黏土型锂矿中锂的赋存形态与分布规律研究

doi:10.3964/j.issn.1000-0593(2025)04-1137-06

摘要
参考文献
相关文章 (0)

全文: PDF (10401 KB)
输出: BibTeX | EndNote (RIS)

摘要：黏土型锂矿作为重要的战略锂资源，因其广泛分布、丰富储量和易于开采而备受关注。锂在矿石中的赋存形式和分布规律尚不明确，阻碍了传统火法或湿法工艺的大规模提锂。通过逐级化学提取，结合矿物解离分析（MLA）、X射线衍射（XRD）、电感耦合等离子发射光谱（ICP-OES）、扫描电子显微镜（SEM）和飞行时间二次离子质谱（TOF-SIMS）等，对云南某地区黏土型锂矿的锂分布规律和结合状态进行了详细分析。研究结果显示，矿石表面呈现颗粒状和片状结构，伴有微小的凹凸颗粒，结合XRD和MLA分析，原矿主要由一水硬铝石、勃姆石、锐钛矿和黏土矿物（如高岭石[Al₂Si₂O₅(OH)₄]和锂绿泥石[LiAl₅Si₃O₁₀(OH)₈）]组成，表明该矿物是一种铝土质碳酸盐黏土型锂矿。矿石中锂的总量为3 293 μg·g^-1，其中88.61%锂以结构稳定的硅酸盐/铝硅酸盐结合态存在，9.64%锂以碳酸盐/磷酸盐结合态存在，其余部分的锂以游离态、离子交换态和硫化物结合态存在。TOF-SIMS结果表明了锂与铝、硅、钾等元素在矿石中的分布重叠，证实锂以较为稳定的、不易被其他阳离子取代的结合态分布在黏土型矿相中。经过浓氢氟酸浸出后黏土矿相消失，进一步验证了锂主要分布于黏土型铝硅酸盐矿物中。该研究为黏土型锂矿中锂的赋存形态和分布规律提供了深入分析，为实现黏土型锂矿中锂的选择性高效提取提供了理论指导。

关键词：黏土型锂矿；逐级化学提取；矿物解离分析；综合利用

Abstract：Clay-type lithium ore, as an integral part of strategic lithium resources, has garnered attention due to its widespread distribution, abundant reserves, and ease of extraction. However, the uncertainty surrounding the occurrence forms and distribution patterns of lithium within ore presents challenges for large-scale development using traditional pyrometallurgical or hydrometallurgical processes. This study conducted a sequential chemical extraction of clay-type lithium ore from a specific region in Yunnan, China, coupled with characterization techniques including mineral liberation analysis (MLA), X-ray fluorescence spectroscopy (XRF), X-ray diffraction (XRD), inductively coupled plasma optical emission spectroscopy (ICP-OES), scanning electron microscopy (SEM), and time-of-flight secondary ion mass spectrometry (TOF-SIMS), to analyze in detail the distribution patterns and binding states of lithium. SEM images unveiled that the ore surface exhibits granular and lamellar structures, accompanied byminute granules and pores. XRD and MLA analyses indicate that the primary mineral components include diaspore, boehmite, anatase, and clay minerals such as kaolinite [Al₂Si₂O₅(OH)₄] and lithium chlorite [LiAl₅Si₃O₁₀(OH)₈], identifying the ore as a bauxitic carbonate-hosted clay-type lithium ore. The total lithium content in the ore is determined to be 3 293 μg·g^-1, with 88.61% of lithium existing in the form of silicate/aluminosilicate, with carbonate/phosphate-bound lithium comprising 9.64%, and the remaining part existing in free, ion-exchange, and sulfide-bound states. TOF-SIMS results further confirmed the overlapping distribution of lithium with aluminum, silicon, potassium, and other elements within the ore, predominantly existing in stable, less substitutable states within clay-type mineral phases. The disappearance of clay mineral phases following concentrated hydrofluoric acid leaching further validates that lithium is predominantly distributed within clay-type aluminosilicate minerals. This study provides an in-depth analysis of lithium occurrence forms and distribution patterns in clay-type lithium ore, offering theoretical guidance for achieving selective and efficient lithium extraction from clay-type lithium ore.

Key words：Clay-type lithium ore; Sequential chemical extraction; Mineral liberation analysis; Comprehensive utilization

收稿日期: 2024-04-23 修订日期: 2024-09-13

中图分类号:

TF802.1

基金资助: 国家重点研发计划课题（2021YFC2903203）, 中国五矿集团有限公司科技专项计划（2022ZXA01）资助

通讯作者: 王晨晔 E-mail: cywang@ipe.ac.cn

作者简介: 厉岩，2000年生，中国科学院大学化学工程学院与中国科学院过程工程研究所硕士研究生 e-mail: liyan227@ipe.ac.cn

引用本文:

厉岩，胡文斌，王晨晔，李会泉，孙振华. 黏土型锂矿中锂的赋存形态与分布规律研究[J]. 光谱学与光谱分析, 2025, 45(04): 1137-1142.
LI Yan, HU Wen-bin, WANG Chen-ye, LI Hui-quan, SUN Zhen-hua. Study on the Occurrence Forms and Distribution Patterns of Lithium in Clay-Type Lithium Ore. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(04): 1137-1142.

链接本文:

https://www.gpxygpfx.com/CN/10.3964/j.issn.1000-0593(2025)04-1137-06 或 https://www.gpxygpfx.com/CN/Y2025/V45/I04/1137

[1] Turner J M. Science, 2022, 376(6600): 1361.
[2] Desaulty A M, Monfort Climent D, Lefebvre G, et al. Nature Communications, 2022, 13(1): 1.
[3] Kesler S E, Gruber P W, Medina P A, et al. Ore Geology Reviews, 2012, 48: 55.
[4] XU Lu, YANG Yao-hui, YAN Shi-qiang, et al(徐璐，杨耀辉，颜世强，等). Multipurpose Utilization of Mineral Resources(矿产综合利用), 2023, 4: 12.
[5] Xie R, Zhao Z, Tong X, et al. Particuology, 2023, 87: 46.
[6] WEN Han-jie, LUO Chong-guang, DU Sheng-jiang, et al(温汉捷，罗重光，杜胜江，等). Chinese Science Bulletin(科学通报), 2020, 65(1): 53.
[7] YU Feng, WANG Deng-hong, YU Yang, et al(于沨，王登红，于扬，等). Rock and Mineral Analysis(岩矿测试), 2019, 38(3): 354.
[8] AI Guang-hua, QIU Yong-hong(艾光华，邱永宏). Mining and Metallurgy(矿冶), 2023, 32(5): 122.
[9] Liu X, Wang Q, Feng Y, et al. Ore Geology Reviews, 2013, 55: 162.
[10] Gu H, Guo T, Wen H, et al. Minerals Engineering, 2020, 145: 106076.
[11] KONG Ling-an, LI Zheng-yao, ZHONG Zhen-yu, et al(孔令安，李正要，钟振宇，等). Nonferrous Metals Engineering(有色金属工程), 2022, 12(12): 66.
[12] SHI Gui-ming, ZHOU Yi-chao, CHEN Hai-jiao, et al(石贵明，周意超，陈海蛟，等). Metal Mine(金属矿山), 2023, 1: 199.
[13] Zhu L, Gu H, Wen H, et al. Hydrometallurgy, 2021, 206: 105759.
[14] CHENG Hong-fei, ZHOU Xuan-ping(程宏飞，周轩平). Metal Mine(金属矿山), 2024, 5: 28.
[15] ZHU Li, YANG Yong-qiong, GU Han-nian, et al(朱丽，杨永琼，顾汉念，等). Nonferrous Metals(Extractive Metallurgy)[有色金属(冶炼部分)], 2020, 11: 35.
[16] XIAO Bin, GONG Da-xing, TIAN En-yuan, et al(肖斌，龚大兴，田恩源，等). Geological Review(地质论评), 2024, 70(S1): 73.
[17] Tian C, Zhang J, Zhao Y, et al. International Journal of Coal Geology, 2014, 131: 162.
[18] Wei D, Han H, Zhu Z, et al. Energy, 2024, 292: 130633.
[19] CHENG Chen, SONG Yang, ZANG Jing-kun, et al(程晨，宋杨，臧静坤，等). Coalfield Geology and Exploration(煤田地质与勘探), 2022, 50(10): 44.
[20] HUANG Xing-zhong, WU Wen-fen, LI Zhan-bing, et al(黄形中，武文粉，李占兵，等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2022, 42(11): 3588.
[21] Hayashi S, Takahashi T, Kanehashi K, et al. Chemosphere, 2010, 80(8): 881.
[22] Yu W, Algeo T J, Yan J, et al. Earth-Science Reviews, 2019, 189: 159.
[23] XU Lin-gang, SUN Li, SUN Kai(徐林刚，孙莉，孙凯). Mineral Deposits(矿床地质), 2023, 42(1): 22.
[24] WANG Qing, LIU Tong, BAI Jing-ru, et al(王擎，柳桐，柏静儒，等). Technology and Development of Chemical Industry(化工技术与开发), 2010, 39(1): 25.
[25] ZHAO Yue, MA Wan-ping, YANG Yang, et al(赵越，马万平，杨洋，等). Acta Mineralogica Sinica(矿物学报), 2022, 42(2): 141.
[26] Zhang Y, Zhang J. Journal of Minerals, Metals, and Materials Society, 2019, 71(12): 4594.