SPEEK/PSI半互穿网络共混膜的制备及其CO2分离研究

doi:10.11949/0438-1157.20200462

化工学报 ›› 2020, Vol. 71 ›› Issue (12): 5813-5820.DOI: 10.11949/0438-1157.20200462

• 材料化学工程与纳米技术 • 上一篇下一篇

SPEEK/PSI半互穿网络共混膜的制备及其CO₂分离研究

高殷¹(),王永洪^1,²,张新儒^1,²(),李晋平^1,²,凌军³

^1.太原理工大学化学化工学院，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
^3.云南中烟工业有限责任公司技术中心，云南昆明 650231

收稿日期:2020-04-30 修回日期:2020-06-09 出版日期:2020-12-05 发布日期:2020-12-05
通讯作者: 张新儒
作者简介:高殷(1995—)，女，硕士研究生，gaoyin0426@163.com
基金资助:
国家自然科学基金面上项目(22078216);国家自然科学基金青年基金项目(21506140);山西省煤层气联合基金项目(2015012009)

Preparation of SPEEK/PSI semi-interpenetrating network blend membrane and its CO₂ separation

GAO Yin¹(),WANG Yonghong^1,²,ZHANG Xinru^1,²(),LI Jinping^1,²,LING Jun³

^1.College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China
^2.Shanxi Key Laboratory of Gas Energy Efficient and Clean Utilization, Taiyuan 030024, Shanxi, China
^3.Technology Center, China Tobacco Yunnan Industrial Co. Ltd. , Kunming 650231, Yunnan, China

Received:2020-04-30 Revised:2020-06-09 Online:2020-12-05 Published:2020-12-05
Contact: ZHANG Xinru

摘要/Abstract

摘要：

为了获得高性能的气体分离膜，实现烟道气中CO₂/N₂高效分离回收，以磺化聚醚醚酮（SPEEK）和聚琥珀酰亚胺（PSI）为原料，己二胺为交联剂，原位交联反应制备富含氨基的半互穿网络共混膜，在膜内构建CO₂传递通道和亲和位点，并采用红外光谱对共混膜的结构进行表征。研究水含量、PSI用量和进料气压力对膜气体分离性能的影响，在混合气条件下考察其气体分离性能和长时间运行稳定性。研究结果表明：SPEEK与PSI两相界面相容性较好，它们之间存在较强的相互作用，且呈半互穿网络微结构；PSI含量为60%（质量）时，纯气和混合气条件下CO₂渗透性分别为652和601 Barrer，对应的CO₂/N₂选择性为67.6和60.3，优于纯SPEEK膜，且超过2008年的Robeson上限；共混膜运行360 h后，CO₂渗透性和CO₂/N₂选择性仍然稳定。这主要是因为SPEEK与PSI形成富含氨基的半互穿网络微结构后，一方面提供了CO₂促进传递载体；另一方面，增强了共混膜的保水性能，形成大量CO₂传递水通道。

关键词: 共混膜, 聚琥珀酰亚胺, 磺化聚醚醚酮, 半互穿网络结构, CO₂分离

Abstract:

To obtain high-performance gas separation membranes and realize high-efficiency separation and recovery of CO₂/N₂ in flue gas, the amino-rich semi-interpenetrating network blend membranes were prepared by in-situ crosslinking reaction, which provided CO₂ transport channels and affinity sites. Sulfonated poly(ether ether ketone) (SPEEK) and polysuccinimide (PSI) were used as raw materials, and hexamethylenediamine was crosslinking agent. The structure of the blend membranes was characterized by Fourier-transform infrared spectroscopy. The effects of water content, PSI dosage and feed gas pressure on the gas separation performance were studied, and its gas separation performance and the long-time stability were investigated under mixed gas conditions. The results showed that SPEEK and PSI have a good compatibility, and there is a strong interaction between them, which exhibited the semi-interpenetrating network microstructure in the membranes. When the PSI loading is 60%(mass), the CO₂ permeability of pure gas and mixed gas are 652 and 601 Barrer, respectively, and the corresponding CO₂/N₂ selectivity is 67.6 and 60.3, which is better than that in pristine SPEEK membrane, surpassing 2008 Robeson upper bound. The CO₂ permeability and CO₂/N₂ selectivity are still stable after 360 h durability test of SPEEK/PSI-60 blend membrane. This is mainly due to the formation of the amino-rich semi-interpenetrating network microstructure between SPEEK and PSI, which not only provides CO₂ facilitated transport carriers, but also enhances the water retention performance of the blend membranes and forms a large number of CO₂ transport water channels.

Key words: blend membrane, polysuccinimide, sulfonated poly(ether ether ketone), semi-interpenetrating network structure, CO₂ separation

中图分类号:

TQ 028.8

高殷,王永洪,张新儒,李晋平,凌军. SPEEK/PSI半互穿网络共混膜的制备及其CO₂分离研究[J]. 化工学报, 2020, 71(12): 5813-5820.

GAO Yin,WANG Yonghong,ZHANG Xinru,LI Jinping,LING Jun. Preparation of SPEEK/PSI semi-interpenetrating network blend membrane and its CO₂ separation[J]. CIESC Journal, 2020, 71(12): 5813-5820.

图/表 7

图1 半互穿网络共混膜制备图

Fig.1 Preparation diagram of semi-interpenetrating network blend membranes

图2 纯SPEEK膜、PSI和SPEEK/PSI-60共混膜的全反射红外光谱图

Fig.2 ATR-FTIR spectra of the pristine SPEEK membrane, PSI and SPEEK/PSI-60 blend membrane

图3 PSI含量与吸水量之间的关系(a)；CO2渗透性与总水量之间的关系(b)；CO2/N2选择性与结合水之间的关系(c)；不同PSI含量的SPEEK/PSI共混膜的溶胀面积(d)

Fig.3 Relation between PSI loading and water uptake (a); Relation between CO2 permeability and total water content (b); Relation between CO2/N2 selectivity and bound water content(c)； Area swelling of SPEEK/PSI blend membranes with different PSI loading(d)

图4 PSI含量对SPEEK/PSI共混膜气体分离性能的影响

Fig.4 Effect of PSI loading on gas separation performance of the SPEEK/PSI blend membranes

图5 进料气压力对纯SPEEK膜和SPEEK/PSI共混膜CO2渗透性(a)和CO2/N2选择性(b)的影响

Fig.5 Effect of feed gas pressure on CO2 permeability (a) and CO2/N2 selectivity (b) of the pristine SPEEK membrane and the SPEEK/PSI blend membranes

图6 所制膜在纯气与混合气中的CO2渗透性(a)和CO2/N2选择性(b)(混合气：15%(体积) CO2和85%(体积) N2；1 bar；室温；气体相对湿度100%)

Fig.6 Comparison of CO2 permeability (a) and CO2/N2 selectivity (b) of as-prepared membranes as determined by pure-gas and mixed-gas testing(mixed gas: 15%(vol) CO2 and 85%(vol) N2; 1 bar; room temperature; 100% relative humidity)

图7 SPEEK/PSI-60共混膜的稳定性(a)及Robeson上限(b)

Fig.7 The stability (a) and Robeson upper bound (b) of SPEEK/PSI-60 blend membrane

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SPEEK/PSI半互穿网络共混膜的制备及其CO₂分离研究

Preparation of SPEEK/PSI semi-interpenetrating network blend membrane and its CO₂ separation

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