基于TiO2溶胶杂化的分子筛炭膜制备及其结构与性能

doi:10.11949/0438-1157.20201679

摘要/Abstract

摘要：

以聚酰亚胺为前体，TiO₂溶胶为掺杂剂，经成膜和炭化制得杂化炭膜。采用热失重、电子显微镜、X-射线衍射、红外光谱和渗透法对前体的热性能、炭膜的微观形貌、微结构、表面官能团和气体分离性进行了表征。考察了TiO₂溶胶用量、渗透温度和渗透压力对炭膜的结构与性能影响。结果显示，掺杂TiO₂溶胶显著提高了最终炭膜渗透性和选择性；采用TiO₂溶胶量为10%前体所制备的杂化炭膜对H₂、CO₂、O₂渗透性分别为1993.8、1555.6、266.9 Barrer，同时H₂/N₂、CO₂/N₂、O₂/N₂选择性分别为93.6、73.0、12.5。

关键词: 膜, 气体, 分离, 聚酰亚胺, 二氧化钛

Abstract:

Using polyimide as the precursor and TiO₂ sol as the dopant, hybrid carbon membranes were prepared through membrane formation and carbonization. The thermal property of precursor, the microscopic morphology, microstructure, surface functional groups and gas permeation of carbon membranes were characterized by thermogravimetric analysis, electron microscope, X-ray diffraction, infrared spectroscopy and permeation testing, respectively. The effects of TiO₂ sol dosage, permeation temperature and permeation pressure on the structure and property of carbon membranes were investigated. Results show that the incorporation of TiO₂ sol obviously improves the permeability and selectivity of final carbon membranes. For hybrid carbon membranes prepared by the precursor containing 10% TiO₂, the permeability can respectively reach to 1993.8 Barrer for H₂, 1555.6 Barrer for CO₂ and 266.9 Barrer for O₂, along with the selectivity of 93.6 for H₂/N₂, 73.0 for CO₂/N₂ and 12.5 for O₂/N₂.

Key words: membranes, gas, separation, polyimide, titanium dioxide

中图分类号:

TQ 028.8

姚彦虎, 杨晨, 张兵, 吴永红, 王同华. 基于TiO₂溶胶杂化的分子筛炭膜制备及其结构与性能[J]. 化工学报, 2021, 72(8): 4418-4424.

Yanhu YAO, Chen YANG, Bing ZHANG, Yonghong WU, Tonghua WANG. Preparation, structure and properties of carbon molecular sieving membranes enabled by hybridization of TiO₂ sol[J]. CIESC Journal, 2021, 72(8): 4418-4424.

图/表 9

图1 TiO2溶胶杂化炭膜的制备示意图

Fig.1 Schematic of preparation of TiO2 sol hybrid carbon membrane

图2 前体的热失重曲线

Fig.2 Thermal weight loss curves of precursors

图3 膜的红外光谱图

Fig.3 Infrared spectra of membranes

图4 炭膜的XRD谱图

Fig.4 XRD patterns of carbon membranes

图5 杂化炭膜的SEM图片

Fig.5 SEM images of hybrid carbon membranes

图6 温度对杂化炭膜的气体渗透性影响.

Fig.6 Influence of temperature on the gas permeability of hybrid carbon membranes

图7 压力对炭膜气体渗透性影响

Fig.7 Influence of pressure on the gas permeability of carbon membranes

表1 杂化炭膜的气体分离性能（30℃，0.02 MPa）

Table 1 Gas separation performance of hybrid carbon membranes （30℃， 0.02 MPa）

Samples	Permeability /Barrer				Selectivity			Source
Samples	H₂	CO₂	O₂	N₂	H₂/N₂	CO₂/N₂	O₂/N₂	Source
CM-0%	114.4	159.0	85.8	8.51	13.4	18.8	10.1	This work
CM-5%	622.6	463.6	302.1	17.8	35.0	26.0	17.0
CM-10%	1993.8	1555.6	266.9	21.3	93.6	73.0	12.5
TiO₂ hybrid carbon membranes	—	120.22	4.87	2.07	—	31.88	2.35	[18]
FeO hybrid carbon membranes	280	110	30	8.3	33.7	13.3	3.6	[28]
CNTs hybrid carbon membranes	5824	6661	1259	253	23.02	26.33	4.98	[29]
SBA-15 hybrid carbon membranes	667.5	222.5	57.8	8.9	11.5	25	7.5	[30]

图8 Robeson上限图

Fig.8 Plots of Robeson’s upper bound

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基于TiO₂溶胶杂化的分子筛炭膜制备及其结构与性能

Preparation, structure and properties of carbon molecular sieving membranes enabled by hybridization of TiO₂ sol

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