盐湖提锂萃取剂及萃取体系研究进展

doi:10.11962/1006-4990.2020-0372

Abstract

Abstract:

There are abundant lithium resources in China’s salt lakes.Solvent extraction is one of the most widely studied and in-depth methods at present.A large number of studies have shown that the molecular structure of extractants is the key factor to determine the extraction efficiency.The research progress of extractants and extraction systems for lithium ex-traction from salt lake brine in recent years was summarized,focusing on the research status of different types of extractants and extraction systems,such as alcohol+ketone,organophosphorus,quaternary ammonium salt-azo ion chelation-association,crownether and ionic liquid.The mechanism,characteristics and existing problems of various extractants in the process of extracting lithium were analyzed,and on this basis,the development direction of the solvent extraction method for extracting lithium from salt lake was prospected.Through this review,it can be concluded that all the five extractants have specific functional groups or structures which are complex with Li⁺,so lithium can be extracted from salt lake brine.The organic phosphorus extraction system has high selectivity for lithium,relatively stable chemical properties and low price,so it is the most promising extractant for industrialization.The design and synthesis of new efficient organic phosphorus extractants and the construction of efficient green extraction system have broad prospects.

Key words: salt lake lithium extraction, solvent extraction, extractants, extraction mechanism

CLC Number:

TQ131.11

Wei Lina,Kang Jin,Li Hu,Li Enze,Cheng Huaigang,Cheng Fangqin. Research progress of lithium extractants and extraction systems from salt lakes[J]. Inorganic Chemicals Industry, 2021, 53(5): 21-25.

Figures/Tables 7

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References 39

[1]	Chen S Q, Nan X J, Zhang N, et al. Solvent extraction process and extraction mechanism for lithium recovery from high Mg/Li-ratio brine[J]. Journal of Chemical Engineering of Japan, 2019,52(6):508-513. doi: 10.1252/jcej.17we230
[2]	Nguyen T H, Lee M S. A review on the separation of lithium ion from leach liquors of primary and secondary resources by solvent extrac-tion with commercial extractants[J]. Processes, 2018,6(5):55. doi: 10.3390/pr6050055
[3]	Zhou Z Y, Qin W, Liu Y, et al. Extraction equilibria of lithium with tributyl phosphate in kerosene and FeCl₃[J]. Journal of Chemical & Engineering Data, 2011,57(1):82-86. doi: 10.1021/je200803h
[4]	Sekimotot T, Nishihama S, Yoshizuka K. Extraction of lithium from salt lake brine with tributyl phosphate and an ionic liquid[J]. Japan Association of Solvent Extraction, 2018,25(2):117-123.
[5]	Shi D, Li L J, Li J F, et al. Extraction of lithium from salt lake brine using N523-TBP mixture system[J]. Journal of Salt Lake Research, 2019,27(2):95-110.
[6]	Liu G, Zhao Z W, Ghahreman A. Novel approaches for lithium extra-ction from salt-lake brines:A review[J]. Hydrometallurgy, 2019,187:81-100. doi: 10.1016/j.hydromet.2019.05.005
[7]	余疆江, 郑绵平, 伍倩. 富锂盐湖提锂工艺研究进展[J]. 化工进展, 2013,32(1):13-21.
[8]	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.
[9]	Wang X Q, Jing Y, Liu H, et al. Extraction of lithium from salt lake brines by bis[(trifluoromethyl)sulfonyl]imide-based ionic liqui-ds[J]. Chemical Physics Letters, 2018,707:8-12. doi: 10.1016/j.cplett.2018.07.030
[10]	宁占玉, 杨春梅, 曹兆江, 等. 青海盐湖锂资源开发现状及存在问题和对策分析[J]. 化工设计通讯, 2019,45(6):194-195.
[11]	Zhou Z, Fan J H, Liu X T, et al. Recovery of lithium from salt-lake brines using solvent extraction with TBP as extractant and FeCl₃ as co-extraction agent[J]. Hydrometallurgy, 2020,191.Doi: 10.1016/j.hydromet.2019.105244 doi: 10.1016/j.hydromet.2019.105244
[12]	张燕辉, 李丽娟, 李晋峰, 等. 磷酸三丁酯从盐湖卤水中萃取锂的机理研究[J]. 无机盐工业, 2012,44(3):12-15.
[13]	Zhang L C, Li L J, Shi D, et al. Selective extraction of lithium from alkaline brine using HBTA-TOPO synergistic extraction system[J]. Separation and Purification Technology, 2017,188:167-173. doi: 10.1016/j.seppur.2017.07.028
[14]	Zhang L C, Li L J, Shi D, et al. Recovery of lithium from alkaline brine by solvent extraction with β-diketone[J]. Hydrometallurgy, 2018,175:35-42. doi: 10.1016/j.hydromet.2017.10.029
[15]	Zhou Z Y, Qin W, Fei W Y, et al. A Study on stoichiometry of co-mplexes of tributyl phosphate and methyl isobutyl ketone with lithium in the presence of FeCl₃[J]. Chinese Journal of Chemical Engineering, 2012,20(1):36-39. doi: 10.1016/S1004-9541(12)60360-7
[16]	杨立新, 邬赛祥, 刘肖丽, 等. 共萃剂ClO₄^-作用下磷酸三丁酯分离盐湖卤水锂镁[J]. 高等学校化学学报, 2013,34(1):55-60.
[17]	朱华芳, 高洁, 郭亚飞, 等. 溶剂萃取法提锂的研究进展[J]. 广东微量元素科学, 2010,17(11):25-30.
[18]	李丽娟, 彭小五, 时东, 等. 含锂卤水中锂资源高效利用与绿色分离的新型萃取体系[J]. 盐湖研究, 2018,26(4):1-10.
[19]	张桂平, 秦炜, 谭元忠, 等. 二(2-乙基己基)磷酸(D2EHPA)萃取分离镁和锂[J]. 清华大学学报:自然科学版, 2010,50(3):430-433.
[20]	Ji L M, Hu Y H, Li L J, et al. Lithium extraction with a synergistic system of dioctyl phthalate and tributyl phosphate in kerosene and FeCl₃[J]. Hydrometallurgy, 2016,162:71-78. doi: 10.1016/j.hydromet.2016.02.018
[21]	Zhou Z Y, Qin W, Fei W Y. Extraction equilibria of lithium with tri-butyl phosphate in three diluents[J]. Journal of Chemical & Engin-eering Data, 2011,56(9):3518-3522.
[22]	Xiang W, Liang S K, Zhou Z Y, et al. Lithium recovery from salt lake brine by counter-current extraction using tributyl phosphate/FeCl₃ in methyl isobutyl ketone[J]. Hydrometallurgy, 2017,171:27-32. doi: 10.1016/j.hydromet.2017.04.007
[23]	贾旭宏, 李丽娟, 曾忠民, 等. 磷酸三丁酯萃取体系从盐湖卤水提取锂[J]. 无机盐工业, 2011,43(8):29-32.
[24]	李慧芳, 李丽娟, 时东, 等. 磷酸三丁酯从盐湖卤水中萃取锂的动力学研究[J]. 广州化工, 2015,43(5):68-71.
[25]	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.
[26]	Shi D, Cui B, Li L J, et al. Lithium extraction from low-grade salt lake brine with ultrahigh Mg/Li ratio using TBP-kerosene-FeCl₃ system[J]. Separation and Purification Technology, 2019,211:303-309. doi: 10.1016/j.seppur.2018.09.087
[27]	赵旭, 张琦, 武海虹, 等. 盐湖卤水提锂[J]. 化学进展, 2017,29(7):796-808. doi: 10.7536/PC170313 pmid: 38BADEC0-6959-4FB4-AE2D-E9CB875D8170
[28]	Ji L M, Li L J, Shi D, et al. Extraction equilibria of lithium with N,N-bis(2-ethylhexyl)-3-oxobutanamide and tributyl phosphate in kerosene and FeCl₃[J]. Hydrometallurgy, 2016,164:304-312. doi: 10.1016/j.hydromet.2016.06.022
[29]	时东, 李晋峰, 张波, 等. N523-TBP-磺化煤油萃取体系从饱和氯化镁卤水中萃取锂的工艺研究[J]. 盐湖研究, 2013,21(2):52-57.
[30]	Li H F, Li L J, Shi D, et al. Extraction kinetics of lithium ions by N,N-bis (2-ethylhexyl)acetamide from simulated brine using ri-sing single drop method[J]. Hydrometallurgy, 2016,160:1-5. doi: 10.1016/j.hydromet.2015.11.002
[31]	杨山虎. 单苯并-12-冠-4的合成及对锂离子选择性研究[D]. 成都:成都理工大学, 2012.
[32]	梁渠, 闫书一, 吴忠忠, 等. 冠醚聚氨酯泡塑的合成及其在锂镁分离中的应用[J]. 成都理工大学学报:自然科学版, 2009,36(3):326-332.
[33]	赵晓乐, 梁渠, 蔡静. 二苯并-14-冠-4超声波合成及其用于锂镁分离的研究[J]. 化学研究与应用, 2016,28(8):1098-1102.
[34]	束玉珍, 吴继宗, 邓惟勤, 等. 苯并-15-冠-5/离子液体体系液液萃取锂[J]. 核化学与放射化学, 2017,39(2):151-157.
[35]	Li E Z, Kang J, Ye P Y, et al. A prospective material for the highly selective extraction of lithium ions based on a photochromic cro-wned spirobenzopyran[J]. Journal of Material Chemistry B, 2019,7(6):903-907. doi: 10.1039/C8TB02906G
[36]	Shi C L, Duan D P, Jia Y Z, et al. A highly efficient solvent system containing ionic liquid in tributyl phosphate for lithium ion extrac-tion[J]. Journal of Molecular Liquids, 2014,200:191-195. doi: 10.1016/j.molliq.2014.10.004
[37]	Shi C L, Jia Y Z, Zhang C, et al. Extraction of lithium from salt lake brine using room temperature ionic liquid in tributyl phosphate[J]. Fusion Engineering and Design, 2015,90:1-6. doi: 10.1016/j.fusengdes.2014.09.021
[38]	Shi C L, Jing Y, Jia Y Z. Solvent extraction of lithium ions by tri-n-butyl phosphate using a room temperature ionic liquid[J]. Journal of Molecular Liquids, 2016,215:640-646. doi: 10.1016/j.molliq.2016.01.025
[39]	Shi C L, Jing Y, Xiao J, et al. Solvent extraction of lithium from aqueous solution using non-fluorinated functionalized ionic liquids as extraction agents[J]. Separation and Purification Technology, 2017,172:473-479. doi: 10.1016/j.seppur.2016.08.034

提锂萃取剂	典型代表
醇+酮类	丙醇、丁醇、苯甲酰三氟丙酮（HBTA）、甲基异丁基酮（MIBK）、环己酮
有机磷类	磷酸三丁酯（TBP）、三辛基氧化膦（TOPO）、二（2-乙基己基）磷酸（D2EHPA）
季胺盐-偶氮离子螯合-缔合类	N,N-二（1-甲基庚基）乙酰胺（N503）、N,N-二（2-乙基己基）乙酰胺（N523）、N,N-二（2-乙基己基）-3-丁酮乙酰胺（NB2EHOTA）
冠醚类	二苯并-14-冠-4（DB14C4）、苯并-15-冠-5（B15C5）
离子液体类	咪唑类六氟磷酸盐（[C_nmim][PF₆]）、咪唑类双（三氟甲基磺酰）酰亚胺[C_nmim][NTf₂]、四丁基铵双（2-乙基己基）-磷酸盐[N₄₄₄₄][DEHP]、双（2-乙基己基）-磷酸四辛基铵[N₈₈₈₈][DEHP]

National Inorganic Salts Information Center

Inorganic Acid-Base-Salt Committee of CIESC

Research progress of lithium extractants and extraction systems from salt lakes

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