化工学报 ›› 2021, Vol. 72 ›› Issue (6): 3014-3021.DOI: 10.11949/0438-1157.20201711
李恩泽1(),叶培远1,王亚欣1,康锦1,阴彩霞2,程芳琴1()
收稿日期:
2020-11-30
修回日期:
2021-03-05
出版日期:
2021-06-05
发布日期:
2021-06-05
通讯作者:
程芳琴
作者简介:
李恩泽(1988—),男,博士,副教授,基金资助:
LI Enze1(),YE Peiyuan1,WANG Yaxin1,KANG Jin1,YIN Caixia2,CHENG Fangqin1()
Received:
2020-11-30
Revised:
2021-03-05
Online:
2021-06-05
Published:
2021-06-05
Contact:
CHENG Fangqin
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。
中图分类号:
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+
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(Kd) | 选择性分离因子(α) |
---|---|---|---|---|
Li+ | 3.553 | 63.946 | 0.056 | 56 |
Mg2+ | 0.069 | 67.430 | 0.001 |
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(Kd) | 选择性分离因子(α) |
---|---|---|---|---|
Li+ | 3.553 | 63.946 | 0.056 | 56 |
Mg2+ | 0.069 | 67.430 | 0.001 |
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