Application of IPE-23 extractant in the recovery of lithium from lithium-containing waste liquors

doi:10.16085/j.issn.1000-6613.2024-0784

Abstract

Abstract:

The further extraction of lithium ions from waste lithium-ion battery recycling solutions offers both economic and environmental benefits. β-diketone solvent extraction systems have garnered extensive attention due to their excellent lithium extraction capabilities. However, the limited variety of β-diketone extractants currently available results in certain selection constraints. This study conducted theoretical calculations of the molecular surface electrostatic potential of the extractant and the Gibbs free energy change of the lithium extraction reaction using Gaussian 16 and Multiwfn software. The results indicate that substituents such as —NO₂, —CF₃, and —CN can enhance lithium extraction performance by altering the electrostatic potential extrema of the β-diketone's van der Waals surface. Based on this theoretical foundation, a selective lithium extraction agent, IPE-23, was developed. The impact of operational factors such as extractant concentration, temperature, phase ratio, and base addition was investigated using lithium extraction efficiency, separation ratio, extraction phase separation, and the loss of extractant in the aqueous phase(measured by the chemical oxygen demand in the aqueous phase) as evaluation metrics. Through a process of three-stage countercurrent extraction, three-stage countercurrent washing, and CO₂ acidification stripping, the lithium extraction rate reached 97%, with a distribution ratio D_Li of 21.90 and a lithium-sodium separation factor of 423.85. The pH of the remaining liquid was 11.3, with a COD of 675.2mg/L, and the lithium concentration in the stripping solution reached 6.66g/L. This study provides technical reference and theoretical support for the efficient recycling and reuse of lithium resources from lithium-containing wastewater.

Key words: lithium-containing waste liquid, solvent extraction, separation, recovery, lithium extraction by wet method

摘要：

从废旧锂电池回收废液中进一步提取锂资源兼具经济和环境效益，β-双酮类溶剂萃取体系因其良好的萃锂性能得到了广泛的关注，但目前β-双酮类萃取剂的种类较少导致在选择上有一定的局限性。本研究通过Gaussian 16、Multiwfn软件进行了萃取剂分子表面静电势和萃锂反应吉布斯自由能变的理论计算，结果表明—NO₂、—CF₃、—CN取代基通过改变β-二酮分子范德华表面的静电势极值来提升萃锂性能，在此理论基础上开发出β-二酮类选择性提锂萃取剂IPE-23；以锂萃取率、分离比、萃取分相、萃取剂在水相中的溶损（以水相中的化学需氧量COD计）等衡量指标，研究了萃取剂浓度、温度、相比、加碱量等因素的影响，经过三级逆流萃取-三级逆流洗涤-CO₂酸化反萃工艺处理，锂的萃取率达到97%，分配比D_Li=21.90，锂钠分离系数为423.85，萃余液pH为11.3，COD为675.2mg/L，反萃液中锂浓度达到6.66g/L。本研究有望为废旧锂电回收废液中锂资源的高效循环回用提供技术参考与理论支撑。

关键词: 含锂废液, 溶剂萃取, 分离, 回收, 湿法提锂

CLC Number:

TF826.1

HE Fang, XU Gaojie, PEI Xiang, SUN Dezhi, NING Pengge, CAO Hongbin. Application of IPE-23 extractant in the recovery of lithium from lithium-containing waste liquors[J]. Chemical Industry and Engineering Progress, 2024, 43(S1): 627-639.

何方, 许高洁, 裴翔, 孙德智, 宁朋歌, 曹宏斌. IPE-23萃取剂在含锂废液中回收锂的应用[J]. 化工进展, 2024, 43(S1): 627-639.

Figures/Tables 14

References 27

1	YANG Sixie, ZHANG Fan, DING Huaiping, et al. Lithium metal extraction from seawater[J]. Joule, 2018, 2(9): 1648-1651.
2	KANAGASUNDARAM Thines, MURPHY Olivia, HAJI Maha N, et al. The recovery and separation of lithium by using solvent extraction methods[J]. Coordination Chemistry Reviews, 2024, 509: 215727.
3	吕峥, 宋佳丽, 孙峙, 等. 中国锂离子电池回收技术知识产权分析[J]. 清华大学学报(自然科学版), 2019, 59(7): 551-557.
	Zheng LYU, SONG Jiali, SUN Zhi, et al. Intellectual property analysis of lithium-ion battery recycling methods in China[J]. Journal of Tsinghua University (Science and Technology), 2019, 59(7): 551-557.
4	MROZIK Wojciech, RAJAEIFAR Mohammad ALI, HEIDRICH Oliver, et al. Environmental impacts, pollution sources and pathways of spent lithium-ion batteries[J]. Energy & Environmental Science, 2021, 14(12): 6099-6121.
5	FAN Ersha, LI Li, WANG Zhenpo, et al. Sustainable recycling technology for Li-ion batteries and beyond: Challenges and future prospects[J]. Chemical Reviews, 2020, 120(14): 7020-7063.
6	林娇, 刘春伟, 曹宏斌, 等. 基于高温化学转化的废旧锂离子电池资源化技术[J]. 化学进展, 2018, 30(9): 1445-1454.
	LIN Jiao, LIU Chunwei, CAO Hongbin, et al. Recovery of spent lithium ion batteries based on high temperature chemical conversion[J]. Progress in Chemistry, 2018, 30(9): 1445-1454.
7	宋佳丽, 孙峙, 高文芳, 等. 锂离子电池正极废料中有价元素的选择性回收及其动力学模型[J]. 过程工程学报, 2017, 17(4): 845-852.
	SONG Jiali, SUN Sun, GAO Wenfang, et al. Selective recovery and kinetics of valuable elements from waste lithium-ion battery cathodes[J]. The Chinese Journal of Process Engineering, 2017, 17(4): 845-852.
8	曹宏斌. 锂动力电池高效循环与污染控制[J]. 高科技与产业化, 2023, 29(6): 18-21.
	CAO Hongbin. Efficient cycling and pollution control of lithium power batteries[J]. High-Technology & Commercialization, 2023, 29(6): 18-21.
9	ZHENG Xiaohong, ZHU Zewen, LIN Xiao, et al. A mini-review on metal recycling from spent lithium ion batteries[J]. Engineering, 2018, 4(3): 361-370.
10	LI Yukun, Weiguang LYU, HUANG Hanlin, et al. Recycling of spent lithium-ion batteries in view of green chemistry[J]. Green Chemistry, 2021, 23(17): 6139-6171.
11	李丽娟, 彭小五, 时东, 等. 含锂卤水中锂资源高效利用与绿色分离的新型萃取体系[J]. 盐湖研究, 2019, 26(4): 1-10.
	LI Lijuan, PENG Xiaowu, SHI Dong, et al. Eco-friendly separation and effective applications of lithium resources from various brine with lithium: Their extractant and extraction system[J]. Journal of Salt Lake Research, 2019, 26(4): 1-10.
12	许庆仁. 从氯化镁饱和溶液中萃取锂的研究[J]. 有机化学, 1979(1): 13-33.
	XU Qingren. Study on extracting lithium from saturated solution of magnesium chloride[J]. Chinese Journal of Organic CHEMISTRY, 1979(1): 13-33.
13	张金才, 王敏, 戴静. 卤水提锂的萃取体系概述[J]. 盐湖研究, 2005, 13(1): 42-48, 54.
	ZHANG Jincai, WANG Min, DAI Jing. Summarization of the lithium extraction system[J]. Journal of Salt Lake Research, 2005, 13(1): 42-48, 54.
14	时东, 李晋峰, 张波, 等. N523-TBP-磺化煤油萃取体系从饱和氯化镁卤水中萃取锂的工艺研究[J]. 盐湖研究, 2013, 21(2): 52-57.
	SHI Dong, LI Jinfeng, ZHANG Bo, et al. Process study on N523-TBP-sulfonated kerosene extraction system for extraction of lithium from brine saturated by magnesium chloride[J]. Journal of Salt Lake Research, 2013, 21(2): 52-57.
15	时东, 李丽娟, 宋富根, 等. N523-TBP混合萃取体系从盐湖卤水中萃取锂的机理研究[J]. 盐湖研究, 2017, 25(1): 57-63.
	SHI Dong, LI Lijuan, SONG Fugen, et al. Mechanism study of extracting lithium from brine with N523-TBP mixed extraction system[J]. Journal of Salt Lake Research, 2017, 25(1): 57-63.
16	束玉珍, 吴继宗, 邓惟勤. 冠状化合物在锂同位素分离中的应用[J]. 核化学与放射化学, 2015, 37(1): 12-17.
	SHU Yuzhen, WU Jizong, DENG Weiqin. Application of crown compounds in lithium isotopes separation[J]. Journal of Nuclear and Radiochemistry, 2015, 37(1): 12-17.
17	王苏. 不同侧链冠醚-离子液体萃取分离锂同位素的研究[D]. 西宁: 中国科学院大学(中国科学院青海盐湖研究所), 2018.
	WANG Su. Study on extraction and separation of lithium isotopes from different side chain crown ether - ionic liquids[D]. Xining: Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, 2018.
18	石成龙. 离子液体体系用于盐湖卤水中提取锂的研究[D]. 西宁: 中国科学院大学(中国科学院青海盐湖研究所), 2017.
	SHI Chenglong. Study on the application of ionic liquid systems for extraction oflithium from salt lake brine[D]. Xining: Qinghai Institute of Salt Lakes, Chinese Academy of Sciences, 2017.
19	肖江, 贾永忠, 姚颖, 等. 溶剂萃取法分离锂同位素研究进展[J]. 盐湖研究, 2016, 24(3): 62-72.
	XIAO Jiang, JIA Yongzhong, YAO Ying, et al. A review of separation of lithium isotopes by solvent extraction[J]. Journal of Salt Lake Research, 2016, 24(3): 62-72.
20	ZHANG Licheng, LI Lijuan, SHI Dong, et al. Selective extraction of lithium from alkaline brine using HBTA-TOPO synergistic extraction system[J]. Separation and Purification Technology, 2017, 188: 167-173.
21	PRANOLO Yoko, ZHU Zhaowu, CHENG CHU yong. Separation of lithium from sodium in chloride solutions using SSX systems with LIX 54 and Cyanex 923[J]. Hydrometallurgy, 2015, 154: 33-39.
22	ISHIMORI Ken-ichiro, MORI Seiji, ITO Yuji, et al. Equilibrium and ab initio computational studies on the adduct formation of 1,3-diketonato-lithium(Ⅰ), -sodium(Ⅰ) and -potassium(Ⅰ) with 1,10-phenanthroline and its 2,9-dimethyl derivatives[J]. Talanta, 2009, 78(4/5): 1272-1279.
23	苏慧. 多组分协同溶剂萃取体系应用于高镁盐湖卤水提锂的研究[D]. 北京: 中国科学院大学(中国科学院过程工程研究所), 2021.
	SU Hui. Study on the lithium recovery from salt lake brines containing high megnesium concentration using muitiple component synergistic solvent extraction system[D]. Beijing: Institute of Process Engineering, Chinese Academy of Sciences, 2021.
24	赵晓乐, 梁渠, 蔡静. 二苯并-14-冠-4超声波合成及其用于锂镁分离的研究[J]. 化学研究与应用, 2016, 28(8): 1098-1102.
	ZHAO Xiaole, LIANG Qu, CAI Jing. Study on ultrasonic-aid synthetic method of dibenzo-14-crown-4 and the application in separating lithium and magnesium[J]. Chemical Research and Application, 2016, 28(8): 1098-1102.
25	王万航. 新型杂多酸类共萃剂用于盐湖卤水萃取提锂的应用基础研究[D]. 北京: 北京化工大学, 2022.
	WANG Wanhang. Application fundamental research on lithium extraction from salt lake brines with novel heteropoly acid co-extraction agent[D]. Beijing: Beijing University of Chemical Technology, 2022.
26	ZHANG Licheng, LI Lijuan, SHI Dong, et al. Recovery of lithium from alkaline brine by solvent extraction with β - d i k e t o n e [J]. Hydrometallurgy, 2018, 175: 35-42.
27	张旭堃, 张健, 苏慧, 等. 硫酸锂沉锂母液中锂的回收[J]. 稀有金属, 2022, 46(1): 67-77.
	ZHANG Xukun, ZHANG Jian, SU Hui, et al. Recovery of lithium from the mother solution of lithium precipitation in lithium ore processing[J]. Chinese Journal of Rare Metals, 2022, 46(1): 67-77.

参数	数值
pH	12.68
COD/mg·L^-1	70
盐度/g·L^-1	31.05
金属离子浓度/mg·L^-1
Li	6490
Na	12550
K	58
B	22
Si	10
Ca	8

参数	数值
pH	12.68
COD/mg·L^-1	70
盐度/g·L^-1	31.05
金属离子浓度/mg·L^-1
Li	6490
Na	12550
K	58
B	22
Si	10
Ca	8

R1取代基	ΔG /kcal·mol^-1	ΔG-ΔG_-H /kcal·mol^-1	vdW静电势极小值 /kcal·mol^-1	vdW静电势极大值 /kcal·mol^-1
—H	112.6575	0	-66.19	43.06
—OH	116.4849	3.8274	-42.05	60.23
—NO₂	107.5073	-5.1502	-43.07	56.57
—F	111.9443	-0.7132	-57.03	51.1
—CN	195.6406	82.9831	-45.3	44.09
—CF₃	108.7517	-3.9058	-38.03	50.08
—Ph	114.3678	1.7103	-47.09	44.32
—OCH₃	117.8343	5.1768	-45.05	39.65
—N(CH₃)₂	118.5974	5.9399	-59.32	44.9
—CH₃	115.0102	2.3527	-47.26	41.9
—CH₂CHCH₂	115.2835	2.6260	-49.17	43.41
—CH₂CH₃	115.6481	2.9906	-48.28	41.61
—C(CH₃)₃	115.3681	2.7106	-50.27	43.24

R1取代基	ΔG /kcal·mol^-1	ΔG-ΔG_-H /kcal·mol^-1	vdW静电势极小值 /kcal·mol^-1	vdW静电势极大值 /kcal·mol^-1
—H	112.6575	0	-66.19	43.06
—OH	116.4849	3.8274	-42.05	60.23
—NO₂	107.5073	-5.1502	-43.07	56.57
—F	111.9443	-0.7132	-57.03	51.1
—CN	195.6406	82.9831	-45.3	44.09
—CF₃	108.7517	-3.9058	-38.03	50.08
—Ph	114.3678	1.7103	-47.09	44.32
—OCH₃	117.8343	5.1768	-45.05	39.65
—N(CH₃)₂	118.5974	5.9399	-59.32	44.9
—CH₃	115.0102	2.3527	-47.26	41.9
—CH₂CHCH₂	115.2835	2.6260	-49.17	43.41
—CH₂CH₃	115.6481	2.9906	-48.28	41.61
—C(CH₃)₃	115.3681	2.7106	-50.27	43.24

R3取代基	ΔG /kcal·mol^-1	ΔG-ΔG_-H /kcal·mol^-1	vdW静电势极小值 /kcal·mol^-1	vdW静电势极大值 /kcal·mol^-1
—H	112.6575	0	-66.19	43.06
—OH	112.5267	-0.1308	-54.68	82.18
—NO₂	98.6403	-14.0172	-30.79	51.39
—F	113.9283	1.2708	-46.79	44.25
—CN	99.1364	-13.5211	-36.31	53.17
—CF₃	106.1881	-6.4694	-39.01	54.52
—Ph	111.7872	-0.8703	-46.4	43.59
—OCH₃	113.6880	1.0305	-53	35.08
—N(CH₃)₂	112.0872	-0.5703	-46.89	43.85
—CH₃	116.0881	3.4306	-42.61	42.23
—CH₂CHCH₂	111.9502	-0.7073	-63.42	42.08
—CH₂CH₃	112.7878	0.1303	-63.3	40.46
—C(CH₃)₃	115.5021	2.8446	-50.27	43.24