电池级碳酸锂深度除钙工艺研究进展

doi:10.19964/j.issn.1006-4990.2022-0557

Abstract

Abstract:

In recent years，with the development of electric vehicles，the demand for lithium products has been rising，and the quality of battery-grade lithium carbonate as an important basic lithium salt for the preparation of lithium battery cathode materials has been closely followed by various enterprises.In the preparation of lithium carbonate by ore roasting acid immersion and salt lake brine evaporation and concentration，the impurity calcium ions were difficult to remove due to their close properties to lithium ions，which seriously affects the purity of the product and reduces the safety performance of the battery，so it is necessary to conduct in-depth research on the calcium removal process.Based on the existing problems，the basic principles，applicable environment and research progress of deep calcium removal were expounded around the chemical precipitation method，the network method，the hydrogenation decomposition method，the ion exchange method and the electrolysis method.By combining with the process conditions and actual achievements in the preparation of lithium carbonate，and focusing on the application scenarios of different calcium removal methods adopted by current major lithium resource development and production enterprises，the advantages and disadvantages of each method were analyzed and summarized.By combining with cutting-edge development，the improvement means of the existing calcium removal process were discussed，in order to provide a reference for the actual production and research of lithium carbonate，deep calcium removal process.

Key words: lithium carbonate, deep calcium removal, calcium removal methods, research progress

CLC Number:

TQ131.11

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.

Figures/Tables 6

Fig.1

Fig.2

Fig.3

Fig.4

Fig.5

Table 1

References 40

1	赵春龙，孙峙，郑晓洪，等.碳酸锂的制备及其纯化过程的研究进展［J］.过程工程学报，2018，18（1）：20-28.
	ZHAO Chunlong， SUN Sun， ZHENG Xiaohong，et al.Research progress of lithium carbonate preparation and purification proce-
	ss［J］.The Chinese Journal of Process Engineering，2018，18（1）：20-28.
2	XU Xin， CHEN Yongmei， WAN Pingyu，et al.Extraction of lithium with functionalized lithium ion-sieves［J］.Progress in Materials Science，2016，84：276-313.
3	LIU Gui， ZHAO Zhongwei， GHAHREMAN A.Novel approaches for lithium extraction from salt-lake brines：A review［J］.Hydrometallurgy，2019，187：81-100.
4	张苏江，崔立伟，孔令湖，等.国内外锂矿资源及其分布概述［J］.有色金属工程，2020，10（10）：95-104.
	ZHANG Sujiang， CUI Liwei， KONG Linghu，et al.Summarize on the lithium mineral resources and their distribution at home and abroad［J］.Nonferrous Metals Engineering，2020，10（10）：95-104.
5	苏彤，郭敏，刘忠，等.全球锂资源综合评述［J］.盐湖研究，2019，27（3）：104-111.
	SU Tong， GUO Min， LIU Zhong，et al.Comprehensive review of global lithium resources［J］.Journal of Salt Lake Research，2019，27（3）：104-111.
6	任沁沁.我国新能源汽车保有量突破1000万辆［N］.新华每日电讯，2022-07-07（3）.
7	黄开成.电池级锂盐钙杂质的来源及深度除钙工艺研究［J］.中氮肥，2022（4）：74-76，80.
	HUANG Kaicheng.Study on the source of calcium impurities in battery-grade lithium salt and the deep calcium removal process［J］.M-Sized Nitrogenous Fertilizer Progress，2022（4）：74-76，80.
8	孔祥宇，张永生.锂资源：新能源革命的源动力［J］.人民论坛·学术前沿，2022（13）：76-81.
	KONG Xiangyu， ZHANG Yongsheng.Lithium resource：The motive force of new energy revolution［J］.Frontiers，2022（13）：76- 81.
9	YAN Qunxuan， LI Xinhai， WANG Zhixing，et al.Extraction of lithium from lepidolite by sulfation roasting and water leaching［J］.International Journal of Mineral Processing，2012，110/111：1-5.
10	LUONG V T， KANG Dongjun， AN J W，et al.Iron sulphate roasting for extraction of lithium from lepidolite［J］.Hydrometallurgy，2014，141：8-16.
11	张选旭.宜春锂云母采用硫酸盐法制取碳酸锂工艺净化除杂试验［J］.江西有色金属，1995（1）：45-47.
	ZHANG Xuanxu.Experiment on purification and impurity removal of lithium carbonate from Yichun lepidolite by sulfate met-
	hod［J］.Nonferrous Metals Science and Engineering，1995（1）：45-47.
12	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.
	TAN Bo， LIU Xianghuan， LIU Xudong，et al.Study on law of lithium extraction and impurity removal from spodumene leaching solution［J］.Inorganic Chemicals Industry，2021，53（4）：56- 60.
13	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.
	ZHANG Liang， YANG Huipeng， LIU Lin，et al.Global technology trends of lithium extraction［J］.Conservation and Utilization of Mineral Resources，2020，40（5）：24-31.
14	AN J W， KANG Dongjun， TRAN K T，et al.Recovery of lithium from uyuni salar brine［J］.Hydrometallurgy，2012，117/118：64- 70.
15	刘东帆，孙淑英，于建国.盐湖卤水提锂技术研究与发展［J］.化工学报，2018，69（1）：141-155.
	LIU Dongfan， SUN Shuying， YU Jianguo.Research and development on technique of lithium recovery from salt lake brine［J］.CIESC Journal，2018，69（1）：141-155.
16	李青林.柴达木盆地油田卤水提锂实验研究［J］.化工矿物与加工，2006（8）：16-17.
	LI Qinglin.Extraction of lithium from oil field brine in Chaidamu basin［J］.Industrial Minerals & Processing，2006（8）：16-17.
17	谈庆光，李银兰.察尔汗盐湖卤水制取碳酸锂除杂技术探讨［J］.科技创新与应用，2012（27）：15.
	TAN Qingguang， LI Yinlan.Discussion on impurity removal technology of preparing lithium carbonate from brine in Chaerhan salt lake［J］.Technology Innovation and Application，2012（27）： 15.
18	邓姝皓，杨子萱，杨佳逸，等.由扎布耶盐湖粗盐制备高纯碳酸锂新工艺研究［J］.无机盐工业，2016，48（4）：26-30.
	DENG Shuhao， YANG Zixuan， YANG Jiayi，et al.New process for preparation of high purity lithium carbonate from coarse salt in Zabuye salt lake［J］.Inorganic Chemicals Industry，2016，48（4）：26-30.
19	LINNEEN N， BHAVE R， WOERNER D.Purification of industrial grade lithium chloride for the recovery of high purity battery grade lithium carbonate［J］.Separation and Purification Technology，2019，214：168-173.
20	吴鉴，姚耀春，龙萍.循环氢化对电池级碳酸锂制备中钙镁去除的影响［J］.材料导报，2013，27（S1）：150-153.
	WU Jian， YAO Yaochun， LONG Ping.Effect of cyclic carbonation on the removal of calcium and magnesium in preparation of battery-grade lithium carbonate［J］.Materials Review，2013，27（S1）：150-153.
21	吴鉴，赵泉峰，龙萍，等.电池级碳酸锂制备过程中磷酸锂除钙的研究［J］.电源技术，2016，40（11）：2110-2111，2147.
	WU Jian， ZHAO Quanfeng， LONG Ping，et al.Research of removing calcium using lithium phosphate in preparation process of battery-grade lithium carbonate［J］.Chinese Journal of Power So-
	urces，2016，40（11）：2110-2111，2147.
22	周晓东，叶华，郭晴，等.碳化分解法提纯碳酸锂粗品［J］.有色金属（冶炼部分），2018（4）：42-45.
	ZHOU Xiaodong， YE Hua， GUO Qing，et al.Purification of lithi-
	um carbonate by carbonation-decomposition method［J］.Nonferrous Metals（Extractive Metallurgy），2018（4）：42-45.
23	许鑫，曾祖亮，廖文华，等.连续碳化——分解法制备高纯碳酸锂［Z］.新余：江西赣锋锂业股份有限公司，2018.
24	GRIKO Y V.Energetics of Ca²⁺-EDTA interactions：Calorimetric study［J］.Biophysical Chemistry，1999，79（2）：117-127.
25	周有池，王林生，刘帆，等.从含锂废渣中回收制备碳酸锂的工艺研究［J］.稀有金属与硬质合金，2017，45（4）：16-20，41.
	ZHOU Youchi， WANG Linsheng， LIU Fan，et al.Study on preparation of lithium carbonate from lithium-containing residue［J］.Rare Metals and Cemented Carbides，2017，45（4）：16-20，41.
26	马爱军，鲁兴武，张恩玉，等.电池级碳酸锂生产中钙镁硼的络合分离试验研究［J］.稀有金属与硬质合金，2015，43（1）：36-38.
	MA Aijun， LU Xingwu， ZHANG Enyu，et al.Experimental study on Ca-Mg-B complexation separation in the production of battery-grade lithium carbonate［J］.Rare Metals and Cemented Carbides，2015，43（1）：36-38.
27	张海军，苏怡兵，杨瑛.一种除去电池级碳酸锂中钙、镁、铁、钠、钾阳离子杂质的方法：中国，102398910A［P］.2014-07-16.
28	李鹏武，尹晓刚，杨锦瑜，等.电池级碳酸锂精制工艺技术研究［J］.无机盐工业，2018，50（6）：51-54，62.
	LI Pengwu， YIN Xiaogang， YANG Jinyu，et al.Study on purification technology of battery grade lithium carbonate［J］.Inorganic Chemicals Industry，2018，50（6）：51-54，62.
29	李鹏武，尹晓刚，程琥，等.氢化分解法制备电池级碳酸锂过程中钙、镁除杂工艺技术［J］.稀有金属与硬质合金，2018，46（4）：69-72，77.
	LI Pengwu， YIN Xiaogang， CHENG Hu，et al.Technology of calcium and magnesium removal during preparation of battery grade lithium carbonate by hydrogenation decomposition［J］.Rare Metals and Cemented Carbides，2018，46（4）：69-72，77.
30	李良彬，胡耐根，黄学武，等.一种利用氯化锂溶液制备电池级碳酸锂的方法：中国，101609888A［P］.2009-12-23.
31	耿慧，许颖，戴晓虎，等.离子交换树脂在污泥处理中的应用及展望［J］.中国环境科学，2022，42（11）：5220-5228.
	GENG Hui， XU Ying， DAI Xiaohu，et al.Overview and prospect of the application of ion exchange resin in treatment of sewage sludge［J］.China Environmental Science，2022，42（11）：5220-5228.
32	GRÁGEDA M， GONZÁLEZ A， GRÁGEDA M，et al.Purification of brines by chemical precipitation and ion-exchange processes for obtaining battery-grade lithium compounds［J］.International Journal of Energy Research，2018，42（7）：2386-2399.
33	王人杰，李明兴，李新义.基于氢化分解法的粗碳酸锂制备电池级碳酸锂工艺研究［J］.化工设计通讯，2020，46（7）：140- 142.
	WANG Renjie， LI Mingxing， LI Xinyi.Study on preparation of battery-grade lithium carbonate from crude lithium carbonate based on hydrogenation decomposition method［J］.Chemical Engineering Design Communications，2020，46（7）：140-142.
34	张燕，赵振中，马朝辉，等.碳化法制备电池级碳酸锂工艺优化研究［J］.无机盐工业，2020，52（3）：68-71.
	ZHANG Yan， ZHAO Zhenzhong， MA Zhaohui，et al.Optimization of process for preparation of battery grade lithium carbonate by carbonization［J］.Inorganic Chemicals Industry，2020，52（3）：68-71.
35	YI Wentao， YAN Chunyan， MA Peihua.Removal of calcium and magnesium from LiHCO₃ solutions for preparation of high-purity Li₂CO₃ by ion-exchange resin［J］.Desalination，2009，249（2）：729-735.
36	盛亮.一种从工业级碳酸锂提取超纯度碳酸锂的方法及装置：中国，107055577B［P］.2018-08-07.
37	余心亮，李靖，詹稳，等.4N级高纯碳酸锂［Z］.湖州：浙江天能新材料有限公司，2020.
38	DÍAZ NIETO C H， PALACIOS N A， VERBEECK K，et al.Membrane electrolysis for the removal of Mg²⁺ and Ca²⁺ from lithium rich brines［J］.Water Research，2019，154：117-124.
39	祝增虎，李法强，朱朝梁，等.电解法制备氢氧化锂的研究进展［J］.无机盐工业，2014，46（8）：6-9.
	ZHU Zenghu， LI Faqiang， ZHU Chaoliang，et al.Research progress on preparation of lithium hydroxide by electrolysis［J］.Inorganic Chemicals Industry，2014，46（8）：6-9.
40	TORRES W R， DÍAZ NIETO C H， PRÉVOTEAU A，et al.Lithium carbonate recovery from brines using membrane electrolysis［J］.Journal of Membrane Science，2020，615：118416.

除钙工艺	优点	缺点
化学沉淀法	工艺成熟、成本低、母液可循环、效率高	引入Na和K杂质、收率低、难以深度除钙、污染环境
氢化分解法	不引入杂质、工艺成熟	伴随Ca（HCO₃）₂进入产物、 CO₂利用率低、生产周期长
络合法	减少试剂用量、工艺简单、成本低	络合物伴随进入产物、影响晶型、产品发黑
离子交换法	深度除钙、循环使用、环保	循环寿命低、需反复活化、成本高、周期较长、引入Na离子
电解法	选择性高、综合利用率高	成本高、受配套基础设施影响、周期长、产生有害气体、杂质残留

[1]	ZHAO Runze, QIAN A′niu. Research progress of lithium recovery for spent lithium-ion batteries and preparation in battery-grade lithium carbonate [J]. Inorganic Chemicals Industry, 2024, 56(12): 70-78.
[2]	CHENG Chunchun, LI Yulong, ZHANG Zhiqiang, ZUO Shuo, QIN Donglan, ZHOU Na, WANG Jiaqin. Study on agglomeration phenomenon and regulation method of lithium carbonate crystal prepared from potassium carbonate [J]. Inorganic Chemicals Industry, 2024, 56(10): 47-54.
[3]	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.
[4]	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.
[5]	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.
[6]	Tan Bo,Liu Xianghuan,Liu Xudong,Yi Meigui. Study on law of lithium extraction and impurity removal from spodumene leaching solution [J]. Inorganic Chemicals Industry, 2021, 53(4): 56-60.
[7]	HU Yue,XU Lele,ZHOU Yanfang,XU Zhe,TIAN Shoushuai,LIAO Fan,YANG Xiaojun. Research progress on alkaline substance on surface of nickel-rich ternary cathode materials [J]. Inorganic Chemicals Industry, 2021, 53(12): 74-79.
[8]	Xu Xinfang,Zhou Xiaoping,Liu Zhengfeng,Li Lei,Chen Hu,Li Changming. Study on causticization and purification of salt lake lithium ore and recovery of fluorine-containing lithium carbonate [J]. Inorganic Chemicals Industry, 2020, 52(7): 62-65.
[9]	Yao Yong,Guo Rui. Research progress of metal element doped spinel type MgGa₂O₄ [J]. Inorganic Chemicals Industry, 2020, 52(4): 23-28.
[10]	Zhang Yan,Zhao Zhenzhong,Ma Zhaohui,Zhao Yancai,Chen Zhiyu,Ma Zhengqiang. Optimization of process for preparation of battery grade lithium carbonate by carbonization [J]. Inorganic Chemicals Industry, 2020, 52(3): 68-71.
[11]	Hu Min,Gong Hanzhang,Wu Huadong,Guo Jia,Zhang Linfeng,Zhou Yuxin. Preparation of battery-grade lithium carbonate from lithium-containing industrial waste [J]. Inorganic Chemicals Industry, 2020, 52(3): 80-84.
[12]	Liu Gousheng,Wang Linlin,Liu Yuelong. Preparation of lithium carbonate from medium-and low-grade lithium clay by ammonium sulfate process [J]. Inorganic Chemicals Industry, 2020, 52(10): 125-129.
[13]	Dong Xiongbo,Zhang Xiangwei,Liu Xiaorui,Zheng Shuilin. Progress and development trend of inorganic coated titanium powder [J]. Inorganic Chemicals Industry, 2020, 52(10): 30-36.
[14]	Chen Jie,Chen Xia. Crystallization process optimization for preparation of lithium carbonate [J]. Inorganic Chemicals Industry, 2019, 51(8): 29-32.
[15]	Liu Guowang,Zhou Xiaojun,Zhang Shichun,Yang Shangming,Dong Shoulong,Li Binshou. Recycle method of lithium extracted mother solution and phase diagram analysis [J]. Inorganic Chemicals Industry, 2019, 51(6): 38-40.

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Research progress of deep calcium removal process of battery-grade lithium carbonate

RichHTML

PDF (PC)

Knowledge

Abstract

Cite this article

share this article

Figures/Tables 6

References 40

Related Articles 15

Metrics

Comments

Recommended 0