膜科学与技术

氨基苯并-15-冠-5接枝聚砜多孔膜填充膜色谱构建及锂同位素吸附分离性能研究

作者：刘丛丛¹， ²，裴洪昌¹， ²，刘耀龙¹， ³，严峰¹， ³，李建新¹， ²，崔振宇¹， ²，何本桥¹， ²

单位： 1天津工业大学分离膜与膜过程国家重点实验室/分离膜科学与技术国际联合研究中心，天津 300387；2天津工业大学材料科学与工程学院，天津 300387；3天津工业大学环境与化学化工学院，天津 300387

关键词： 4-氨基苯并-15冠-5接枝氯甲基化聚砜（PSf-g-AB15C5）；聚合物多孔膜；膜色谱；锂同位素分离；分离因子

出版年,卷(期):页码： 2018,38(4):14-22

摘要：

本文以4-氨基苯并-15-冠-5（AB15C5）和氯甲基化聚砜（CMPSf）为原料，通过亲核取代制备4-氨基苯并-15-冠-5接枝氯甲基化聚砜聚合物（PSf-g-AB15C5），并采用反应-控制浸没沉淀相转化法制备冠醚接枝聚砜多孔膜。以该膜为填充介质，采用层层叠加方法构筑出20层膜色谱柱，以淋洗色谱法探索其锂同位素吸附分离规律及膜色谱分离动力学。结果表明，相较于原始丰度，膜色谱一次淋洗对7Li和6Li丰度分别提升了0.06%和0.04%。7Li富集在色谱带前端，6Li富集在色谱带后端；膜色谱分离因子为1.014。冠醚接枝聚砜聚合物膜对锂离子的吸附过程更适合于准二级动力学方程，其吸附速率的大小由化学吸附所控制。

4-aminobenzo-15-crown-5 (AB15C5) as the membrane ligand and chloromethylated polysulfone (CMPSf) as bulk polymer were used to prepare polysulfone-graft-4’-aminobenzo-15-crown-5-ether (PSf-g-AB15C5) polymer via nucleophilic substitution, which was employed to fabricate PSf-g-AB15C5 porous membrane by immersion precipitation phase inversion method. 20 layers of porous membranes as media were packed by layer by layer in a chromatography column with 75 mm (height) ×24 mm (I.D). The elution chromatography method was used to study the adsorption kinetics and lithium isotopes separation performance by PSf-g-AB15C5 membrane chromatography. The results showed that the membrane chromatography process for lithium isotopes separation fitted pseudo-second-order kinetic model. That is to say, the lithium ions were adsorbed by PSf-g-AB15C5 porous membrane through the chemisorption. Compared with the original abundance, the abundance of 7Li and 6Li increased 0.06% and 0.04%, respectively. The heavier isotope, 7Li is enriched at the front boundary, whereas the lighter isotope, 6Li enriched at the rear boundary of the band. A single separation factor was up to 1.014. In a word, this study provides a new pave for a green and efficient separation of lithium isotope.

第一作者简介：刘丛丛（1992-），女，山东聊城人，硕士生，从事分离膜及锂同位素分离研究。 *通讯作者：李建新，E-mail：jxli@tjpu.edu.cn

参考文献：

[1] Nishizawa K, Watanabe H, Ishino S, et al. Lithium isotope separation by cryptand (2B, 2, 1) polymer[J]. J Nucl Sci Technol, 1984, 21(2): 133–138.
[2] 严峰, 袁威津, 李建新, 等. 冠醚化学交换分离锂同位素的影响因素分析及进展[J]. 化工进展, 2014, 33(s1): 47–56.
[3] Imai M. Isotope effects of lithium ions in electromigration in aqueous solutions[J]. J Inorg Nucl Chem, 1975, 37(1): 123–126.
[4] Arisawa T, Maruyama Y, Suzuki Y, et al. Lithium isotope separation by laser[J]. Appl Phys B, 1982, 28(1): 73–76.
[5] Benarie M M. Enrichment of the 6 Li-isotope in dekagram quantities by electromigration in molten lithium chloride[J]. J Inorg Nucl Chem, 1961, 18: 32–41.
[6] Nishizawa K, Takano T, Ikeda I, et al. Extractive separation of lithium isotopes by crown ethers[J]. Sep Sci Technol, 1988, 23(4–5): 333–345.
[7] Sun X L, Gu L, Qiu D, et al. The solid–liquid extraction separation of lithium isotopes by porous composite materials doped with ionic liquids and 2,2′-binaphthyldiyl-17-crown-5[J]. J Radioanal Nucl Chem, 2015, 303(3): 1–12.
[8] Kim D W, Kim H J, Jeon J S, et al. Separation of lithium isotopes by aminobenzo-15-crown-5 bonded merrifield resin[J]. J Radioanal Nucl Chem, 2000, 245(3): 571–574.
[9] Kim D W, Jeon Y S, Eom T Y, et al. Lithium isotope separation on a monobenzo-15-crown-5 resin[J]. J Radioanal Nucl Chem, 1991, 150(2): 417–426.
[10] Pedersen C J. Cyclic polyethers and their complexes with metal salts[J]. JACS, 1967, 89(26): 7017–7036.
[11] Lewis G N, Macdonald R T. The separation of lithium isotopes[J]. JACS, 2002, 58(12): 2519–2524.
[12] Fujine S, Saito K, Shiba K. Lithium isotope separation by displacement chromatography using cryptand resin[J]. J Nucl Sci Technol, 1983, 20(5): 439–440.
[13] Zeng Y, Pei H C, Wang Z, et al. Chitosan-graft-benzo-15-crown-5-ether/PVA blend membrane with sponge-like pores for lithium isotope adsorptive separation[J]. ACS Omega, 2018, 3(1): 554–561.
[14] Ungaro R, Haj B E, Smid J. ChemInform Abstract: Substituent effects on the stability of cation complexes of 4′-substituted monobenzo crown ethers [J]. Chem Inform, 1976, 7(47):5198–5202.
[15] Du R K, Gao B J, Li Y B, et al. Preparation and structure/property relationship of polysulfone anion-exchange membranes[J]. Acta Polym Sin, 2010, 10(7): 924–931.
[16] Yan F, Pei H C, Pei Y C, et al. Preparation and characterization of polysulfone-graft- 4’-aminobenzo-15-crown-5-ether for lithium isotope separation[J]. Ind Eng Chem Res, 2015, 54(13): 3473–3479.
[17] Guiochon G, Shirazi S G, Katti A M. Fundamentals of preparative and nonlinear chromatography[J]. Anal Chim Acta, 1995, 302(1): 127–128.
[18] Glueckauf E. Theory of chromatography. Part 11.—Enrichment of isotopes by chromatography[J]. Trans Faraday Soc, 1958, 54: 1203–1205.
[19] Yu Z, Karkaria T, Espina M, et al. Comparing multi-module connections in membrane chromatography scale-up[J]. J Biotechnol, 2015, 206: 38–41.
[20] Mikeš J, ?urišová J, Jelínek L. Enrichment of lithium isotope 6Li by ion exchange resin with specific particle size[J]. J Radioanal Nucl Chem, 2017, 312(1): 13–18.
[21] 杨利, 陈小明, 贾凌云, 等. 疏水膜色谱法对生物大分子的快速纯化[J]. 色谱, 1999, 17(4):335–338.
[22] Chen Y C, LU C. Kinetics, thermodynamics and regeneration of molybdenum adsorption in aqueous solutions with NaOCl-oxidized multiwalled carbon nanotubes[J]. J Ind Eng Chem, 2014, 20(4): 2521–2527.
[23] Langmuir I. The adsorption of gases on plane surfaces of glass, mica and platinum[J]. J Chem Phys, 2015, 40(12): 1361–1403.
[24] Tennikova T B, Svec F. High-performance membrane chromatography: Highly efficient separation method for proteins in ion-exchange, hydrophobic interaction and reversed-phase modes[J]. J Chromatogr A, 1993, 646(2): 279–288.
[25] 张玉忠, 肖长发. 膜色谱技术的进展[J]. 天津工业大学学报, 2004, 23(4):94-97.
[26] Jeon Y S, Han J, Kang B M, et al. Separation of lithium isotopes by tetraazamacrocycles tethered to Merrifield peptide resin[J]. Bull Korean Chem Soc, 2007, 28(3): 451–456.
[27] Oi T, Kondoh A, Ohno E. Lithium isotope effects in cation exchange chromatography of lithium lactate in water-dimethyl sulfoxide and water-acetone mixed solvent media[J]. Z Naturforsch, A Phys Sci, 1993, 48(7): 811–818.
[28] Kim D W, Park S R, Kim S J, et al. Separation of lithium isotope by NTOE compound[J]. J Radioanal Nucl Chem, 1998, 229(1–2): 165–168.

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