溶剂极性响应型丁基-环四联吡啶提锂分子的合成及性能研究

doi:10.11949/0438-1157.20201711

摘要/Abstract

摘要：

盐湖卤水提锂已逐渐成为我国锂及锂产品的生产途径之一，而我国盐湖卤水高镁锂比的特点导致锂离子提取难度大。传统溶剂萃取提锂过程中需使用大量协萃剂和高浓度酸，产品纯度低、危险度高。设计合成了一种具有溶剂极性响应性分子结构“异构互变”的丁基-环四联吡啶提锂分子，实现极性条件下“络合”锂，非极性条件下“释放”锂。核磁共振氢谱和高分辨质谱证实了目标分子结构的准确性，通过对比Li⁺和Mg²⁺存在时目标分子的光谱性质表明丁基-环四联吡啶分子对锂离子具有较强的选择性。此外，支撑液膜的离子跨膜传输结果进一步表明，丁基-环四联吡啶分子在不同极性溶剂条件下可以实现对锂离子的高选择性提取。

关键词: 溶剂极性, 环四联吡啶, 提锂分子, 合成, 传递, 膜

Abstract:

The extraction of lithium from salt lake brine has gradually become one of the crucial ways for the production of lithium and lithium related products in China. However, the high magnesium-to-lithium ratio of salt lake brines in China makes it difficult to extract lithium ions. Traditional solvent extraction processing of lithium from salt lake brine always requires a lot of co-extract and high concentration of acid, resulting in low product purity and high risk. A kind of butyl-cyclic tetrapyridine molecules for lithium extraction with solvent polar responsive molecular structure “isomerism” was designed and synthesized to realize “lithium-complexing” under polar conditions and “lithium-releasing” under non-polar conditions. The ¹H NMR and high resolution mass spectrometry were used to characterize the molecular structure of the target molecule. By comparing the spectral properties of the target molecule in the presence of Li⁺ and Mg²⁺, it is shown that the butyl-cyclotetrapyridine molecule has a strong selectivity to lithium ions. In addition, the results of ion transport across the supporting liquid membrane further indicate that butyl-cyclotetrapyridine molecules can achieve high selective extraction of lithium ions under different polar solvent conditions.

Key words: solvent polarity, cyclic tetrapyridine, molecule for lithium extraction, synthesis, transport, membrane

中图分类号:

TD 983

李恩泽, 叶培远, 王亚欣, 康锦, 阴彩霞, 程芳琴. 溶剂极性响应型丁基-环四联吡啶提锂分子的合成及性能研究[J]. 化工学报, 2021, 72(6): 3014-3021.

LI Enze, YE Peiyuan, WANG Yaxin, KANG Jin, YIN Caixia, CHENG Fangqin. Synthesis and properties of solvent polar responsive butyl-cyclic tetrapyridine molecule for lithium extraction[J]. CIESC Journal, 2021, 72(6): 3014-3021.

图/表 10

图1 6-丁基-3,6-二氰基-环四联吡啶分子的合成路线及不同溶剂极性下分子结构的可逆变化和络合锂离子示意图

Fig.1 The synthetic route of butyl tetrapyridine, reversible changes of molecular structure under different solvent polarity and schematic complexion of lithium ion

图2 离子的跨膜传输装置及过程

Fig.2 Schematic illustration of cation transmembrane transport devices and processing

图3 化合物C和化合物B的FT-IR谱图

Fig.3 FT-IR spectrum of compound C and compound B

图4 化合物C的1H NMR谱图

Fig.4 1H NMR spectrum of compound C

图5 化合物C的高分辨质谱图

Fig.5 HRMS spectrum of compound C

图6 化合物C的1,4-二氧六环溶液中逐渐加入微量纯水的紫外-可见光谱变化

Fig.6 The UV-Vis absorption spectral change of compound C by addition of water in 1,4-dioxane

图7 Li+和Mg2+存在时化合物C在1,4-二氧六环-水溶剂中的紫外-可见光谱图（实验中采用LiCl和MgCl2，Li+和Mg2+的浓度均为6×10-2 mol/L，1,4-二氧六环和水的体积比为1∶1）

Fig.7 The UV-Vis absorption spectra of compound C in the presence of Li+ or Mg2+ in 1,4-dioxan aqueous solution (LiCl and MgCl2 were used as salts, both the concentrations of Li+ and Mg2+ were 6×10-2 mol/L, the volume ratio of 1,4-dioxane to H2O was 1∶1)

图8 Li+或Mg2+存在时化合物C在1,4-二氧六环-水溶液中的高分辨质谱图（化合物C的浓度为1×10-6 mol/L，1,4-二氧六环和水的体积比为1∶1）

Fig.8 HRMS spectrum of compound C in the presence of Li+ or Mg2+ in 1,4-dioxan aqueous solution (the concentration of compound C was 1×10-6 mol/L, the volume ratio of 1,4-dioxane to H2O was 1∶1)

图9 Li+和Mg2+在跨膜传输过程中接收相阳离子浓度增加量随时间的变化

Fig.9 The increment of the receiving phase cation concentration varies against time during the transmembrane transmission of Li+ and Mg2+

表1 跨膜传输后Li+和Mg2+的分配系数和选择性分离因子

Table 1 The partition coefficient and selective separation factor of Li+ and Mg2+ after membrane transport

离子	接收相增加质量（m_接）/mg	原料相剩余质量（m_原）/mg	分配系数（K_d）	选择性分离因子（α）
Li⁺	3.553	63.946	0.056	56
Mg²⁺	0.069	67.430	0.001	56

参考文献 31

1	Liu X H, Chen X Y, He L H, et al. Study on extraction of lithium from salt lake brine by membrane electrolysis[J]. Desalination, 2015, 376: 35-40.
2	Swain B. Recovery and recycling of lithium: a review[J]. Separation and Purification Technology, 2017, 172: 388-403.
3	Li H F, Li L J, Peng X W, et al. Extraction kinetics of lithium from salt lake brine by N, N-bis(2-ethylhexyl) acetamide using Lewis cell[J]. Hydrometallurgy, 2018, 178: 84-87.
4	Shi D, Zhang L C, Peng X W, et al. Extraction of lithium from salt lake brine containing boron using multistage centrifuge extractors[J]. Desalination, 2018, 441: 44-51.
5	Song J F, Nghiem L D, Li X M, et al. Lithium extraction from Chinese salt-lake brines: opportunities, challenges, and future outlook[J]. Environmental Science: Water Research & Technology, 2017, 3(4): 593-597.
6	Song J F, Huang T, Qiu H B, et al. Recovery of lithium from salt lake brine of high Mg/Li ratio using Na[FeCl₄*2TBP] as extractant: thermodynamics, kinetics and processes[J]. Hydrometallurgy, 2017, 173: 63-70.
7	Sun Y, Wang Q, Wang Y H, et al. Recent advances in magnesium/lithium separation and lithium extraction technologies from salt lake brine[J]. Separation and Purification Technology, 2021, 256: 117807.
8	Xiang W, Liang S K, Zhou Z Y, et al. Extraction of lithium from salt lake brine containing borate anion and high concentration of magnesium[J]. Hydrometallurgy, 2016, 166: 9-15.
9	Wang Y, Liu H T, Fan J H, et al. Recovery of lithium ions from salt lake brine with a high magnesium/lithium ratio using heteropolyacid ionic liquid[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(3): 3062-3072.
10	赵旭, 张琦, 武海虹, 等. 盐湖卤水提锂[J]. 化学进展, 2017, 29(7): 796-808.
	Zhao X, Zhang Q, Wu H H, et al. Extraction of lithium from salt lake brine[J]. Progress in Chemistry, 2017, 29(7): 796-808.
11	Nie X Y, Sun S Y, Song X F, et al. Further investigation into lithium recovery from salt lake brines with different feed characteristics by electrodialysis[J]. Journal of Membrane Science, 2017, 530: 185-191.
12	Zhang C Y, Mu Y X, Zhang W, et al. PVC-based hybrid membranes containing metal-organic frameworks for Li⁺/Mg²⁺ separation[J]. Journal of Membrane Science, 2020, 596: 117724.
13	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, 2012, 57(1): 82-86.
14	Zhou Z Y, Liu H T, Fan J H, et al. Selective extraction of lithium ion from aqueous solution with sodium phosphomolybdate as a coextraction agent[J]. ACS Sustainable Chemistry & Engineering, 2019, 7(9): 8885-8892.
15	Masmoudi A, Zante G, Trébouet D, et al. Solvent extraction of lithium ions using benzoyltrifluoroacetone in new solvents[J]. Separation and Purification Technology, 2021, 255: 117653.
16	Yu X P, Fan X B, Guo Y F, et al. Recovery of lithium from underground brine by multistage centrifugal extraction using tri-isobutyl phosphate[J]. Separation and Purification Technology, 2019, 211: 790-798.
17	Zhou Z Y, 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: 105244.
18	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, 24.
	Zhang Y H, Li L J, Li J F, et al. Study on mechanism of extraction of lithium from salt lake brine by tributylphosphate[J]. Inorganic Chemicals Industry, 2012, 44(3): 12-15, 24.
19	Zhou Z Y, Qin W, Chu Y F, et al. Elucidation of the structures of tributyl phosphate/Li complexes in the presence of FeCl₃via UV-visible, Raman and IR spectroscopy and the method of continuous variation[J]. Chemical Engineering Science, 2013, 101: 577-585.
20	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.
21	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 crowned spirobenzopyran[J]. Journal of Materials Chemistry B, 2019, 7(6): 903-907.
22	Li E Z, Ye P Y, Kang J, et al. Facile fabrication of photochromic microspheres with multimodal hierarchically porous for selective extraction of lithium ions[J]. Materials Letters, 2020, 270: 127670.
23	Takano K, Furuhama A, Ogawa S, et al. A molecular orbital study on a tetra-aza macrocycle containing 2, 2'-bipyridines and its lithium complex[J]. Journal of the Chemical Society, Perkin Transactions 2, 1999, (6): 1063-1068.
24	Joliat E, Schnidrig S, Probst B, et al. Cobalt complexes of tetradentate, bipyridine-based macrocycles: their structures, properties and photocatalytic proton reduction[J]. Dalton Transactions, 2016, 45(4): 1737-1745.
25	Furuhama A, Takano K, Ogawa S, et al. Theoretical study of a conformational change occurring with lithium complexation to a tetra-aza macrocycle containing 2, 2'-bipyridines[J]. Bulletin of the Chemical Society of Japan, 2001, 74(7): 1241-1249.
26	Iyoda M, Yamakawa J, Rahman M J. Conjugated macrocycles: concepts and applications[J]. Angewandte Chemie International Edition, 2011, 50(45): 10522-10553.
27	Ogawa S, Narushima R, Arai Y. Aza macrocycle that selectively binds lithium ion with color change[J]. Journal of the American Chemical Society, 1984, 106(19): 5760-5762.
28	Ibrahim R, Tsuchiya S, Ogawa S. A color-switching molecule: specific properties of new tetraaza macrocycle zinc complex with a facile hydrogen atom[J]. Journal of the American Chemical Society, 2000, 122(49): 12174-12185.
29	Sakamoto H, Kimura K, Shono T. Lithium separation and enrichment by proton-driven cation transport through liquid membranes of lipophilic crown nitrophenols[J]. Analytical Chemistry, 1987, 59(11): 1513-1517.
30	Kocherginsky N M, Yang Q, Seelam L. Recent advances in supported liquid membrane technology[J]. Separation and Purification Technology, 2007, 53(2): 171-177.
31	Parhi P K, Das N N, Sarangi K. Extraction of cadmium from dilute solution using supported liquid membrane[J]. Journal of Hazardous Materials, 2009, 172(2/3): 773-779.

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