聚乙烯胺/Cu_(3)(BTC)_(2)-MMT-NH_(2)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 Cu_(3)(BTC)_(2)-MMT-NH_(2)

作　　者：王立维 王娟娟 王永洪[1,2] 张新儒 李晋平[1,2] WANG Liwei;WANG Juanjuan;WANG Yonghong;ZHANG Xinru;LI Jinping(College of Chemical Engineering and Technology,Taiyuan University of Technology,Taiyuan 030024,Shanxi,China;Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization,Taiyuan 030024,Shanxi,China)

机构地区：[1]太原理工大学化学工程与技术学院,山西太原030024 [2]气体能源高效清洁利用山西省重点实验室,山西太原030024

出　　处：《化工学报》2022年第7期3068-3077,F0004,共11页CIESC Journal

基　　金：国家自然科学基金面上项目(22078216);山西省回国留学人员科研资助项目(2021-056,2020-027);山西省自然科学基金面上项目(20210302123196)。

摘　　要：采用阳离子交换与Cu_(3)(BTC)_(2)原位合成相结合制备Cu_(3)(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Cu_(3)(BTC)_(2)-MMT-NH_(2)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/Cu_(3)(BTC)_(2)-MMT-NH_(2)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Cu_(3)(BTC)_(2)-MMT-NH_(2)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/Cu_(3)(BTC)_(2)-MMT-NH_(2)混合基质膜中MMT阳离子交换量、Cu_(3)(BTC)_(2)-MMT与KH550的质量比、Cu_(3)(BTC)_(2)-MMT-NH_(2)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CO_(2)渗透性、CO_(2)/N_(2)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Cu_(3)(BTC)_(2)-MMT-NH_(2)负载量为3%(质量)时,膜的气体分离性能最优,CO_(2)渗透率为203 GPU(1GPU=10-6 cm^(3)·cm^(-2)·s^(-1)·cmHg^(-1),1 cmHg=1333.22 Pa),CO_(2)/N_(2)选择性为100.7,远高于添加MMT、Cu_(3)(BTC)_(2)和MMT/Cu_(3)(BTC)_(2)混合物的混合基质膜。这是由于Cu_(3)(BTC)_(2)-MMT-NH_(2)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CO_(2)分离性能稳定性。In this paper,Cu_(3)(BTC)_(2)-MMT was prepared by combining cation exchange with in situ synthesis of Cu_(3)(BTC)_(2),while Cu_(3)(BTC)_(2)-MMT-NH_(2)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/Cu_(3)(BTC)_(2)-MMT-NH_(2)).The crystalline and chemical structures of the hybrid materials were characterized by XRD and FTIR,and hydrogen bonding between the Cu_(3)(BTC)_(2)-MMT-NH_(2)hybrid materials and the PVAm matrix was confirmed using ATR-FTIR.The effects of exchange of copper and sodium ions,mass ratio of Cu_(3)(BTC)_(2)-MMT to KH550,loading of Cu_(3)(BTC)_(2)-MMT-NH_(2),operating pressure,wet membrane thickness,operating temperature,and under mixed gas feed on membrane CO_(2)permeability and CO_(2)/N_(2)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 CO_(2)permeation rate of 203 GPU and CO_(2)/N_(2)selectivity of 100.7,which is much higher than that of the mixed matrix membrane with MMT,Cu_(3)(BTC)_(2)or the mixture of MMT and Cu_(3)(BTC)_(2).This is attributed to the interlayer transmission channel of Cu_(3)(BTC)_(2)-MMT-NH_(2)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 CO_(2)separation performance over 360 h.

关 键 词：聚乙烯胺 混合基质膜 蒙脱土 传递通道 CO_(2)分离 

分 类 号：TQ028.8[化学工程]