碳纳米管/环糊精金属有机骨架协同强化混合基质膜的CO2分离

doi:10.11949/0438-1157.20220627

摘要/Abstract

摘要：

为了实现混合基质膜中CO₂的高效分离，设计了羧基化多壁碳纳米管(CNT)和氨基化β-环糊精金属有机骨架(β-CD MOF)双填料(CM)，并将其引入磺化聚醚醚酮(SPEEK)基质中，在膜内同时构建CO₂扩散通道和亲和位点，增强了混合基质膜的分离性能。采用FTIR和BET表征了CM的化学结构和孔结构，借助膜的SEM、FTIR和力学性能表征了填料-聚合物界面相互作用。研究了CM的合成比例、含量、压力、温度和混合气等因素对混合基质膜分离性能的影响。结果表明：CM与SPEEK之间具有良好的相容性并为气体分子提供了快速的传递通道。在改性CNT与MOF的质量比为5∶5、添加量为7%(质量)以及0.1 MPa和25℃的条件下，混合基质膜的分离性能最优，CO₂渗透性为844 Barrer，CO₂/N₂选择性为84，与纯SPEEK膜相比，分别提升了178%和163%，超过2019年上限。羧基化CNT的直孔通道缩短了CO₂的扩散路径，同时改性β-CD MOF表面的氨基载体提升了CO₂的溶解性，两者协同提高了混合基质膜的分离性能。此外，负载双填料的膜比单独负载相同含量的羧基化CNT或氨基化MOF的膜具有更好的分离性能。在360 h的测试过程中，混合基质膜保持较好的分离稳定性。

关键词: 混合基质膜, 磺化聚醚醚酮, β-环糊精金属有机骨架, 碳纳米管, CO₂/N₂分离

Abstract:

To achieve the CO₂ efficient separation in mixed matrix membranes (MMMs), a dual-filler (CM) of carboxyl modified multi-walled carbon nanotubes (CNT) and amino modified β-cyclodextrin metal organic framework (β-CD MOF) was designed and introduced to sulfonated poly(ether ether ketone) (SPEEK) to construct both CO₂ diffusion channels and affinity sites within the membranes, which enhanced the separation performance of MMMs. The chemical and pore structures of the dual-filler were characterized by FTIR and BET, and the filler-polymer interfacial interactions were verified by SEM, FTIR and mechanical properties of the membranes. The effects of the proportion, content, pressure, temperature and mixed gas on the separation performance of MMMs were investigated. The results showed that CM was compatible with SPEEK and provided fast transport channels for gas molecules. The SPEEK/CM-7 MMMs with mass ratio of 5∶5 displayed the optimal separation performance with a CO₂ permeability of 844 Barrer and a CO₂/N₂ selectivity of 84 at 0.1 MPa and 25℃, which were 178% and 163% higher than those of the pristine SPEEK membrane, respectively, surpassing the 2019 upper bound. The straight pore channels of functional CNT shortened the CO₂ diffusion path, while the amino carriers on the surface of modified MOF enhanced the CO₂ dissolution, which synergistically improved the separation performance of MMMs. Moreover, the membranes loaded with dual-filler had preferable separation performance than those loaded with the same amount of carboxyl modified CNT or amino modified MOF alone. During 360 h testing, the SPEEK/CM-7 MMMs remained good stability.

Key words: mixed matrix membrane, sulfonated poly(ether ether ketone), β-cyclodextrin metal organic framework, carbon nanotube, CO₂/N₂ separation

中图分类号:

TQ 028.8

裴仁花, 王永洪, 张新儒, 李晋平. 碳纳米管/环糊精金属有机骨架协同强化混合基质膜的CO₂分离[J]. 化工学报, 2022, 73(9): 3904-3914.

Renhua PEI, Yonghong WANG, Xinru ZHANG, Jinping LI. Synergistic of carbon nanotube/cyclodextrin metal organic framework for enhancing CO₂ separation of mixed matrix membranes[J]. CIESC Journal, 2022, 73(9): 3904-3914.

图/表 15

图1 β-CD MOF, 氨基化β-CD MOF, CM (质量比5∶5) 和羧基化CNT的红外光谱图

Fig.1 FTIR spectra of β-CD MOF, amino modified β-CD MOF, CM (mass ratio 5∶5) and carboxyl modified CNT

图2 羧基化CNT, CM (质量比5∶5) 和氨基化β-CD MOF的氮气吸-脱附曲线(a)和孔径分布(b)

Fig.2 N2 adsorption-desorption isotherms (a) and pore size distribution (b) of carboxyl modified CNT, CM (mass ratio 5∶5) and amino modified β-CD MOF

图3 纯SPEEK膜和SPEEK/CM混合基质膜的扫描电镜图

Fig.3 SEM images of the pristine SPEEK membrane and SPEEK/CM MMMs

图4 纯SPEEK膜和SPEEK/CM混合基质膜的红外光谱图

Fig.4 FTIR spectra of the pristine SPEEK membrane and SPEEK/CM MMMs

图5 CM含量对SPEEK/CM混合基质膜力学性能的影响

Fig.5 Effect of CM content on the mechanical properties of SPEEK/CM MMMs

图6 (a) 含水量与CM含量的关系; (b) CO2渗透性与总水量的相关性; (c) CO2/N2选择性与结合水的相关性; (d) 不同CM含量的膜的面积溶胀

Fig.6 (a) Relationship between water uptake and CM content; (b) Correlations between CO2 permeability and total water; (c) Correlations between CO2/N2 selectivity and bound water; (d) Area swelling of the membranes with different CM content

图7 羧基化CNT和氨基化β-CD MOF的质量比对SPEEK/CM混合基质膜分离性能的影响

Fig.7 Effect of mass ratio of carboxyl modified CNT and amino modified β-CD MOF on the separation performance of SPEEK/CM MMMs

表1 羧基化CNT， CM （质量比5∶5）和氨基化β-CD MOF的孔结构参数

Table 1 Pore structure parameters of carboxyl modified CNT， CM （mass ratio 5∶5） and amino modified β-CD MOF

样品	BET比表面积/(m²·g^-1)	总孔体积/ (cm³·g^-1)	BJH平均孔径/nm
羧基化CNT	117	0.26	8.90
CM	34	0.08	9.52
氨基化β-CD MOF	20	0.01	5.31

图8 CM含量对SPEEK/CM混合基质膜分离性能的影响

Fig.8 Effect of CM content on the separation performance of SPEEK/CM MMMs

图9 进料气压力对纯SPEEK膜和SPEEK/CM混合基质膜的CO2渗透性和CO2/N2选择性的影响

Fig.9 Effect of feed pressure on the CO2 permeability and CO2/N2 selectivity of the pristine SPEEK membrane and SPEEK/CM MMMs

图10 温度对膜性能的影响

Fig.10 Effect of temperature on the performance of the as-prepared membranes

图11 纯气和混合气条件下纯SPEEK膜和SPEEK/CM混合基质膜的CO2渗透性和CO2/N2选择性

Fig.11 CO2 permeability and CO2/N2 selectivity of the pristine SPEEK membrane and SPEEK/CM MMMs under pure gas and mixed gas conditions

图12 添加不同填料混合基质膜的气体分离性能

Fig.12 Gas separation performance of the MMMs with different fillers

图13 SPEEK/CM-7混合基质膜的稳定性

Fig.13 Stability of SPEEK/CM-7 MMMs

图14 所制备的膜与负载其他复合材料的膜的分离性能对比

Fig.14 Comparison of separation performance of the as-prepared membranes with MMMs loaded with other composite materials

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碳纳米管/环糊精金属有机骨架协同强化混合基质膜的CO₂分离

Synergistic of carbon nanotube/cyclodextrin metal organic framework for enhancing CO₂ separation of mixed matrix membranes

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