PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO2渗透分离性能

doi:10.11949/0438-1157.20200974

摘要/Abstract

摘要：

采用壳层具有介孔结构的聚吡咯中空纳米微球作为填料，和聚氧化乙烯单体共混自由基聚合制备了混合基质膜。结果表明，聚吡咯微球与基质相容性较好，未见明显团聚现象和缺陷。混合基质膜的渗透系数随填料含量的增加先增大后减少，在0.5%处达到最大值，CO₂渗透系数增长31%；CO₂/N₂分离系数有所降低，CO₂/CH₄分离系数则变化不大。研究表明，由于聚合物链段对微球壳层的介孔填充，气体在膜内的扩散系数不升反降，渗透系数的提高主要是由于溶解度系数的变化，而这也导致了溶解选择性的变化，进而影响了分离系数。

关键词: 二氧化碳, 纳米粒子, 膜, 中空粒子, 混合基质

Abstract:

The hollow polypyrrole nanoparticle with porous shell was incorporated into poly(ethylene oxide) monomer to fabricate the mixed matrix membrane by free radical polymerization. Morphology of the membranes showed the polymeric filler had good interfacial compatibility with the polymeric matrix without obvious defect. The results showed that the gas permeability of membranes increased at first and then decreased as the filler loading increased, while the permselectivity of CO₂/N₂decreased_{and_{that of CO₂/CH₄maintained constant basically. The research showed that the diffusion coefficients decreased due to the blockage of the pore in shell of nanoparticles by polymeric matrix, the improvement of the gas permeability was mainly contributed by the improvement of the solubility coefficient, which also affected the solubility selectivity and then the permselectivity. The optimum nanoparticle loading was around 0.5%. In this case, the permeability of CO₂ was about 6.5×10^-11 cm³?cm?cm^-2?s^-1?Pa^-1 (31% higher than the pristine polymeric membranes), while the permselectivity of CO₂/N₂ was about 30 (34% lower than that of the pristine polymeric membranes) and the permselectivity of CO₂/CH₄ was about 14 without significant sacrifice. The result showed the polypyrrole nanoparticles with porous shell was potential for application in CO₂/CH₄ separation.}}

Key words: carbon dioxide, nanoparticles, membranes, hollow particles, mixed matrix

中图分类号:

TQ 028.8

赵红永, 曹金城, 丁晓莉, 曹倩倩, 王鑫兰, 张玉忠. PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO₂渗透分离性能[J]. 化工学报, 2020, 71(S2): 210-215.

Hongyong ZHAO, Jincheng CAO, Xiaoli DING, Qianqian CAO, Xinlan WANG, Yuzhong ZHANG. Synthesis of PEO/hollow polypyrrole nanoparticle mixed matrix membranes for CO₂ separation[J]. CIESC Journal, 2020, 71(S2): 210-215.

图/表 8

图1 混合基质膜的红外谱图（聚吡咯中空纳米微球负载量1.5%）

Fig.1 FTIR spectrum of MMMs modified with 1.5% hollow polypyrrole nanoparticles

图2 膜表面电镜照片

Fig.2 Surface SEM images of samples

图3 膜广角X射线衍射谱图

Fig.3 Wide angle X-ray diffraction patterns of membranes

图4 膜差示扫描量热曲线

Fig.4 Differential scanning calorimetry thermo-grams of membranes

图5 微球负载量对渗透系数的影响

Fig.5 Effect of filler loading on permeability coefficients

图6 微球负载量对扩散系数的影响

Fig.6 Effect of filler loading on diffusion coefficients

图7 微球负载量对溶解度系数的影响

Fig.7 Effect of filler loading on solubility coefficients

图8 微球负载量对选择性的影响

Fig.8 Effect of filler loading on selectivity

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PEO/聚吡咯中空纳米微球混合基质膜的制备及其CO₂渗透分离性能

Synthesis of PEO/hollow polypyrrole nanoparticle mixed matrix membranes for CO₂ separation

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