磷酸锂渣制备电池级碳酸锂工艺研究

doi:10.19964/j.issn.1006-4990.2021-0292

Abstract

Abstract:

The slag containing lithium phosphate as the recovery product of low concentration lithium containing waste liquid is hardly used as the production raw material of lithium battery due to its high impurity content.In order to make full use of this kind of lithium phosphate slag to alleviate the demand pressure of lithium resources for the rapid development of new energy vehicle industry,according to the large solubility difference between lithium salt and calcium salt under weak acid conditions,acid and soluble calcium salt were added to lithium phosphate to directly realize separation of lithium and phosphorus from lithium phosphate slag under acidic conditions.The effect of acid addition amount,calcium addition amount,pH of conversion end point,conversion liquid-solid ratio and conversion time on lithium conversion efficiency was studied.It was found that the conversion rate of lithium could reach 96.8% when the volume mass ratio of acid addition amount to solid raw material was 1.04 mL/g,calcium addition amount was 0.9 times of the amount of phosphorus in lithium phosphate and the pH end point was 4.0.After pH adjustment,chemical impurity removal and ion exchange depth removal of the converted liq-uid,battery grade lithium carbonate could be prepared by strictly controlling the lithium concentration in the purified liquid,the filtration accuracy of sodium carbonate,the temperature of the reaction system.The product contained the main component of about 99.65%,with the impurity content up to the requirements of YS/T 582—2013.The comprehensive recovery of lithium was 93.4%.

Key words: lithium phosphate, conversion rate, recycling, battery-grade, lithium carbonate

CLC Number:

TQ131.11

GUO Chunping,ZHOU Youchi,WEN Xiaoqiang,LIU Wenwen,HONG Kan,HUANG Yetian. Study on preparation process of battery-grade lithium carbonate from slag containing lithium phosphate[J]. Inorganic Chemicals Industry, 2022, 54(3): 82-86.

Figures/Tables 10

Table 1

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Fig.6

Table 2

Table 3

Fig.7

References 16

[1]	王冬斌, 梁精龙, 邓孝纯, 等. 锂资源提取与回收及锂制备工艺研究现状[J]. 无机盐工业, 2020, 52(6):8-12.
[2]	谭博, 刘香环, 刘旭东, 等. 锂辉石浸出液提锂除杂规律研究[J]. 无机盐工业, 2021, 53(4):56-60.
[3]	ZHOU Z, FAN L, WEI Q, et al. Coupled reaction and solvent extrac-tion process to form Li₂CO₃:Mechanism and product characteriza-tion[J]. American Institute of Chemical Engineers Journal, 2014, 60(1):282-288. doi: 10.1002/aic.v60.1
[4]	YAN Q, LI X, WANG Z, et al. Extraction of lithium from lepidolite by sulfation roasting and water leaching[J]. International Journal of Mineral Processing, 2012, 110-111:1-5. doi: 10.1016/j.minpro.2012.03.005
[5]	熊攀, 赖先熔, 钟辉. 磷酸盐沉淀法用于高镁锂比盐湖卤水锂镁分离研究[J]. 化工矿物与加工, 2019, 48(3):58-60,64.
[6]	戴江洪, 王宏岩, 李平. 高纯碳酸锂制备研究进展[J]. 中国有色冶金, 2020(1):49-53.
[7]	杜国山, 唐建文, 羡鹏飞. 锂辉石制备碳酸锂工艺节能分析[J]. 有色冶金节能, 2020, 36(3):8-11.
[8]	南东东, 曾小毛, 刘剑叶, 等. 基于一步法对以锂云母为原料制备电池级碳酸锂的方法研究[J]. 冶金与材料, 2020, 40(5):41-42.
[9]	徐陈栋, 方舒杰, 潘超杰, 等. 新能源汽车产量的影响因素分析[J]. 汽车工程师, 2021(2):11-14.
[10]	柴文帅. 新冠疫情影响下的全球锂资源供需情况分析[J]. 新材料产业, 2020(4):46-50.
[11]	张亮, 杨卉芃, 柳林, 等. 全球提锂技术进展[J]. 矿产保护与利用, 2020, 40(5):24-31.
[12]	邢佳韵, 彭浩, 张艳飞, 等. 世界锂资源供需形势展望[J]. 资源科学, 2015, 37(5):988-997.
[13]	乔延超, 陈若葵, 王榆彬, 等. 一种以粗制磷酸锂制备碳酸锂的方法:中国, 109264748A[P]. 2019-01-25.
[14]	陈亚, 甘辉, 曹利涛, 等. 一种从含磷酸锂废渣中提取高纯碳酸锂或氢氧化锂的方法：中国,108285156A[P]. 2018-07-17.
[15]	魏述彬, 李振华, 员江平, 等. 一种由磷酸锂直接制备电池级碳酸锂的方法：中国,110127731A[P]. 2019-08-16.
[16]	郭春平, 文小强, 周有池, 等. 一种低品位磷酸锂酸性转化法制备电池用碳酸锂的方法：中国,108675323A[P]. 2018-10-19.

元素	质量分数/%	元素	质量分数/%
Li	15.65	Na	1.04
P	24.49	Al	<0.1
Ni	1.36	Fe	<0.005
Ca	0.004 6	O	50.68
Mg	0.001 3	水分	6.65

元素	除杂前后杂质质量浓度/（mg·L^-1）		元素	除杂前后杂质质量浓度/（mg·L^-1）
元素	除杂前	除杂后	元素	除杂前	除杂后
Ca	56.3	3.82	Fe	4.77	3.54
Mg	0.95	0.61	Al	<5	<5
Ni	37.6	4.13	P	7.16	0.38

碳酸锂		w（Li₂CO₃）/%	w（杂质）/%
碳酸锂		w（Li₂CO₃）/%	Na	Mg	Ca	K	Fe	Zn	Cu	Pb	Si	Al	Mn	Ni	SO₄^2-	Cl^-
行业标准		≥ 99.5	≤ 0.025	≤ 0.008	≤ 0.005	≤ 0.001	≤ 0.001	≤ 0.000 3	≤ 0.000 3	≤ 0.000 3	≤ 0.003	≤ 0.001	≤ 0.000 3	≤ 0.001	≤ 0.080	≤ 0.003
自制样品	1	99.65	0.016	0.002 7	0.004 1	<0.001	<0.001	<0.000 1	<0.000 1	<0.000 1	<0.001	<0.001	<0.000 1	<0.000 1	0.073 5	0.002 8
	2	99.58	0.021	0.002 4	0.004 0	<0.001	<0.001	<0.000 1	<0.000 1	<0.000 1	<0.001	<0.001	<0.000 1	<0.000 1	0.071 8	0.002 5
	3	99.71	0.012	0.002 6	0.003 9	<0.001	<0.001	<0.000 1	<0.000 1	<0.000 1	<0.001	<0.001	<0.000 1	<0.000 1	0.063 5	0.002 6

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Study on preparation process of battery-grade lithium carbonate from slag containing lithium phosphate

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 10

References 16

Related Articles 15

Metrics

Comments

Recommended 0

[1]	BAI Chaopeng, PENG Hui, CHEN Yuting, LUO Jiang, ZHANG Shengming. Research progress of recovery，purification and recycling of ruthenium from scrap ruthenium materials [J]. Inorganic Chemicals Industry, 2024, 56(4): 24-33.
[2]	LI Yaguang, HAN Dongzhan, QI Lijuan. Recent research on pretreatment of waste lithium-ion batteries and electrolyte recovery technology [J]. Inorganic Chemicals Industry, 2024, 56(2): 1-10.
[3]	WANG Hang, XU Chuan, YAN Xinxing, TU Mingjiang, CHEN Xin. Research progress of deep calcium removal process of battery-grade lithium carbonate [J]. Inorganic Chemicals Industry, 2023, 55(7): 18-24.
[4]	YU Hui, WANG Yubin, LIAO Zhejun, YANG Yunguang. Overview of recycling and utilization process of waste ternary lithium-ion power batteries [J]. Inorganic Chemicals Industry, 2023, 55(7): 32-37.
[5]	PANG Fei, XU Yingrui, CHAI Chunling, SHEN Jingjing, BAI Liguang, ZHAO Xiaodong. Overview on recycling of waste activated alumina in production of hydrogen peroxide by anthraquinone process [J]. Inorganic Chemicals Industry, 2023, 55(6): 1-7.
[6]	CHEN Yujue, ZHANG Liangjun, KUANG Huan, JIANG Manwen, XIAO Li. Study on roasting and recovery process of waste lithium iron phosphate powder with sodium bisulfate [J]. Inorganic Chemicals Industry, 2023, 55(3): 113-117.
[7]	TANG Di,WANG Junxiong,CHEN Wen,JI Guanjun,MA Jun,ZHOU Guangmin. Research status and prospect on direct regeneration of cathode materials from retired lithium-ion batteries [J]. Inorganic Chemicals Industry, 2023, 55(1): 15-25.
[8]	ZHOU Shiyu,HE Ting,FU Tongtong,GUO Zirui,GU Shuai,YU Jianguo. Life cycle and economic assessment of recycling spent lithium-ion batteries with hydrometallurgical process [J]. Inorganic Chemicals Industry, 2023, 55(1): 26-32.
[9]	LI Li,LI Yu,JIN Yan,QIU Jun,YANG Ying,ZHANG Yonghong,XIAO Fang,YU Jianguo. Key technology and application of lithium extraction from produced water in high sulfur and high hardness gas fields [J]. Inorganic Chemicals Industry, 2023, 55(1): 74-80.
[10]	LI Yan,WANG Yansong,CHENG Huaigang,KANG Jin,LI Enze,LÜ Hongzhou,LIU Qian. Rapid quality inspection of high-purity lithium carbonate based on determination of magnesium by water-soluble probe method [J]. Inorganic Chemicals Industry, 2023, 55(1): 87-92.
[11]	HUANG Hong,CHEN Shuona,HAN Weijiang,LIU Huiling,TAN Xiao. Recycling technology and contaminants analysis of waste lead paste [J]. Inorganic Chemicals Industry, 2022, 54(7): 35-41.
[12]	HAN Dong,ZHANG Qiang,ZHANG Min. Study on recovery and utilization process of alkali containing sodium silicate solution [J]. Inorganic Chemicals Industry, 2022, 54(2): 106-110.
[13]	HE Ting,KONG Jiao,CUI Jingzhi,CHEN Zhihao,FU Tongtong,GUO Zirui,GU Shuai,YU Jianguo. Study on leaching and thermodynamic of spent lithium-ion batteries with electrochemical reduction [J]. Inorganic Chemicals Industry, 2022, 54(12): 34-43.
[14]	Wen Yanshen,Chen Gang,Wang Weihong,Chen Changming,Gong Chuangzhou,Zhao Jie. Standardization and development trend of utilization of copper-containing etching waste solution on circuit boards [J]. Inorganic Chemicals Industry, 2021, 53(8): 27-30.
[15]	Wang Bin,Deng Xiaochuan,Shi Yifei,Dong Chaochao,Fan Faying,Zhu Chaoliang,Fan Jie. Online determination of the solubility of lithium carbonate in water and NaCl-KCl solution system [J]. Inorganic Chemicals Industry, 2021, 53(7): 73-79.