paper systematically introduced the main technical methods for separating cobalt and iron ions from cobalt-iron alloy leachates with a focus on solvent extraction and precipitation separation. Solvent extraction was widely used due to its high selectivity and separation efficiency, while precipitation separation was favored for its simplicity and low economic cost. Additionally, this paper discussed advances in production high-quality battery-grade iron phosphate from iron-containing waste. This article identified current research challenges and discussed the evolving trends in mineral resource recycling, aiming to pioneer new strategies for resource circularity and to advance applications in fields such as lithium-ion batteries. These endeavors were pivotal for promoting a circular economy and fostering sustainable development.

Key words: cobalt-iron acid leaching solution, separation, battery-grade iron phosphate, waste treatment, recovery

中图分类号:

TQ13

杜璇, 王战宏, 郑彬, 许卫, 王硕, 石鹏, 高国. 钴铁酸浸液分离及电池级磷酸铁回收技术进展[J]. 化工进展, 2025, 44(9): 5327-5338.

DU Xuan, WANG Zhanhong, ZHENG Bin, XU Wei, WANG Shuo, SHI Peng, GAO Guo. Progress on separation of cobalt-iron acid leaching solution and battery grade iron phosphate recovery technology[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5327-5338.

图/表 9

参考文献 33

[1]	LI Yu, ZHANG Jiawei, CHEN Qingguo, et al. Emerging of heterostructure materials in energy storage: A review[J]. Advanced Materials, 2021, 33(27): 2100855.
[2]	邓龙征. 磷酸铁锂正极材料制备及其应用的研究[D]. 北京: 北京理工大学, 2014.
	DENG Longzheng. Study of synthesis and application on lithium iron phosphate cathode materials[D]. Beijing: Beijing Institute of Technology, 2014.
[3]	孙存思. 磷酸铁锂正极材料的改性研究[D]. 镇江: 江苏科技大学, 2021.
	SUN Cunsi. Research on modification of lithium iron phosphate cathode material[D]. Zhenjiang: Jiangsu University of Science and Technology, 2021.
[4]	WANG Shijie. Cobalt—Its recovery, recycling, and application[J]. JOM, 2006, 58(10): 47-50.
[5]	邓凡政, 石影, 陈岩. 用聚乙二醇-硫酸铵-铝试剂体系萃取分离铁(Ⅲ)、铝(Ⅲ)、铜(Ⅱ)、钴(Ⅱ)、镉(Ⅱ)、锰(Ⅱ)、镍(Ⅱ)[J]. 分析化学, 1997, 25(2): 215-218.
	DENG Fanzheng, SHI Ying, CHEN Yan. Extraction separation of iron(Ⅲ), aluminum(Ⅲ), copper(Ⅱ), cobalt(Ⅱ), cadmium(Ⅱ), manganese(Ⅱ) and nickel(Ⅱ) using polyethylene glycol-ammonium sulfate-aluminon system[J]. Chinese Journal of Analytical Chemistry, 1997, 25(2): 215-218.
[6]	TEKE Mustafa, MERCIMEK Bedrettin, ÖZLER M. Ali,et al. Selective extraction of iron(Ⅲ) from aqueous nitrate solution in the presence of cobalt(Ⅱ), copper(Ⅱ) and nickel(Ⅱ) ions using bis(delta2-2-imidazolinyl)-5,5′-dioxime[J]. Analytical Sciences, 20(5): 853-856.
[7]	周学玺, 杜晓宁, 朱屯. 叔胺萃取分离钴(Ⅱ)、铁(Ⅱ)[J]. 过程工程学报, 2001, 1(4): 360-364.
	ZHOU Xuexi, DU Xiaoning, ZHU Tun. Solvent extractive separation of cobalt(Ⅱ) and iron(Ⅱ) with tertiary amine[J]. The Chinese Journal of Process Engineering, 2001, 1(4): 360-364.
[8]	赵永志, 帅国胜, 马莹. Aliquat336络合萃取NdFeB盐酸浸出液中铁、钴的研究[J]. 中国稀土学报, 2022, 40(3): 450-458.
	ZHAO Yongzhi, SHUAI Guosheng, MA Ying. Complex extraction of iron and cobalt with Aliquat336 in NdFeB hydrochloric acid leaching solution[J]. Journal of the Chinese Society of Rare Earths, 2022, 40(3): 450-458.
[9]	MILEVSKII N A, ZINOV’EVA I V, ZAKHODYAEVA Yu A, et al. Separation of Li(Ⅰ), Co(Ⅱ), Ni(Ⅱ), Mn(Ⅱ), and Fe(Ⅲ) from hydrochloric acid solution using a menthol-based hydrophobic deep eutectic solvent[J]. Hydrometallurgy, 2022, 207: 105777.
[10]	周学玺, 汪焕庆, 夏云龙, 等. 用季铵盐萃取分离钴铁锰[J]. 中国有色金属学报, 2000, 10(5): 723-727.
	ZHOU Xuexi, WANG Huanqing, XIA Yunlong, et al. Solvent extractive separation of cobalt, iron and manganese with quaternary ammonium chloride[J]. The Chinese Journal of Nonferrous Metals, 2000, 10(5): 723-727.
[11]	王斌, 洪涛, 姜俊, 等. 一种高浓度钴铁浸出液的掺钴高压钴铁分离方法: CN112662871B[P]. 2022-07-08.
	WANG Bin, HONG Tao, JIANG Jun, et al. A high-pressure cobalt iron separation method with cobalt doping for high concentration cobalt iron leaching solution: CN112662871B[P]. 2022-07-08.
[12]	王艳, 周春山. 含钴废渣硫酸化焙砂浸出液中钴、铁、锰分离研究[J]. 化学世界, 2001, 42(6): 289-290.
	WANG Yan, ZHOU Chunshan. Study on the separation of cobalt, iron and manganese from the leach solution of sulphated calcined cobalt residue[J]. Huaxue Shijie (Chemical World), 2001, 42(6): 289-290.
[13]	李强. 氯盐体系中分离铁、钴、镍新方法的研究[J]. 有色金属, 1997(6): 22-24.
	LI Qiang. A new method for separating iron, cobalt, and nickel in chloride salt systems[J]. Nonferrous Metals, 1997(6): 22-24.
[14]	BHATTACHARJEE S, GUPTA K K, CHAKRAVARTY S, et al. Separation of iron, nickel, and cobalt from sulphated leach liquor of low nickel lateritic oxide ore[J]. Separation Science and Technology, 2005, 39(2): 413-429.
[15]	王宪, 徐鲁荣, 陈丽丹, 等. 海藻生物吸附金属离子技术的特点和功能[J]. 台湾海峡, 2003, 22(1): 120-124.
	WANG Xian, XU Lurong, CHEN Lidan, et al. Characteristics and function of macroalgae biosorption technology to metal ion[J]. Journal of Oceanography in Taiwan Strait, 2003, 22(1): 120-124.
[16]	陈胜文, 李洪, 刘利, 等. 磷酸铁的制备工艺及应用展望[J]. 化纤与纺织技术, 2021, 50(11): 37-39.
	CHEN Shengwen, LI Hong, LIU Li, et al. Preparation process and application prospects of iron phosphate[J]. Chemical Fiber & Textile Technology, 2021, 50(11): 37-39.
[17]	宋晨豪, 王蒙蒙, 吕耀康, 等. 磷酸铁材料的制备方法研究进展[J]. 盐湖研究, 2025, 33(2): 108-114.
	SONG Chenhao, WANG Mengmeng, Yaokang LYU, et al. Research progress in the preparation methods of Iron phosphate materials[J]. Journal of Salt Lake Research, 2025, 33(2): 108-114.
[18]	SONG Yuxuan, FU Zhongtian. Mini-review on the preparation of iron phosphate for batteries[J]. Energy & Fuels, 2024, 38(19): 18194-18207.
[19]	毕胜. 2023年中国钛白粉行业的现状、未来及发展[J]. 钢铁钒钛, 2024, 45(1): 1-3.
	BI Sheng. Status, future and development of China’s titanium dioxide industry in 2023[J]. Iron Steel Vanadium Titanium, 2024, 45(1): 1-3.
[20]	陈朝华, 刘长河. 钛白粉生产及应用技术[M]. 北京: 化学工业出版社, 2006.
	CHEN Chaohua, LIU Changhe. Titanium dioxide production and application technology[M]. Beijing: Chemical Industry Press, 2006.
[21]	GUO Ju, FENG Yulong, MO Xinliang, et al. Preparation of LiFePO₄ using iron(Ⅱ) sulfate as product from titanium dioxide slag purification process and its electrochemical properties[J]. International Journal of Electrochemical Science, 2021, 16(11): 211141.
[22]	孟素芬. 利用钛白副产硫酸亚铁制备电池级磷酸铁的工艺研究[J]. 广东化工, 2019, 46(19): 1-2.
	MENG Sufen. The study on preparation of battery grade iron phosphate with titanium dioxide byproduct ferrous sulfate[J]. Guangdong Chemical Industry, 2019, 46(19): 1-2.
[23]	JIANG Yang, PENG Changhong, ZHOU Kanggen, et al. Recovery of iron from titanium white waste for the preparation of LiFePO₄ battery[J]. Journal of Cleaner Production, 2023, 415: 137817.
[24]	DENG Lin, MA Guangqiang, CHEN Qiyuan. Preparation of iron phosphate battery materials from industrial ferrous sulfate waste by liquid phase method[J]. Integrated Ferroelectrics, 2023, 234(1): 67-78.
[25]	王郎郎, 张韶, 费政富, 等. 黄磷生产中固废处置与资源化利用研究进展[J]. 材料导报, 2024, 38(22): 203-210.
	WANG Langlang, ZHANG Shao, FEI Zhengfu, et al. Research progress of solid waste disposal and resource utilization in yellow phosphorus production[J]. Materials Reports, 2024, 38(22): 203-210.
[26]	郭纪岐, 秦安瑞, 姚耀春, 等. 黄磷副产磷铁渣制备电池级磷酸铁[J]. 有色金属工程, 2023, 13(8): 9-15.
	GUO Jiqi, QIN Anrui, YAO Yaochun, et al. Preparation of battery grade iron phosphate from yellow phosphorus by-product iron phosphide slag[J]. Nonferrous Metals Engineering, 2023, 13(8): 9-15.
[27]	XU Yangming, WANG Lanbin, XIE Wenjie, et al. A novel way to prepare battery-grade FePO₄·2H₂O from copper slag and life cycle assessment[J]. Separation and Purification Technology, 2024, 339: 126686.
[28]	XU Xianqing, GUO Zhengqi, TIAN Xiaoman, et al. Synergetic recovery of rutile and preparation of iron phosphate from titanium-extraction tailings by a co-leaching process[J]. Separation and Purification Technology, 2024, 344: 127234.
[29]	马毅, 沈文喆, 袁梅梅, 等. 磷铁渣制备电池级纳米磷酸铁[J]. 化工进展, 2019, 38(11): 5015-5023.
	MA Yi, SHEN Wenzhe, YUAN Meimei, et al. Preparation of battery grade nano iron phosphate by using ferro-phosphorus as raw material[J]. Chemical Industry and Engineering Progress, 2019, 38(11): 5015-5023.
[30]	YU Biying, ZHAO Zihao, ZHANG Shuai, et al. Technological development pathway for a low-carbon primary aluminum industry in China[J]. Technological Forecasting and Social Change, 2021, 173: 121052.
[31]	ZHANG Xuekai, ZHOU Kanggen, ZENG Dewen, et al. Preparation of battery-grade FePO₄·2H₂O using the stripping solution generated from resource recycling of bauxite residue[J]. Bulletin of Environmental Contamination and Toxicology, 2022, 109(1): 86-94.
[32]	JIANG Tao, TU Yikang, SU Zijian, et al. A novel value-added utilization process for pyrite cinder: Selective recovery of Cu/Co and synthesis of iron phosphate[J]. Hydrometallurgy, 2020, 193: 105314.
[33]	XU Ziyang, TAN Boren, ZHU Boyuan, et al. Sustainable utilization of Fe(Ⅲ) isolated from laterite hydrochloric acid lixivium via ultrasonic-assisted precipitation to synthesize LiFePO₄/C for batteries[J]. Materials, 2024, 17(2): 342.

方法	浸出液类型	分离剂	分离目标	最佳分离率/%
萃取	Fe(Ⅲ)、Al(Ⅲ)、Cu(Ⅱ)、Co(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)、Ni(Ⅱ)标准溶液	聚乙二醇-硫酸铵-铝	Fe(Ⅲ)	>95^[5]
	Fe(Ⅲ)、Co(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)标准溶液	H₂L	Fe(Ⅲ)	99.98^[6]
	Fe(Ⅱ)、Co(Ⅱ)的氯化物体系	叔胺、HA3	Co(Ⅱ)	>98^[7]
	NdFeB盐酸浸出液	Aliquat336	Fe(Ⅲ) Co(Ⅱ)	Fe(Ⅲ) 97.66,Co(Ⅱ) 92.13^[8]
	Fe(Ⅲ)、Co(Ⅱ)、Mn(Ⅱ)、Ni(Ⅱ)、Li(Ⅰ)的标准溶液	HDES	Fe(Ⅲ)	约99^[9]
	Fe(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)的氯化物体系	季铵氯化物、HB	Co(Ⅱ)	>98^[10]
沉淀	Fe(Ⅱ)、Co(Ⅱ)的硫酸浸出液	含钴化合物	Fe(Ⅱ)	95.40^[11]
	Fe(Ⅲ)、Co(Ⅱ)、Mn(Ⅱ)的硫酸浸出液	硫酸铵、过硫酸铵	Fe(Ⅲ)	99.90^[12]
	高铁、低镍钴的氯化介质溶液	铁粉、硫化钠和硫粉	Co(Ⅱ) Ni(Ⅱ)	≥98^[13]
	Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)的硫酸浸出液	碳酸钙	Fe(Ⅲ)	>80^[14]
其他理论方法：膜分离法、电化学分离法、生物吸附法等

方法	浸出液类型	分离剂	分离目标	最佳分离率/%
萃取	Fe(Ⅲ)、Al(Ⅲ)、Cu(Ⅱ)、Co(Ⅱ)、Cd(Ⅱ)、Mn(Ⅱ)、Ni(Ⅱ)标准溶液	聚乙二醇-硫酸铵-铝	Fe(Ⅲ)	>95^[5]
	Fe(Ⅲ)、Co(Ⅱ)、Cu(Ⅱ)、Ni(Ⅱ)标准溶液	H₂L	Fe(Ⅲ)	99.98^[6]
	Fe(Ⅱ)、Co(Ⅱ)的氯化物体系	叔胺、HA3	Co(Ⅱ)	>98^[7]
	NdFeB盐酸浸出液	Aliquat336	Fe(Ⅲ) Co(Ⅱ)	Fe(Ⅲ) 97.66,Co(Ⅱ) 92.13^[8]
	Fe(Ⅲ)、Co(Ⅱ)、Mn(Ⅱ)、Ni(Ⅱ)、Li(Ⅰ)的标准溶液	HDES	Fe(Ⅲ)	约99^[9]
	Fe(Ⅱ)、Co(Ⅱ)、Mn(Ⅱ)的氯化物体系	季铵氯化物、HB	Co(Ⅱ)	>98^[10]
沉淀	Fe(Ⅱ)、Co(Ⅱ)的硫酸浸出液	含钴化合物	Fe(Ⅱ)	95.40^[11]
	Fe(Ⅲ)、Co(Ⅱ)、Mn(Ⅱ)的硫酸浸出液	硫酸铵、过硫酸铵	Fe(Ⅲ)	99.90^[12]
	高铁、低镍钴的氯化介质溶液	铁粉、硫化钠和硫粉	Co(Ⅱ) Ni(Ⅱ)	≥98^[13]
	Fe(Ⅲ)、Co(Ⅱ)、Ni(Ⅱ)的硫酸浸出液	碳酸钙	Fe(Ⅲ)	>80^[14]
其他理论方法：膜分离法、电化学分离法、生物吸附法等