化工学报 ›› 2022, Vol. 73 ›› Issue (8): 3739-3748.DOI: 10.11949/0438-1157.20220625
收稿日期:
2022-05-05
修回日期:
2022-06-01
出版日期:
2022-08-05
发布日期:
2022-09-06
通讯作者:
葛亮,徐铜文
作者简介:
杨宏欣 (1997—),男,硕士研究生,yhx524@mail.ustc.edu.cn
基金资助:
Hongxin YANG1(), Xingya LI1, Liang GE1,2(), Tongwen XU1()
Received:
2022-05-05
Revised:
2022-06-01
Online:
2022-08-05
Published:
2022-09-06
Contact:
Liang GE, Tongwen XU
摘要:
基于超酸催化聚合机理制备了含咔唑片段的聚合物主链结构,并通过调控季铵化反应中N-甲基哌啶单体的用量,得到了不同哌啶离子含量的阴离子选择性分离膜。通过核磁共振氢谱证明了聚合反应和季铵化反应顺利进行。热重和动态机械分析的测试结果表明膜具有优异的热稳定性和力学性能。通过电渗析 (ED) 测试膜的阴离子分离性能,结果显示离子通量和选择性均优于商业膜Neosepta ACS。在NaCl/Na2SO4体系中,QPC-Pip-60的Cl-通量可达3.24 mol·m-2·h-1,选择性可达11.6。在NaOH/Na2WO4碱回收体系下,良好的微相分离结构使得OH-通量可达3.59 mol·m-2·h-1,选择性最高为70。长时间稳定性测试和碱稳定性测试结果表明所制备的系列膜具有优异的循环稳定性和耐碱性能。
中图分类号:
杨宏欣, 李兴亚, 葛亮, 徐铜文. 含哌啶阳离子侧长链型一/二价阴离子选择性分离膜的制备[J]. 化工学报, 2022, 73(8): 3739-3748.
Hongxin YANG, Xingya LI, Liang GE, Tongwen XU. Preparation of mono-/divalent anion permselective membranes with piperidinium-type long side-chain[J]. CIESC Journal, 2022, 73(8): 3739-3748.
膜名称 | PC-Br/mmol | N-甲基哌啶/mmol | NMP/ml | 理论IEC/(mmol·g-1) |
---|---|---|---|---|
QPC-Pip-60 | 4.71 | 2.83 | 22 | 1.24 |
QPC-Pip-80 | 4.71 | 3.77 | 22 | 1.59 |
QPC-Pip-100 | 4.71 | 4.71 | 22 | 1.91 |
表1 季铵化反应的反应物用量
Table 1 The amount of reactants for quaternization reaction
膜名称 | PC-Br/mmol | N-甲基哌啶/mmol | NMP/ml | 理论IEC/(mmol·g-1) |
---|---|---|---|---|
QPC-Pip-60 | 4.71 | 2.83 | 22 | 1.24 |
QPC-Pip-80 | 4.71 | 3.77 | 22 | 1.59 |
QPC-Pip-100 | 4.71 | 4.71 | 22 | 1.91 |
图6 QPC-Pip-x系列膜的IEC、含水率、溶胀度及QPC-Pip-x系列和ACS膜的面电阻和迁移数
Fig.6 The IEC, water uptake and swelling ratio result of QPC-Pip-x series membranes and the surface resistance and transport number of QPC-Pip-x series membranes and ACS membrane
图7 QPC-Pip-x和Neosepta ACS的I-V曲线图及I-V曲线的导数dE/di同电流密度的函数图
Fig.7 The I-V curves of QPC-Pip-x and Neosepta ACS and the derivative of dE/di as a function of current density calculated from the I-V curves
膜名称 | 抗拉强度/MPa | 断裂伸长率/% |
---|---|---|
QPC-Pip-60 | 32.74 | 9.56 |
QPC-Pip-80 | 30.49 | 12.84 |
QPC-Pip-100 | 29.20 | 14.11 |
表2 QPC-Pip-x系列膜的抗拉强度和断裂伸长率
Table 2 The tensile strength and elongation of break of QPC-Pip-x series membrane
膜名称 | 抗拉强度/MPa | 断裂伸长率/% |
---|---|---|
QPC-Pip-60 | 32.74 | 9.56 |
QPC-Pip-80 | 30.49 | 12.84 |
QPC-Pip-100 | 29.20 | 14.11 |
膜名称 | 电流密度/(mA·cm-2) | 进料溶液 | Cl-通量/(mol·m-2·h-1) | 选择性 | 文献 |
---|---|---|---|---|---|
PAES-6C-IM | 5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 1.26 | 7.1 | [ |
PQC76/DSA-0.5 | 5 | 0.2 mol·L-1 NaCl+0.2 mol·L-1 Na2SO4 | 1.80 | 10 | [ |
QPEI/PVA-C10-5 | 20 | 0.05 M NaCl + 0.05 mol·L-1 Na2SO4 | 1.59 | 6.31 | [ |
交联两性AEM | 5 | 0.05 mol·L-1 NaCl + 0.05 mol·L-1 Na2SO4 | 1.33 | 12.5 | [ |
QP-P11-1 | 3.5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 1.04 | 13 | [ |
CrPsf-3 | 12 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 2.97 | 5.7 | [ |
均相共混-15-AIEM | 2.5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | — | 21.8 | [ |
CBTS-integrated CCAPMs | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 1.86 | 7.3 | [ |
AMX-LPDA#DBSA | 8 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 2.47 | 1.4 | [ |
(PSS/PAH)5PSS AEM | 1.13 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 0.242 | 7.4 | [ |
QPC-Pip-60 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.24 | 11.6 | 本工作 |
QPC-Pip-80 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.27 | 11.0 | 本工作 |
QPC-Pip-100 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.32 | 10.5 | 本工作 |
表3 近期文献中单价阴离子选择性渗透膜在Cl-/WO42-体系下的ED性能结果
Table 3 An overview of the ED performance in Cl-/WO42- system of the monovalent anion permselective membranes in recent literatures
膜名称 | 电流密度/(mA·cm-2) | 进料溶液 | Cl-通量/(mol·m-2·h-1) | 选择性 | 文献 |
---|---|---|---|---|---|
PAES-6C-IM | 5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 1.26 | 7.1 | [ |
PQC76/DSA-0.5 | 5 | 0.2 mol·L-1 NaCl+0.2 mol·L-1 Na2SO4 | 1.80 | 10 | [ |
QPEI/PVA-C10-5 | 20 | 0.05 M NaCl + 0.05 mol·L-1 Na2SO4 | 1.59 | 6.31 | [ |
交联两性AEM | 5 | 0.05 mol·L-1 NaCl + 0.05 mol·L-1 Na2SO4 | 1.33 | 12.5 | [ |
QP-P11-1 | 3.5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 1.04 | 13 | [ |
CrPsf-3 | 12 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 2.97 | 5.7 | [ |
均相共混-15-AIEM | 2.5 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | — | 21.8 | [ |
CBTS-integrated CCAPMs | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 1.86 | 7.3 | [ |
AMX-LPDA#DBSA | 8 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 2.47 | 1.4 | [ |
(PSS/PAH)5PSS AEM | 1.13 | 0.05 mol·L-1 NaCl+0.05 mol·L-1 Na2SO4 | 0.242 | 7.4 | [ |
QPC-Pip-60 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.24 | 11.6 | 本工作 |
QPC-Pip-80 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.27 | 11.0 | 本工作 |
QPC-Pip-100 | 10 | 0.1 mol·L-1 NaCl+0.1 mol·L-1 Na2SO4 | 3.32 | 10.5 | 本工作 |
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