疏水性离子液体-中性磷氧萃取剂萃取稀土元素的应用

摘要液液萃取广泛应用于稀土元素的分离回收，为了便于相的分离，通常采用疏水性萃取剂。基于液液萃取的特性，通过微波辅助法合成了疏水性离子液体1-丁基-3-甲基咪唑六氟磷酸盐（[BMIM][PF₆]）。分别探究了[BMIM][PF₆]搭配不同中性磷氧萃取剂对稀土元素中Nd³⁺和Pr³⁺的萃取研究。结果表明1-丁基-3-甲基咪唑六氟磷酸盐-三正辛基氧化磷（[BMIM][PF₆]-TOPO）为最适宜萃取体系。在最适宜萃取体系下，探究了时间、温度、pH值、V（A）/V（O）（水相稀土离子/有机相萃取体系）和萃取组分体积比对萃取效率的影响。结果表明：萃取时间为20 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_{[BMIM][PF₆]}：V_TOPO=1：1，体系对于Nd³⁺的萃取效果最佳，萃取率可达97.8%；萃取时间为25 min、温度为25℃、pH值=6.0、V（A）/V（O）=1.0、V_{[BMIM][PF₆]}：V_TOPO=1：1，体系对于Pr³⁺的萃取效果最佳，萃取率可达94.2%；萃取过程为放热反应，反应焓变分别为ΔH（Nd³⁺）=-38.43 kJ·mol^-1，ΔH（Pr³⁺）=-28.76 kJ·mol^-1。

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关键词：离子液体中性磷氧萃取剂稀土萃取体系焓变

Abstract： Liquid-Liquid extraction is widely used in the separation and recovery of rare earth elements. In order to facilitate phase separation, hydrophobic extracts are usually used. Based on the properties of liquid-liquid extraction, we use microwave-assisted method to synthesize hydrophobic ion liquid 1-butyl-3-methylimidazolium hexafluorophosphate ([BMIM][PF₆]). The extractions of Nd³⁺ and Pr³⁺ from rare earth elements by [BMIM][PF₆] with different neutral phosphorus oxygen extractants were studied. The results showed that 1-butyl-3-methylimidazolium hexafluorophosphate-trioctylphosphine oxide ([BMIM][PF₆]-TOPO) was the best extraction system. The effects of time, temperature, pH, V(A)/V(O) (rare earth ionic aqueous phase/organic phase of extraction system) and volume ratio of extracted components on extraction efficiency were studied in the best extraction system. The results showed that the extraction time was 20 min, the temperature was 25 ℃, the pH=6.0, V_{[BMIM][PF₆]}:V_TOPO=1:1, and the extraction efficiency was the best for Nd³⁺ compared with V(A)/V(O)=1. The extraction rate was 97.8%. The extraction time was 25 min, the temperature was 25 ℃, the pH=6.0, V_{[BMIM][PF₆]}:V_TOPO=1:1, compared with V(A)/V(O)=1, the extraction effect was the best for Pr³⁺. The extraction rate can reach 94.2%. The extraction process of Nd³⁺ and Pr³⁺ is exothermic reactions, and the reaction enthalpy change ΔH is -38.43 kJ·mol^-1 and -28.76 kJ·mol^-1, respectively.

Keywords： ionic liquid； neutral phosphorus oxygen extractants； rare earths； extraction system； enthalpy change

Received 2019-11-22;

Fund:国家自然科学基金（31660482，51162022）。

Corresponding Authors: 涂盛辉,E-mail:tshnc@163.com。 Email: tshnc@163.com

About author: 涂盛辉(1964-),男,主要研究方向包括催化氧化技术与纳米功能材料的化学、物理及性能研究,废水处理及综合利用技术、固废处理及循环利用利用技术、节能减排技术等。

引用本文:

涂盛辉, 张志文, 张超, 彭海龙, 杜军.疏水性离子液体-中性磷氧萃取剂萃取稀土元素的应用[J]. 化学工业与工程, 2020,37(5): 22-30

Tu Shenghui, Zhang Zhiwen, Zhang Chao, Peng Hailong, Du Jun.Application of Hydrophobic Ionic Liquid-Neutral Organophosphorus Extractant in Extraction of Rare Earth Elements[J]. Chemcial Industry and Engineering, 2020,37(5): 22-30

[1] 张逸. 新型功能化离子液体的制备与在CO₂吸收及稀土金属萃取方面的应用[D]. 武汉:武汉大学, 2015 Zhang Yi. Synthesis of novel functionalized ionic liquids and their application in CO₂ absorption and extraction of rare earth elements[D]. Wuhan:Wuhan University, 2015(in Chinese)
[2] 邓永春, 姜银举, 王永强. 高稀土氧化物渣系熔化温度的测定[J]. 过程工程学报, 2017, 17(6):1203-1207 Deng Yongchun, Jiang Yinju, Wang Yongqiang. Melting temperature test of slag rich in rare earth oxides[J]. The Chinese Journal of Process Engineering, 2017, 17(6):1203-1207(in Chinese)
[3] 吴迪, 钱贵霞. 中国稀土产业经济研究现状与发展趋势分析[J]. 稀土, 2014, 35(5):104-112 Wu Di, Qian Guixia. Reseatch situation and development trend of China rare earth industry[J]. Chinese Rare Earths, 2014, 35(5):104-112(in Chinese)
[4] Padhan E, Sarangi K. Recovery of Nd and Pr from NdFeB magnet leachates with bi-functional ionic liquids based on Aliquat 336 and Cyanex 272[J]. Hydrometallurgy, 2017, 167:134-140
[5] 卞玉洋. 从钕铁硼废料中回收稀土元素的新工艺研究[D]. 上海:上海大学, 2016 Bian Yuyang. Development of novel processes on the recovery of rare earth elements from NdFeB-based permanent magnet wastes[D]. Shanghai:Shanghai University, 2016(in Chinese)
[6] 崔佳娜, 王明. 稀土萃取分离皂化工艺研究进展[J]. 稀有金属与硬质合金, 2017, 45(2):1-5 Cui Jiana, Wang Ming. Research progress on saponification process of rare earth extraction separation[J]. Rare Metals and Cemented Carbides, 2017, 45(2):1-5(in Chinese)
[7] Chen J, Huang C, Wang Y, et al. Extraction behavior of bifunctional ionic liquid[N₁₈₈₈] [SOPAA] and TBP for rare earth elements[J]. Journal of Rare Earths, 2016, 34(12):1252-1259
[8] Wang W, Yang H, Cui H, et al. Application of bifunctional ionic liquid extractants[A336] [CA-12] and[A336] [CA-100] to the lanthanum extraction and separation from rare earths in the chloride medium[J]. Industrial & Engineering Chemistry Research, 2011, 50(12):7534-7541
[9] 肖海建, 蓝桥发, 黄金, 等. P₅₀₇-N₂₃₅体系稀土萃取分离试验研究[J]. 稀土, 2015, 36(6):32-38 Xiao Haijian, Lan Qiaofa, Huang Jin, et al. Research on extraction and separation of rare earth in P₅₀₇-N₂₃₅ system[J]. Chinese Rare Earths, 2015, 36(6):32-38(in Chinese)
[10] 邱玉珍, 王超, 徐海波, 等. P₅₀₇-盐酸体系中氯化铵对RE³⁺萃取分离的影响研究[J]. 稀土, 2017, 38(4):68-75 Qiu Yuzhen, Wang Chao, Xu Haibo, et al. Influences of ammonium chloride on extraction and separation of rare earth ions in P₅₀₇-hydrochloric acid system[J]. Chinese Rare Earths, 2017, 38(4):68-75(in Chinese)
[11] Zhang J, Li M, Yang M, et al. Magnetic retrieval of ionic liquids:Fast dispersive liquid-liquid microextraction for the determination of benzoylurea insecticides in environmental water samples[J]. Journal of Chromatography. A, 2012, 1254:23-29
[12] Stojanovic A, Keppler B K. Ionic liquids as extracting agents for heavy metals[J]. Separation Science and Technology, 2012, 47(2):189-203
[13] Jha M K, Kumari A, Panda, R et al. Review on hydrometallurgical recovery of rare earth metals[J]. Hydrometallurgy, 2016, 165:2-26
[14] Liao C, Li Z, Zeng Y, et al. Selective extraction and recovery of rare earth metals from waste fluorescent powder using alkaline roasting-leaching process[J]. Journal of Rare Earths, 2017, 35(10):1008-1013
[15] Huang C, Wang Y, Huang B, et al. The recovery of rare earth elements from coal combustion products by ionic liquids[J]. Minerals Engineering, 2019, doi:10.1016/j.mineng.2018.10.002
[16] Namboodiri V V, Varma R S. Solvent-Free sonochemical preparation of ionic liquids[J]. Organic Letters, 2002, 4(18):3161-3163
[17] Ramenskaya L M, Grishina E P. Intensification phenomenon of weak ionic interactions of 1-butyl-3-methylimidazolium hexafluorophosphate ionic liquid macro-dispersed in poly(methyl methacrylate):FTIR spectroscopic evidence[J]. Journal of Molecular Liquids, 2016, 218:133-137
[18] 徐光宪. 稀土的溶剂萃取[M]. 北京:科学出版社,1987 Xu Guangxian. Solvent extraction of rare earth[M]. Beijing:Science Press, 1987
[19] Batchu N K, Vander Hoogerstraete T, Banerjee D, et al. Non-aqueous solvent extraction of rare-earth nitrates from ethylene glycol to n-dodecane by Cyanex 923[J]. Separation and Purification Technology, 2016, doi:10.1016/j.seppur.2016.10.039
[20] Coll M T, Fortuny A, Kedari C S, et al. Studies on the extraction of Co(Ⅱ) and Ni(Ⅱ) from aqueous chloride solutions using Primene JMT-Cyanex272 ionic liquid extractant[J]. Hydrometallurgy, 2012, 125-126
[21] 陈莉莉, 邱祖民, 黄金莲, 等. PMBP缩2-ABT/TBP/离子液体双水相对稀土离子的协同萃取[J]. 稀土, 2011, 32(3):68-71 Chen Lili, Qiu Zumin, Huang Jinlian, et al. Synergistic extraction of lanthanide ions with PMBP-2-ABT and TBP in ionic liquid two-phase aqueous system[J]. Chinese Rare Earths, 2011, 32(3):68-71(in Chinese)
[22] Shen L, Chen J, Chen L, et al. Extraction of mid-heavy rare earth metal ions from sulphuric acid media by ionic liquid[A336] [P507] [J]. Hydrometallurgy, 2016, doi:10.1016/j.hydromet.2016.01.015
[23] Xiong Y,Kuang W, Zhao J, et al, Ionic liquid-based synergistic extraction of rare earths nitrates without diluent:Typical ion-association mechanism[J]. Separation and Purification Technology, 2017, 179:349-356