GO-TSC/聚酰亚胺混合基质膜的制备及气体分离性能研究

doi:10.19964/j.issn.1006-4990.2020-0658

摘要/Abstract

摘要：

使用氨基硫脲（TSC）对氧化石墨烯（GO）进行改性,制备GO-TSC层状复合材料。随后,将该复合材料加入到Matrimid^®5218（PI）基质中,制备用于二氧化碳分离的混合基质膜（MMMs）。通过TGA、SEM及气体分离性能测试考察了GO-TSC对膜热稳定性、结构和气体分离性能等的影响。SEM结果显示GO-TSC可均匀分散在聚合物基质上并与基质紧密结合;TGA结果显示混合基质膜在250 ℃以上仍保持稳定。与纯PI膜相比,MMMs显著增强了二氧化碳的渗透性。GO-TSC中所含的氨基与二氧化碳具有良好的亲和力,增加的碱性位点可以有效地转运二氧化碳。GO-TSC的层状结构增加了气体的传输路径,不利于大动态直径气体（甲烷、氮气）的通过,从而提高了分离性能。GO-TSC负载量为0.75%（质量分数）时混合基质膜的分离性能最佳。相比较纯PI膜,混合基质膜的二氧化碳渗透系数和二氧化碳/甲烷、二氧化碳/氮气分离系数分别提高了42.16%、95.79%和83.72%。

关键词: 氧化石墨烯, 聚酰亚胺, 混合基质膜, 气体分离

Abstract:

Graphene oxide（GO） was modified using thiosemicarbazide（TSC） for the fabrication of flat sheet GO-TSC cmpo-site.Subsequently,this composite was incorporated into the Matrimid^®5218（PI） matrix to fabricate mixed matrix membranes（MMMs） for CO₂ separation.Through TGA,SEM and gas separation performance tests,influence of GO-TSC on thermal sta-bility,structure and gas separation performance of the mixed matrix membrane was investigated.SEM showed that GO-TSC could be uniformly dispersed in the polymer matrix and tightly combined with the matrix;TGA result showed that decomposi-tion temperature of mixed matrix membranes was above 250 ℃.MMMs showed significantly enhanced CO₂ permeability com-pared with pure PI membrane.The amino group contained in GO-TSC had a good affinity with CO₂,and the increased amidogen sites could effectively transport CO₂.The GO-TSC lamellar structure increased the gas transmission path,which was not conducive to the passage of large dynamic diameter gases（CH₄,N₂）,thereby improving the separation performance.The MMMs doped with GO-TSC-0.75% showed optimal gas separation performance.Compared with pure PI membrane,the CO₂ permeability,CO₂/CH₄ selectivity and CO₂/N₂ selectivity of the MMMs were increased by 42.16%,95.79% and 83.72%,respectively.

Key words: graphene oxide, polyimide, mixed matrix membrane, gas separation

中图分类号:

TQ028.8

郭欣,衣华磊,袁玮良,郝蕴,段翠佳,陈赞. GO-TSC/聚酰亚胺混合基质膜的制备及气体分离性能研究[J]. 无机盐工业, 2021, 53(10): 74-80.

Guo Xin,Yi Hualei,Yuan Weiliang,Hao Yun,Duan Cuijia,Chen Zan. Study on preparation of GO-TSC/polyimide mixed matrix membrane and its gas separation performance[J]. Inorganic Chemicals Industry, 2021, 53(10): 74-80.

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混合基质膜	度数/（°）	间距/nm
PI	15.90	0.562
PI/GO-TSC-0.5%	16.17	0.553
PI/GO-TSC-0.75%	16.29	0.549
PI/GO-TSC-1%	16.35	0.547
PI/GO-TSC-1.25%	16.47	0.543
PI/GO-TSC-1.5%	16.61	0.538

填料	P （CO₂）/Barrer	α （CO₂/CH₄）	α （CO₂/N₂）	测试条件
SO₃H-MCM-41^[25]	11.20	40.50	37.40	0.4 MPa,35 ℃
POSS-Zn^2+[26]	4.00	57.60	30.76	1.0 MPa,35 ℃
PEGSS^[27]	10.42	49.62	47.36	0.1 MPa,40 ℃
C60^[28]	3.79	34.80	23.70	1.0 MPa,35 ℃
CU-BPY-HFS^[29]	10.40	27.40	33.40	0.39 MPa,35 ℃
MCM-48^[30]	9.35	33.39	31.16	0.25 MPa,35 ℃
GO-TSC	10.11	60.55	51.86	0.2 MPa,35 ℃

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