基于管式陶瓷载体的碳化ZIF-67掺入PDMS混合基质膜及其渗透汽化回收乙醇应用

doi:10.16085/j.issn.1000-6613.2024-1412

摘要/Abstract

摘要：

在聚合物基体中加入疏水性纳米多孔填料制备混合基质膜（MMM），是提高低浓度乙醇水溶液渗透汽化分离性能十分有效的策略。本文为适应工业化应用要求，在管式陶瓷载体上制备了ZIF-67颗粒填充的聚二甲基硅氧烷（PDMS）基MMM，但存在ZIF-67颗粒在基质膜中出现一定程度的团聚导致分散性不好、ZIF-67与基质膜之间的界面相溶性不理想等不足。进而进一步制备了ZIF-67衍生纳米多孔碳（C-ZIF-67），以取代传统MMM中的ZIF-67。通过各种表征研究了ZIF-67及其碳化颗粒的化学结构，并对所得MMMs的形态和性质进行了测试。由于碳成分固有的强疏水性质、相对较好的分散性以及与PDMS更好的相溶性，C-ZIF-67/PDMS MMM表现出比ZIF-67/PDMS MMM和纯PDMS膜更优异的分离性能。在60℃下质量分数5%的乙醇水溶液中，C-ZIF-67/PDMS-15% MMM的性能最佳，通量为1.04kg/(m²·h)，相应的分离因子为9.2。综合来看，相关实验结果已初步表明C-ZIF-67/PDMS MMM在低浓度乙醇水溶液分离中具有潜在的应用价值。

关键词: ZIF-67衍生的纳米多孔碳, 聚二甲基硅氧烷, 膜, 管式陶瓷载体, 渗透蒸发

Abstract:

It is a very effective strategy to prepare mixed matrix membranes (MMM) by incorporating hydrophobic nanoparticle into the polymer matrix to improve the pervaporation separation performance in the process of recovering ethanol from aqueous solution. In this study, polydimethylsiloxane (PDMS) based MMM filled with ZIF-67 particles was prepared on ceramic tubes, but there were some associated problems such as severe reunion, poor compatibility, etc. In order to improve the diffusion process, ZIF-67-derived nanoporous carbon (C-ZIF-67) was prepared to replace ZIF-67 in conventional MMM.ZIF-67 and carbonized particles were studied by various characterization, and the morphology and properties of MMMs were tested. Compared with ZIF-67/PDMS MMM and pure PDMS membrane, C-ZIF-67/PDMS MMM exhibited better enhanced separation performance: the best performance with a total flux of 1.04kg/(m²·h) and a separation factor of 9.2 at 60℃ for 5% ethanol solution. In summary, the relevant experimental results had preliminarily indicated that C-ZIF-67/PDMS MMM had potential application value in the separation of dilute ethanol aqueous solution.

Key words: ZIF-67-derived nanoporous carbon, polydimethysiloxane, membranes, tubular ceramic support, pervaporation

中图分类号:

TQ31

袁博, 勾佳宣, 李玉壮, 刘群, 徐坤, 张钰. 基于管式陶瓷载体的碳化ZIF-67掺入PDMS混合基质膜及其渗透汽化回收乙醇应用[J]. 化工进展, 2025, 44(9): 5211-5223.

YUAN Bo, GOU Jiaxuan, LI Yuzhuang, LIU Qun, XU Kun, ZHANG Yu. Carbonized ZIF-67 incorporated PDMS mixed matrix membranes on ceramic tubes for recovery of ethanol via pervaporation[J]. Chemical Industry and Engineering Progress, 2025, 44(9): 5211-5223.

图/表 20

图1 渗透汽化性能测试装置示意图

图2 ZIF-67及C-ZIF-67颗粒的XRD图谱和TGA曲线

图3 ZIF-67和C-ZIF-67颗粒的FTIR图

图4 ZIF-67和C-ZIF-67颗粒的SEM图

图5 ZIF-67和C-ZIF-67颗粒的粒径分布

图6 ZIF-67和C-ZIF-67颗粒的氮气吸附-脱附等温线和孔径分布

表1 ZIF-67和C-ZIF-67的孔结构特性

样品	总孔体积/cm³·g^-1	微孔体积/cm³·g^-1	平均孔径/nm
ZIF-67	0.74	0.71	2.18
C-ZIF-67	0.32	0.17	3.57

图7 纯PDMS膜、ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM的XRD图和FTIR图

图8 纯PDMS膜、ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM的TGA和DTG曲线

图9 纯PDMS膜、ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM表面和截面的SEM图

图10 纯PDMS膜、ZIF-67/PDMS-15% MMM和不同负载量的C-ZIF-67/PDMS MMM的水接触角

表2 ZIF-67/PDMS MMM的水接触角

膜	水接触角/(°)
PDMS	115
ZIF-67/PDMS-5%	118
ZIF-67/PDMS-10%	122
ZIF-67/PDMS-15%	129
ZIF-67/PDMS-20%	130
ZIF-67/PDMS-25%	132

图11 纯PDMS膜、ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM在乙醇中的溶胀度对比

图12 不同ZIF-67负载下ZIF-67/PDMS MMM和不同C-ZIF-67负载下C-ZIF-67/PDMS MMM的渗透汽化性能（5.0%乙醇水溶液，60℃）

图13 纯PDMS膜、ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM的渗透汽化性能对比（5.0%乙醇水溶液，60℃）

图14 操作温度对ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM渗透蒸发性能的影响（5.0%乙醇水溶液）J=J0exp(-EJRT) (5)

图15 个体通量与ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM的温度的Arrhenius关系

图16 料液乙醇浓度（质量分数）对ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM渗透蒸发性能的影响（操作温度60℃）

图17 ZIF-67/PDMS-15% MMM和C-ZIF-67/PDMS-15% MMM的长期渗透汽化性能（5.0%乙醇水溶液，120h，60℃）

表3 不同PDMS混合基质膜在乙醇水溶液中渗透汽化性能的比较

膜	操作温度/℃	料液质量分数/%	渗透通量/kg·m^-2·h^-1	分离因子	参考文献
ZIF-8/PDMS	40	5	1.60	8.5	[43]
ZIF-L/PDMS	40	5	1.12	12.3	[44]
MCM-41@ZIF-8	50	5	1.20	8.1	[45]
UiO-66/α-Al₂O₃	50	10	1.40	4.9	[46]
Silicalite-1/PDMS	60	5	0.40	14.7	[47]
Silicalite-1/PDMS	35	6	0.05	9.2	[48]
POSS-GO/PDMS	40	5	1.35	11.2	[49]
PDMS	60	5	1.62	5.9	本工作
Silicalite-1/PDMS	60	5	0.43	6.4	本工作
ZIF-67/PDMS	60	5	0.85	7.9	本工作
C-ZIF-67/PDMS	60	5	1.04	9.2	本工作

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