聚乙烯胺/Cu3（BTC）2-MMT-NH2混合基质膜的制备及气体传递性能

doi:10.11949/0438-1157.20220464

摘要/Abstract

摘要：

采用阳离子交换与Cu₃(BTC)₂原位合成相结合制备Cu₃(BTC)₂-MMT，同时，借助3-氨基丙基三乙氧基硅烷(KH550)氨基功能化制备Cu₃(BTC)₂-MMT-NH₂杂化材料。然后，将杂化材料添加到聚乙烯胺(PVAm)基质中作为选择性涂层涂覆到聚砜(PSf)支撑体上，制备了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜。通过XRD和FTIR对杂化材料的晶态结构和化学结构进行了表征，同时采用ATR-FTIR证实了Cu₃(BTC)₂-MMT-NH₂杂化材料与PVAm基质之间存在氢键相互作用。系统性研究了PVAm/Cu₃(BTC)₂-MMT-NH₂混合基质膜中MMT阳离子交换量、Cu₃(BTC)₂-MMT与KH550的质量比、Cu₃(BTC)₂-MMT-NH₂的负载量、操作压力、湿膜厚度、操作温度以及混合气作为原料气对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：在纯气气氛，操作温度为25℃、操作压力为1 bar(1 bar=0.1 MPa)的条件下，当Cu₃(BTC)₂-MMT-NH₂负载量为3%(质量)时，膜的气体分离性能最优，CO₂渗透率为203 GPU(1GPU=10^-6 cm³·cm^-2·s^-1·cmHg^-1，1 cmHg=1333.22 Pa)，CO₂/N₂选择性为100.7，远高于添加MMT、Cu₃(BTC)₂和MMT/Cu₃(BTC)₂混合物的混合基质膜。这是由于Cu₃(BTC)₂-MMT-NH₂具有层间快速传递通道且与聚合物基质有良好的相容性。此外，混合气测试条件下，混合基质膜运行360 h，仍能保持优异的CO₂分离性能稳定性。

关键词: 聚乙烯胺, 混合基质膜, 蒙脱土, 传递通道, CO₂分离

Abstract:

In this paper, Cu₃(BTC)₂-MMT was prepared by combining cation exchange with in situ synthesis of Cu₃(BTC)₂, while Cu₃(BTC)₂-MMT-NH₂ hybrid materials were prepared by amino functionalization of 3-aminopropyltriethoxysilane (KH550). Hybrid materials were added to polyvinylamine (PVAm) matrix as selective coating solution, which was coated on polysulfone (PSf) support to obtain mixed matrix membrane (PVAm/Cu₃(BTC)₂-MMT-NH₂). The crystalline and chemical structures of the hybrid materials were characterized by XRD and FTIR, and hydrogen bonding between the Cu₃(BTC)₂-MMT-NH₂hybrid materials and the PVAm matrix was confirmed using ATR-FTIR. The effects of exchange of copper and sodium ions, mass ratio of Cu₃(BTC)₂-MMT to KH550, loading of Cu₃(BTC)₂-MMT-NH₂, operating pressure, wet membrane thickness, operating temperature, and under mixed gas feed on membrane CO₂ permeability and CO₂/N₂ selectivity in mixed matrix membranes were systematically investigated. The results show that under the conditions of pure gas atmosphere, operating temperature of 25℃ and operating pressure of 1 bar, the membrane had the best gas separation performance with a CO₂ permeation rate of 203 GPU and CO₂/N₂ selectivity of 100.7, which is much higher than that of the mixed matrix membrane with MMT, Cu₃(BTC)₂ or the mixture of MMT and Cu₃(BTC)₂. This is attributed to the interlayer transmission channel of Cu₃(BTC)₂-MMT-NH₂ and its good compatibility with polymer matrix. In addition, under the mixed gas test condition, the mixed matrix membrane can still maintain excellent stability in CO₂ separation performance over 360 h.

Key words: polyvinylamine, mixed matrix membrane, montmorillonite, transport passway, CO₂ separation

中图分类号:

TQ 028.8

王立维, 王娟娟, 王永洪, 张新儒, 李晋平. 聚乙烯胺/Cu₃（BTC）₂-MMT-NH₂混合基质膜的制备及气体传递性能[J]. 化工学报, 2022, 73(7): 3068-3077.

Liwei WANG, Juanjuan WANG, Yonghong WANG, Xinru ZHANG, Jinping LI. Gas transport properties of PVAm-based mixed matrix membranes by incorporating with Cu₃(BTC)₂-MMT-NH₂[J]. CIESC Journal, 2022, 73(7): 3068-3077.

图/表 15

图1 Cu3(BTC)2-MMT-NH2的制备

Fig.1 The fabrication of Cu3(BTC)2-MMT-NH2

图2 PVAm/Cu3(BTC)2-MMT-NH2混合基质膜的制备

Fig.2 The fabrication of PVAm/Cu3(BTC)2-MMT-NH2 MMMs

图3 无机填料的X射线衍射图

Fig.3 XRD patterns of inorganic fillers

图 4 MMT、Cu3(BTC)2、Cu3(BTC)2-MMT和Cu3(BTC)2-MMT-NH2的红外光谱图

Fig.4 FTIR spectra of MMT, Cu3(BTC)2, Cu3(BTC)2-MMT and Cu3(BTC)2-MMT-NH2

图5 膜的衰减全反射红外光谱图

Fig.5 ATR-FTIR spectra of the membranes

图6 MMT阳离子交换量对混合基质膜气体分离性能的影响

Fig.6 Effect of the cation exchange capacity of MMT on gas separation performance of the MMMs

图7 Cu3(BTC)2-MMT与KH550质量比对混合基质膜气体分离性能的影响

Fig.7 Effect of the Cu3(BTC)2-MMT to KH550 mass ratio on gas separation performance of the MMMs

图8 Cu3(BTC)2-MMT-NH2 负载量对混合基质膜气体分离性能的影响

Fig.8 Effect of the Cu3(BTC)2-MMT-NH2 loading on the CO2 permeance and CO2/N2 selectivity of the MMMs

图9 操作压力对混合基质膜CO2渗透率(a)和CO2/N2选择性(b)的影响

Fig.9 Effect of the operating pressure on the CO2 permeance (a) and CO2/N2 selectivity (b) of the MMMs

图10 湿涂层厚度对混合基质膜CO2渗透率(a)和CO2/N2选择性(b)的影响

Fig.10 Effect of the wet coating thickness on the CO2 permeance (a) and CO2/N2 selectivity (b) of MMMs

图11 操作温度对PVAm纯膜和混合基质膜CO2渗透率(a)与CO2/N2选择性(b)的影响

Fig.11 Effect of the operating temperature on the CO2 permeance (a) and the CO2/N2 selectivity (b) of the PVAm pure membrane and MMMs

图12 在混合气和纯气体条件下混合基质膜的CO2渗透率(a)和CO2/N2选择性(b)

Fig.12 CO2 permeance (a) and CO2/N2 selectivity (b) of the MMMs under the mixed and pure gas conditions

图13 不同填料(负载量：3%(质量))对混合基质膜气体分离性能的影响(a)；不同填料含量对混合基质膜的气体分离性能的CO2渗透率(b)和CO2/N2选择性(c)的影响

Fig.13 Gas separation performance of MMMs with different fillers (loading: 3% (mass)) (a); The effects of different filler loadings on CO2 permeance (b) and CO2/N2 selectivity (c) of MMMs gas separation performance

图14 PVAm/Cu3(BTC)2-MMT-NH2-3 混合基质膜的稳定性

Fig.14 The stability of the PVAm/Cu3(BTC)2-MMT-NH2-3 MMMs

图15 CO2/N2性能增加百分数和以前报道的混合基质膜的CO2/N2分离性能对比

Fig.15 Comparison of CO2/N2 performance enhancement percentage and previously reported MMMs

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聚乙烯胺/Cu₃（BTC）₂-MMT-NH₂混合基质膜的制备及气体传递性能

Gas transport properties of PVAm-based mixed matrix membranes by incorporating with Cu₃(BTC)₂-MMT-NH₂

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