Electro-membrane extraction of Li(Ⅰ) by Cyanex923/TBP/PHEN in collaboration with 2-thiophenecarbonyltrifluoroacetone

doi:10.11949/0438-1157.20240495

Abstract

Abstract:

Lithium resource plays an important role in energy strategy. Membrane extraction technology is expected to solve the green sustainability problem of liquid lithium resource extraction. Binary composite extraction membranes PT-PIMs (PTC-PIM /PTT-PIM/PTP-PIM) with 2-thiophenoyltrifluoroacetone (TTA) synergistically solvated carriers [trialkylphosphine oxide mixture (Cyanex923)/tributyl phosphate (TBP)/phenanthroline (PHEN)] were prepared. The mass transfer behaviour of $P T - P I M s - L i (Ⅰ)$ system by electric field enhancement was investigated under optimized membrane phase conditions, and the stability and Li/Na/K selective separation performance of the kerosene-modified $P K - P I M s - L i (Ⅰ)$ system were evaluated. The results show that the membrane phase composition has a large effect on the mass transfer rate of Li(Ⅰ), the main extractant TTA plays a dominant role in Li(Ⅰ) mass transfer, and the mass transfer rate increases with the voltage. The permeability coefficient of PTC-PIM-Li(Ⅰ) system increases linearly with increasing voltage. The permeability coefficient of PTC-PIM-Li(Ⅰ) system is 33.20 μm·s^-1 at 40 V. The permeation rate of Li(Ⅰ) in the PT-PIMs-Li(Ⅰ) system modified by kerosene decreased by <21% after four cycles; When the mass concentration ratio of Li(Ⅰ)∶Na(Ⅰ)∶K(Ⅰ) in liquid phase is 20∶20∶20, the separation factors S_{Li(Ⅰ)/Na(Ⅰ)} and S_{Li(Ⅰ)/K(Ⅰ)} of PT-PIMs system are 8.41, 4.88, 3.88 and 7.99, 4.64, 3.81, respectively, indicating the selective separation ability of Li. The combined permeability coefficient, stability and PK-PIMs-Li(Ⅰ) systems: PCK-PIM > PTK-PIM > PPK-PIM. This paper provides an important idea for sustainable extraction technology of lithium resources with green energy saving.

Key words: lithium, membrane, electro-membrane extraction, HTTA+synergist, stability, selectivity

摘要：

为强化2-噻吩甲酰三氟丙酮（HTTA）萃锂体系的性能，分别制备了以三烷基氧化膦、磷酸三丁酯、邻菲罗啉3种协萃剂配伍的聚氯乙烯基二元复合萃取膜（PT-PIMs），用于研究电场强化的膜萃取提锂技术。考察了膜相组成和操作电压对Li（Ⅰ）传质性能的影响规律，结合表面红外和扫描电镜对PT-PIMs的表征结果，初步探索了PTC-PIM-Li（Ⅰ）电膜萃取机制。研究表明：在PT-PIMs体系中，HTTA通过烯醇化结构与Li（Ⅰ）形成离子型配合物，在PT-PIMs中起主萃作用。3种协萃剂通过对HTTA的去质子化协同传质，并因协萃剂的碱性及塑化能力的不同而导致3种PT-PIMs对Li（Ⅰ）的传质能力不同。Li（Ⅰ）在膜界面的传质机制为“离子交换-中和”，外加电场通过强化TTA-Li（Ⅰ）配合物解离而促进传质，但同时会受限于PT-PIMs膜界面的化学反应速率。经煤油改性后的PT-PIMs-Li（Ⅰ）体系在四次循环后Li（Ⅰ）的渗透速率下降率<21%；在料液相 Li（Ⅰ）∶Na（Ⅰ）∶K（Ⅰ）质量浓度比为20∶20∶20时，PT-PIMs体系分离因子S_{Li(Ⅰ)/Na(Ⅰ)}和S_{Li(Ⅰ)/K(Ⅰ)}分别为8.41、4.88、3.88和7.99、4.64、3.81，显示了Li选择性分离能力。

关键词: 锂, 膜, 电膜萃取, HTTA+协萃剂, 稳定性, 选择性

CLC Number:

TQ 317.4

Xiaorong MENG, Chi SUN, Yiwen LONG. Electro-membrane extraction of Li(Ⅰ) by Cyanex923/TBP/PHEN in collaboration with 2-thiophenecarbonyltrifluoroacetone[J]. CIESC Journal, 2024, 75(12): 4606-4616.

孟晓荣, 孙驰, 龙伊文. Cyanex923/TBP/PHEN协同2-噻吩甲酰三氟丙酮对Li（Ⅰ）的电膜萃取研究[J]. 化工学报, 2024, 75(12): 4606-4616.

Figures/Tables 2

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