Based on the Analysis of Infrared Spectroscopy and XPS, the Mechanism of the Influence of Metal Ions on Fluorite Flotation Was Studied
LÜ Zhi-yan1, LIU Rong-xiang1*, CAO Zhao2, LI Jie3
1. Shanxi Institute of Technology, Shuozhou 036000, China
2. School of Mining and Coal, Inner Mongolia University of Science and Technology, Baotou 014010, China
3. School of Rare Earth Industry, Inner Mongolia University of Science & Technology, Baotou 014010, China
Abstract：As a national strategic mineral resource, the efficient recovery of fluorite (CaF2) faces major challenges: on the one hand, it is closely associated with calcareous minerals such as calcite; on the other hand, the interference of metal ions (Ca2+, Ba2+, Fe3+) in the flotation system leads to low selective separation efficiency. In this study, solution chemical calculation, zeta potential analysis, infrared spectroscopy (FT-IR), and X-ray photoelectron spectroscopy (XPS) analysis techniques were used to systematically reveal the microscopic mechanism of metal ions regulating the adsorption of octyl hydroxamic acid (OHA) on fluorite surface. It shows that the dominant components of metal cations change the surface zeta potential by compressing the double electron layer on the surface of fluorite under a certain range of pH values, resulting in a decrease in the negative zeta potential of the mineral surface, and the surface potential regulation of fluorite increases the adsorption capacity of OHA. FTIR results showed that OHA tube energy groups appeared in many places in the fluorite spectrum after OHA treatment, indicating that OHA was chemically adsorbed on the surface of fluorite. The absorption peaks of —CH3, —CH2—, CO, C—N, C—C—C, C—O, and N—O appeared in the spectra of fluorite treated with metal ions and OHA, and the absorption peaks were enhanced. XPS depth analysis revealed that the content of OHA adsorbed by fluorite after metal ions was significantly higher than that of OHA adsorbed by fluorite without metal ions. After the treatment of fluorite with metal ions and OHA, the binding energy offset of Ca(2p) increases. Ba and Fe can replace the surface Ca lattice site, and the intensity of the N(1s) peak increases, and a new bonding mode of Me—O—N is formed. Combined with zeta potential, FTIR and XPS analysis, the adsorption efficiency sequence of metal ions on fluorite and OHA is: Fe3+>Ba2+>(Ca2+/Ba3+/Fe3+)≥(Ca2+/Ba2+)≥(Ca2+/Fe3+)>Ca2+. The ternary interaction model of “metal ion-interface-reagent” established in this study provides theoretical support for the efficient flotation of fluorite under complex water quality conditions. The synergistic mechanism of lattice substitution-chemical adsorption found in this study points out the direction for the design of new flotation reagents.
吕志岩，刘荣祥，曹 钊，李 解. 基于红外光谱、XPS分析金属离子对萤石浮选影响的机理研究[J]. 光谱学与光谱分析, 2025, 45(11): 3246-3253.
LÜ Zhi-yan, LIU Rong-xiang, CAO Zhao, LI Jie. Based on the Analysis of Infrared Spectroscopy and XPS, the Mechanism of the Influence of Metal Ions on Fluorite Flotation Was Studied. SPECTROSCOPY AND SPECTRAL ANALYSIS, 2025, 45(11): 3246-3253.
[1] ZHANG Dan-xian, KANG Jian-hua, HUANG Hong-jun, et al(张丹仙, 亢建华, 黄红军, 等). The Chinese Journal of Process Engineering(过程工程学报), 2023, 23(1): 1.
[2] YANG Hua-ling, WANG Chang-fu, LIU Ming, et al(阳华玲, 王长福, 刘 铭, 等). Mining and Metallurgical Engineering(矿冶工程), 2022, 42(4): 67.
[3] LI Yu-biao, YANG Xu(李育彪, 杨 旭). Conservation and Utilization of Mineral Resources(矿产保护与利用), 2022, 42(2): 49.
[4] LIU Si-han, WANG Chun-lian, LIU Dian-he, et al(刘思晗, 王春连, 刘殿鹤, 等). Acta Petrologica et Mineralogica(岩石矿物学杂志), 2022, 41(5): 903.
[5] TANG Jia-yan, ZHAO Fang, HE Jia-ning, et al(汤家焰, 赵 芳, 何嘉宁, 等). Metal Mine(金属矿山), 2024, 482(12): 125.
[6] WU Wang-ni, TAO Li-ming, FAN Rui-hua, et al(吴望妮, 陶黎明, 范瑞华, 等). The Chinese Journal of Nonferrous Metals(中国有色金属学报), 2024, 34(2): 598.
[7] Han Wenjie, Zhu Yimin, Ge Wencheng, et al. Journal of Central South University, 2023, 30(3): 800.
[8] Jong Kwangsok, Paek Inchol, Kim Yonggwang, et al. Minerals Engineering, 2020, 146: 106017.
[9] Gao Zhiyong, Jiang Zheyi, Sun Wei, et al. Transactions of Nonferrous Metals Society of China, 2021, 31(7): 2081.
[10] SUN Wen-juan, HAN Hai-sheng, HU Yue-hua, et al(孙文娟, 韩海生, 胡岳华, 等). The Chinese Journal of Nonferrous Metals(中国有色金属学报), 2020, 30(4): 927.
[11] GAO Yue-sheng, GAO Zhi-yong, SUN Wei(高跃升, 高志勇, 孙 伟). The Chinese Journal of Nonferrous Metals(中国有色金属学报), 2017, 27(4): 859.
[12] NING Jiang-feng, LI Mao-lin, CUI Rui, et al(宁江峰, 李茂林, 崔 瑞, 等). Conservation and Utilization of Mineral Resources(矿产保护与利用), 2020, 40(6): 64.
[13] Liu Hang, Zhao Wenqing, Zhai Jihua, et al. Minerals, 2020, 10(6): 567.
[14] Pan Chen, Lu Xiaolong, Chai Xujian, et al. Colloids and Surfaces A: Physicochemical and Engineering Aspects, 2021, 612: 125964.
[15] LU Jia, GAO Hui-min, JIN Jun-xun(卢 佳, 高惠民, 金俊勋). Metal Mines(金属矿山), 2015, 464(2): 73.
[16] LIN Jia-wei, LI Jie, WU Jing-xuan, et al(林嘉威, 李 解, 武靖轩, 等). Spectroscopy and Spectral Analysis(光谱学与光谱分析), 2021, 41(4): 1281.
[17] Xie Haiyun, Jin Yanling, Zhang Pei, et al. Applied Surface Science, 2022, 579: 152129.
[18] WENG Shi-fu, XU Yi-zhuang(翁诗甫, 徐怡庄). Fourier Transform Infrared Spectrum Analysis(傅里叶变换红外光谱分析). Beijing: Chemical Industry Press(北京: 化学工业出版社), 2016. 4.
[19] SONG Ting-lu, ZOU Mei-shuai, LU De-feng(宋廷鲁, 邹美帅, 鲁德风). X-ray Photoelectron Spectroscopy Data Analysis(X射线光电子能谱数据分析). Beijing: Beijing Institute of Technology Press(北京: 北京理工大学出版社), 2022. 11.
