CO2捕集炭膜的前驱体结构设计及性能

doi:10.7503/cjcu20170058

高等学校化学学报 ›› 2017, Vol. 38 ›› Issue (10): 1850.doi: 10.7503/cjcu20170058

CO₂捕集炭膜的前驱体结构设计及性能

宋晶¹, 李琳¹(), 鲁云华^1,², 徐瑞松¹, 金鑫¹, 王春雷¹, 王同华¹()

1. 大连理工大学化工学院, 精细化工国家重点实验室, 炭素实验室, 大连 116024
2. 辽宁科技大学化学工程学院, 鞍山 114051

收稿日期:2017-01-23 出版日期:2017-10-10 发布日期:2017-09-22
作者简介:联系人简介: 李琳, 女, 博士, 讲师, 主要从事炭基膜材料的开发及应用. E-mail:lilin121@dlut.edu.cn;王同华, 男, 教授, 博士生导师, 主要从事炭材料和膜材料制备及应用的研究. E-mail:wangth@dlut.edu.cn
基金资助:
国家自然科学基金(批准号: 21436009, 21376037, 21406102, 21576035, 21506020)、中央高校基本科研业务费(批准号: DUT16RC(4)05)和中国博士后科学基金(批准号: 2014M561232)资助

Precursors Structural Design and Property of Carbon Membrane for CO₂ Capture^†

SONG Jing¹, LI Lin^1,^*(), LU Yunhua^1,², XU Ruisong¹, JIN Xin¹, WANG Chunlei¹, WANG Tonghua^1,^*()

1. Carbon Research Lab, State Key Lab of Fine Chemicals, School of Chemical Engineering,Dalian University of Technology, Dalian 116024, China
2. School of Chemical Engineering, University of Science and Technology Liaoning, Anshan 114051, China

Received:2017-01-23 Online:2017-10-10 Published:2017-09-22
Contact: LI Lin,WANG Tonghua E-mail:lilin121@dlut.edu.cn;wangth@dlut.edu.cn
Supported by:
† Supported by the National Natural Science Foundation of China(Nos.214360092, 21376037, 21406102, 21576035, 21506020), the Fundamental Research Funds for the Central Universities, China[No.DUT16RC(4)05] and the China Postdoctoral Science Foundation(No.2014M561232)

摘要/Abstract

摘要：

从分子结构设计出发, 合成了一系列新型刚性、高自由体积的聚酰亚胺炭膜前驱体, 并制备了炭膜. 采用热重分析(TGA)、傅里叶变换红外光谱(FTIR)、 X射线衍射(XRD)和高分辨透射电子显微镜(HRTEM)研究了不同聚酰亚胺前驱体的热分解特性及在热解炭化过程中化学结构、微结构的变化规律; 测试了所制备炭膜的气体分离性能. 结果表明, 前驱体的自由体积分数显著影响炭膜的气体分离性能; 聚合物结构越具刚性, 自由体积越大, 所得炭膜结构越疏松, 极微孔道尺寸越大, 越有利于气体分子在炭膜极微孔道中的渗透、扩散与传输. 其中, 刚性大体积基团芴基、酚酞cardo基团和六氟异丙基的引入能有效破坏分子链间的堆积, 提高聚合物的自由体积, 所形成炭膜的结构较疏松, 均表现出优异的气体渗透性和分离选择性,超越了Robeson上限, 解决了传统炭膜气体渗透性能低的问题. 特别是采用羟基官能化聚酰亚胺前驱体制备的炭膜在保持较高气体分离选择性的同时, CO₂气体的渗透性高达24770 Barrer(1 Barrer≈7.5×10^-18 m²·s^-1·Pa^-1), 可实现对CO₂的有效分离和捕集, 展现出良好的商业化应用前景.

关键词: 炭膜, 气体分离, 前驱体结构, 自由体积, 聚酰亚胺

Abstract:

A series of novel polyimide precursors with rigidity and high free volume was designed and synthesized for the preparation of carbon membranes. The pyrolytic characteristics of polyimides and chemical structures and microstructures of derived carbon membranes were characterized by means of thermogravimetric analysis(TG), Fourier transform infrared spectroscopy(FTIR), X-ray diffraction(XRD) and high-resolution transmission electron microscopy(HRTEM). The gas separation performance of carbon membranes was evaluated using pure gases H₂, O₂, N₂, CO₂ and CH₄. The results indicated that space configuration and free volume of polyimide precursors significantly affected the microstructures and gas separation performance of derived carbon membranes. The higher the structure rigidity of polyimide was, the higher its fractional free volume(FFV) was, the microstructure of prepared carbon membrane became looser and ultramicropore size became larger, resulting in the higher gas permeability of carbon membrane. Wherein, introduction of rigid groups such as fluorene, phthalide, hexafluoroisopropyl in polyimides could effectively disrupt the packing between the molecular chains and enhance the FFV of polyimides. The derived carbon membranes with looser microstructures exhibited excellent gas separation performance which surpassed the Robeson upper bond. Especially, the carbon membrane prepared from ortho-hydroxyl functionalized polyimide exhibited the highest gas permeability among the seven carbon membranes, that was 24770 Barrer(1 Barrer≈7.5×10^-18 m²·s^-1·Pa^-1) for CO₂, showing an attractive application prospect for the CO₂ separation and capture.

Key words: Carbon membrane, Gas separation, Precursor structure, Fractional free volume, Polyimide

中图分类号:

O647
O626

TrendMD:

宋晶, 李琳, 鲁云华, 徐瑞松, 金鑫, 王春雷, 王同华. CO₂捕集炭膜的前驱体结构设计及性能. 高等学校化学学报, 2017, 38(10): 1850.

SONG Jing, LI Lin, LU Yunhua, XU Ruisong, JIN Xin, WANG Chunlei, WANG Tonghua. Precursors Structural Design and Property of Carbon Membrane for CO₂ Capture^†. Chem. J. Chinese Universities, 2017, 38(10): 1850.

图/表 12

Fig.1 Upper bound correlation for CO2/CH4 separation[9]

Fig.2 Chemical structures of different polyimides

Table 1 Fractional free volume of different polyimides

Precursor structure	Fractional free volume^[26]	Precursor structure	Fractional free volume^[26]
BAF:BAHF-6FDA	0.212	BAF-CBDA	0.168
BAF-6FDA	0.213	BAF-BPDA	0.161
BATPPP-6FDA	0.194	BAF-ODPA	0.153
BAPPP-6FDA	0.192

Fig.3 TGA(A) and DTG(B) curves of different polyamic acids

Fig.4 FTIR spectra of carbon membranes based on different polyimides

Fig.5 XRD patterns of carbon membranes based on different polyimides

Table 2 d(002) values of carbon membranes based on different polyimides

Precursor structure	2θ/(°)	d(002)/nm
BAF:BAHF-6FDA	19.25	0.461
BAF-6FDA	19.92	0.445
BATPPP-6FDA	20.99	0.423
BAPPP-6FDA	21.04	0.422
BAF-CBDA	22.44	0.396
BAF-ODPA	23.69	0.375
BAF-BPDA	24.32	0.366

Fig.6 TEM images of carbon membranes based on BAF:BAHF-6FDA(A) and BAF-CBDA(B)

Table 3 Pure gas separation properties of carbon membranes based on different polyimides

Precursor structure	Pure gas permeability/Barrer^*					Selectivity
Precursor structure	H₂	O₂	N₂	CO₂	CH₄	O₂/N₂	CO₂/CH₄
BAF:BAHF-6FDA	11638	3297	798	24770	851	4.13	29.11
BATPPP-6FDA	10054	1849	351	9676	321	5.28	30.13
BAF-6FDA	6773	1423	215	7362	206	6.63	35.68
BAPPP-6FDA	4494	912	130	5253	108	6.99	48.68
BAF-ODPA	1465	330	114	1685	128	2.89	13.14
BAF-BPDA	927	215	49	1497	55	4.42	26.99
BAF-CBDA	784	159	32	1047	26	5.01	40.36

Fig.7 CO2 permeability of carbon membranes based on different polyimides as a function of their reciprocal FFV

Fig.8 Permeability of carbon membranes based on different polyimides as a function of kinetic diameter of gas molecules

Fig.9 Gas separation performance of membranes for CO2/CH4 gas pairs against Robeson trade-off line● Carbon membranes in this study; ▲ carbon membranes from Ref.[7]; ■ polymer membranes from Ref.[9,10].

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CO₂捕集炭膜的前驱体结构设计及性能

Precursors Structural Design and Property of Carbon Membrane for CO₂ Capture^†

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