中国盐湖卤水提锂产业化技术研究进展

doi:10.19964/j.issn.1006-4990.2022-0542

摘要/Abstract

摘要：

近年来,在新能源产业的推动下,新能源汽车和储能技术快速发展,带动锂盐消费飞速增长。目前,全球锂盐产业一片火热,正在跑马圈地和快速扩产中。中国拥有丰富的锂资源,尤其是盐湖卤水锂资源,而且通过多年技术攻关和产业化实践,中国盐湖卤水提锂技术逐渐成熟,新技术不断涌现,在全球锂盐行情火热的背景下,中国锂盐湖具备快速扩产的潜力。介绍了中国目前已经成功产业化的盐湖卤水提锂技术,分析各技术的优缺点,探讨正在研究中的有望实现产业化应用的提锂新技术,并研判了盐湖卤水提锂技术的发展方向,从绿色高效提锂工艺的角度出发,对于盐湖锂资源供应未来的发展趋势进行了分析和展望。通过研究,有望对中国盐湖提锂行业技术现状和技术发展方向有较清晰的认识,并对今后国内外锂盐湖的开发提供技术参考。

关键词: 盐湖卤水, 锂资源, 提锂技术, 产业化

Abstract:

In recent years,the rapid development of new energy vehicles and energy storage technology driven by the new energy industry,has led to rapid growth in lithium salt consumption.At present,the global lithium salt industry is booming,and in the process of staking and rapidly expanding production.China has abundant lithium resources,especially in salt lake brine.Through years of technical research and industrialization practice,the lithium extraction technology from salt lake brine of China is gradually matured,and new technologies are emerging.Under the background of the hot global lithium salt market,lithium salt lake of China has the potential for rapid expansion.The lithium extraction technologies from salt lake brine that had been successfully industrialized in China were introduced,the advantages and disadvantages of each technology were analyzed,the new lithium extraction technologies that were under research and expected to achieve industrial application were discussed,and the development direction of lithium extraction technology from salt lake brine was judged.From the perspective of green and efficient lithium extraction process,the future development trend of lithium resource supply from salt lake was analyzed and prospected.Through the research,it was expected to have a clearer understanding of the technical status and technical development direction of the domestic lithium extraction industry from salt lake,and to provide the technical reference for the development of lithium salt lakes at home and abroad in the future.

Key words: salt lake brine, lithium resources, lithium extraction technology, industrialization

中图分类号:

TQ131.11

乜贞,伍倩,丁涛,卜令忠,王云生,余疆江,侯献华. 中国盐湖卤水提锂产业化技术研究进展[J]. 无机盐工业, 2022, 54(10): 1-12.

NIE Zhen,WU Qian,DING Tao,BU Lingzhong,WANG Yunsheng,YU Jiangjiang,HOU Xianhua. Research progress on industrialization technology of lithium extraction from salt lake brine in China[J]. Inorganic Chemicals Industry, 2022, 54(10): 1-12.

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参考文献 40

[1]	孙景文.全球锂资源供需现状与展望[EB/OL].（2022-02-23）. https://doc.mbalib.com/view/5599a510205fa18303b9d90c342e38fb.html.
[2]	National Minerals Information Center.Mineral commodity summaries[R].Reston,Virginia: USGS-NMIC, 2022.
[3]	伍倩, 刘喜方, 郑绵平, 等. 我国盐湖锂资源开发现状、存在问题及对策[J].现代化工, 2017, 37(5): 1-5.
	WU Qian, LIU Xifang, ZHENG Mianping, et al.Present situation,existing problems and countermeasures of development of salt lake lithium resources in China[J].Modern Chemical Industry, 2017, 37(5): 1-5.
[4]	孙景文, 吴霜.全球盐湖提锂的变革: 技术为资源加持,唤醒“高原上的沉默宝藏”[EB/OL].（2022-07-04）. https://www.vzkoo.com/document/20220705b16ea1e41404fba4aef6928e.html.
[5]	马珍.盐湖锂资源高效分离提取技术研究进展[J].无机盐工业, 2022.Doi:10.19964/j.issn.1006-4990.2022-0293 . doi: 10.19964/j.issn.1006-4990.2022-0293
	MA Zhen.Research progress on high-efficient separation and extraction technology of lithium resources in salt lakes[J].Inorganic Chemicals Industry, 2022.Doi:10.19964/j.issn.1006-4990.2022-0293 . doi: 10.19964/j.issn.1006-4990.2022-0293
[6]	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.
[7]	葛涛, 徐亮, 孟金伟, 等. 盐湖卤水提锂工艺技术研究进展[J].有色金属工程, 2021, 11(2): 55-62.
	GE Tao, XU Liang, MENG Jinwei, et al.Research progress of lithium extraction technology from salt lake brine[J].Nonferrous Metals Engineering, 2021, 11(2): 55-62.
[8]	丁涛, 郑绵平, 张雪飞, 等. 盐湖卤水提锂技术及产业化发展[J].科技导报, 2020, 38(15): 16-23.
	DING Tao, ZHENG Mianping, ZHANG Xuefei, et al.Development of lithium extraction technology and industrialization in brines of salt lake[J].Science ＆ Technology Review, 2020, 38(15): 16-23.
[9]	苏慧, 朱兆武, 王丽娜, 等. 从盐湖卤水中提取与回收锂的技术进展及展望[J].材料导报, 2019, 33(13): 2119-2126.
	SU Hui, ZHU Zhaowu, WANG Lina, et al.Advances and prospects of extracting and recovering lithium from salt lake brines[J].Materials Reports, 2019, 33(13): 2119-2126.
[10]	许乃才, 史丹丹, 黎四霞, 等. 利用吸附技术提取盐湖卤水中锂的研究进展[J].材料导报, 2017, 31(17): 116-121.
	XU Naicai, SHI Dandan, LI Sixia, et al.Advances in extracting lithium from salt-lake brines by adsorption technique[J].Materials Review, 2017, 31(17): 116-121.
[11]	SHEIKO S S, SUN F C, RANDALL A, et al.Adsorption-induced scission of carbon-carbon bonds[J].Nature, 2006, 440(7081): 191-194.
[12]	何宏平, 郭龙皋, 谢先德, 等. 蒙脱石等粘土矿物对重金属离子吸附选择性的实验研究[J].矿物学报, 1999, 19(2): 231-235.
	HE Hongping, GUO Longgao, XIE Xiande, et al.Experimental studies on the selective adsorption of Cu²⁺,Pb²⁺,Zn²⁺,Cd²⁺,Cr³⁺ ions on montmorillonite,illite and kaolinite and the influence of medium conditions[J].Acta Mineralogica Sinica, 1999, 19(2): 231-235.
[13]	DING Tao, ZHENG Mianping, LIN Yuhan.Adsorption of Li（Ⅰ） ions through new high-performance electrospun PAN/Kaolin nano-fibers:A combined experimental and theoretical calculation[J].ACS Omega, 2022, 7(13): 11430-11439.
[14]	程鹏高, 黄传峰, 甘善甜, 等. 铝基锂吸附剂制备及其在泰和地下卤水提锂中的应用[J].无机盐工业, 2021, 53(6): 140-144.
	CHENG Penggao, HUANG Chuanfeng, GAN Shantian, et al.Preparation of aluminum-based lithium adsorbent and its application in extracting lithium from Taihe underground brine[J].Inorganic Chemicals Industry, 2021, 53(6): 140-144.
[15]	马培华, 邓小川, 温现民.从盐湖卤水中分离镁和浓缩锂的方法: 中国,1626443[P].2005-06-15.
[16]	郑绵平, 卜令忠, 邓月金, 等. 利用太阳池从碳酸盐型卤水中结晶析出碳酸锂的方法: 中国,1179885C[P].2004-12-15.
[17]	WU Qian, YU Jiangjiang, BU Lingzhong, et al.The application of an enhanced salinity-gradient solar pond with nucleation matrix in lithium extraction from Zabuye salt lake in Tibet[J].Solar Energy, 2022, 244: 104-114.
[18]	郭志远, 纪志永, 陈华艳, 等. 电化学提锂技术中电极材料和电极体系的研究进展[J].化工进展, 2020, 39(6): 2294-2303.
	GUO Zhiyuan, JI Zhiyong, CHEN Huayan, et al.Progress of electrode materials and electrode systems in electrochemical lithium extraction process[J].Chemical Industry and Engineering Progress, 2020, 39(6): 2294-2303.
[19]	ZHAO Zhongwei, SI Xiufen, LIU Xuheng, et al.Li extraction from high Mg/Li ratio brine with LiFePO₄/FePO₄ as electrode materials[J].Hydrometallurgy, 2013, 133: 75-83.
[20]	LIU Gui, ZHAO Zhongwei, GHAHREMAN A.Novel approaches for lithium extraction from salt-lake brines:A review[J].Hydrometallurgy, 2019, 187: 81-100.
[21]	石成龙, 景燕, 肖江, 等. 离子液体体系用于盐湖卤水提取锂[J].化工学报, 2015, 66(S1): 265-271.
	SHI Chenglong, JING Yan, XIAO Jiang, et al.Application of ionic liquids for extraction of lithium from salt lake brine[J].CIESC Journal, 2015, 66(S1): 265-271.
[22]	李慧芳, 李丽娟, 时东, 等. 磷酸三丁酯—磺化煤油从盐湖卤水中萃取锂的动力学研究[J].盐湖研究, 2015, 23(2): 51-57.
	LI Huifang, LI Lijuan, SHI Dong, et al.Extraction kinetics of lithium from the salt lake brine with tri-butyl-phosphate[J].Journal of Salt Lake Research, 2015, 23(2): 51-57.
[23]	石成龙, 宋桂秀, 秦亚茹, 等. 磷酸三丁酯/丁酸乙酯体系协同萃取提锂的研究[J].化学工程, 2020, 48(2): 16-19, 73.
	SHI Chenglong, SONG Guixiu, QIN Yaru, et al.Synergistic extrac-tion of lithium with tributyl phosphate/ethyl butyrate system[J].Chemical Engineering（China）, 2020, 48(2): 16-19, 73.
[24]	李锦丽, 朱华芳, 王敏, 等. 盐湖卤水协同萃取提锂及基础热力学性质[J].无机化学学报, 2014, 30(10): 2389-2393.
	LI Jinli, ZHU Huafang, WANG Min, et al.Co-extraction of lithium from salt lake and its thermodynamic properties[J].Chinese Journal of Inorganic Chemistry, 2014, 30(10): 2389-2393.
[25]	姬连敏, 李丽娟, 李晋峰, 等. 一种萃取锂的萃取有机相: 中国,104404269A[P].2015-03-11.
[26]	朱兆武, 张健, 王丽娜, 等. 从含锂卤水萃取后的负载有机相中反萃锂的方法: 中国,108893623A[P].2018-11-27.
[27]	朱兆武, 张健, 齐涛, 等. 一种从含锂卤水中提取锂的复合萃取体系及其萃取方法: 中国,107502741A[P].2017-12-22.
[28]	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 magnesium concentration using multiple component synergistic solvent extraction system[D].Beijing:Institute of Process Engineering,Chinese Academy of Sciences, 2021.
[29]	唐娜, 龚经款, 项军.铝基锂吸附剂制备及其吸附性能研究[J].无机盐工业, 2020, 52(8): 51-56.
	TANG Na, GONG Jingkuan, XIANG Jun.Preparation and adsorption properties of aluminum-based lithium adsorbent[J].InorganicChemicals Industry, 2020, 52(8): 51-56.
[30]	张瑞, 钟静, 林森, 等. 盐湖铝系提锂吸附剂成型条件的影响研究[J].化工学报, 2021, 72(12): 6291-6297.
	ZHANG Rui, ZHONG Jing, LIN Sen, et al.Study on the influence of granulation conditions on Li/Al-LDHs for lithium recovery from low grade brine[J].CIESC Journal, 2021, 72(12): 6291-6297.
[31]	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.
[32]	史丹丹, 许乃才.锰氧化物锂离子筛盐湖卤水提锂研究进展[J].无机盐工业, 2015, 47(11): 11-14, 19.
	SHI Dandan, XU Naicai.Progress in extracting lithium from salt lake brine by lithium ionic sieve of manganese oxides[J].Inorganic Chemicals Industry, 2015, 47(11): 11-14, 19.
[33]	孙淑英, 张钦辉, 于建国.尖晶石型LiMn₂O₄的水热合成及其锂吸附性能[J].过程工程学报, 2010, 10(1): 185-189.
	SUN Shuying, ZHANG Qinhui, YU Jianguo.Hydrothermal synthesis and lithium adsorption properties of LiMn₂O₄ spinel[J].The Chinese Journal of Process Engineering, 2010, 10(1): 185-189.
[34]	东方财富网.新型盐湖提锂技术破茧成蝶——揭秘新疆泰利信新型盐湖提锂技术[EB/OL].（2022-05-04）.https://caifuhao.eastmoney.com/news/20220504075507240859010.
[35]	柏春, 郭敏, 张慧芳, 等. 离子筛型锂吸附剂吸附法从盐湖卤水/海水中提锂的研究进展[J].化工进展, 2017, 36(3): 802-809.
	BAI Chun, GUO Min, ZHANG Huifang, et al.The research progress of extracting lithium from brine by lithium ion sieve[J].Che-mical Industry and Engineering Progress, 2017, 36(3): 802-809.
[36]	漆贵财, 海春喜, 周园.锰氧化物锂离子筛型吸附剂提锂进展[J].功能材料, 2018, 49(11): 11023-11032.
	QI Guicai, Chunxi HAI, ZHOU Yuan.Progress of extracting lithi-um by manganese oxide ion-sieve adsorbent[J].Journal of Functional Materials, 2018, 49(11): 11023-11032.
[37]	石西昌, 尹世豪, 唐天罡, 等. 锰钛系复合锂离子筛的制备及其吸附性能研究[J].材料导报, 2014, 28(8): 13-16, 27.
	SHI Xichang, YIN Shihao, TANG Tiangang, et al.Preparation of manganese titanium composite lithium ion-sieve and research on absorptive property[J].Materials Review, 2014, 28(8): 13-16, 27.
[38]	颜辉, 钟辉, 陈念.新型锂吸附剂的制备研究[J].无机盐工业, 2014, 46(2): 38-40.
	YAN Hui, ZHONG Hui, CHEN Nian.Preparation of new lithium adsorbents[J].Inorganic Chemicals Industry, 2014, 46(2): 38-40.
[39]	康为清, 时历杰, 赵有璟, 等. 纳滤法用于盐湖卤水镁锂分离的初步实验[J].无机盐工业, 2014, 46(12): 22-24.
	KANG Weiqing, SHI Lijie, ZHAO Youjing, et al.Preliminary test of separation of Mg²⁺/Li⁺ in salt lake brine by nanofiltration[J].Inorganic Chemicals Industry, 2014, 46(12): 22-24.
[40]	计超, 张杰, 张志君, 等. DK纳滤膜对高镁锂比卤水的分离性能研究[J].膜科学与技术, 2014, 34(3): 79-85.
	JI Chao, ZHANG Jie, ZHANG Zhijun, et al.Separation properties of magnesium and lithium from brine with high Mg²⁺/Li⁺ ratio by DK nanofiltration membrane[J].Membrane Science and Technology, 2014, 34(3): 79-85.

盐湖	开发企业	产品	提锂技术	设计年产能	2021年产量
察尔汗盐湖	青海盐湖蓝科锂业股份有限公司	碳酸锂	吸附法	3	2.1
察尔汗盐湖	格尔木藏格锂业有限公司	碳酸锂	吸附法	1	1.0
东台吉乃尔盐湖	东台吉乃尔锂资源有限公司	电池级碳酸锂	离子膜电渗析法	1	0.3
东台吉乃尔盐湖	青海锂业有限公司	电池级碳酸锂	离子膜电渗析法	1	0.9
西台吉乃尔盐湖	青海中信国安锂业发展有限公司	电池级碳酸锂	煅烧法	1	0.4
西台吉乃尔盐湖	青海恒信融锂业科技有限公司	碳酸锂	纳滤膜法	2	—
一里坪盐湖	五矿盐湖有限公司	碳酸锂	耦合膜法	1	0.9
巴仑马海盐湖	青海锦泰锂业有限公司	氯化锂、碳酸锂	吸附法	0.56	0.1
大柴旦盐湖	青海柴达木兴华锂盐有限公司	氯化锂	萃取法萃取法	1	0.2
大柴旦盐湖	金昆仑锂业有限公司	金属锂	萃取法萃取法	0.15	—
合计				11.71	5.90

盐湖	所在位置	卤水类型	开发企业	开发进程	提锂技术	资源量
扎布耶	日喀则仲巴县	碳酸盐型	西藏日喀则扎布耶锂业高科技有限公司	开发（0.5万t/a碳酸锂）	太阳池法、纳滤膜法	211.71
麻米错	阿里改则县	硫酸钠亚型	西藏阿里麻米措矿业开发有限公司	中试研究	吸附法	250.11
拉果错	阿里改则县	硫酸钠亚型	西藏阿里拉果资源有限责任公司	中试研究	沉淀法	247.68
龙木错	阿里日土县	硫酸镁亚型	西藏国能矿业发展有限公司	产业化试验	吸附法	216.95
结则茶卡	阿里日土县	碳酸盐型	西藏国能矿业发展有限公司	产业化试验	纳滤膜法、萃取法	230.69
当雄错	那曲尼玛县	碳酸盐型	西藏旭升矿业开发有限公司	中试研究	吸附法	86.00
捌千错	阿里革吉县	硫酸钠亚型	金圆环保股份有限公司	产业化试验	电化学脱嵌法	18.60

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