UiO-66/PI混合基质气体分离膜研究
作者： 1大连理工大学化工学院，精细化工国家重点实验室，炭膜及多孔炭材料研究室，大连， 116024；2辽宁科技大学化工学院，鞍山， 114051
单位： 1大连理工大学化工学院，精细化工国家重点实验室，炭膜及多孔炭材料研究室，大连， 116024；2辽宁科技大学化工学院，鞍山， 114051
关键词： UiO-66；聚酰亚胺；混合基质膜；气体分离
DOI号：
分类号： TQ031.2
出版年,卷(期):页码： 2020, 40(6):71-78

摘要：

本文以具有较高热稳定性的UiO-66为掺杂剂、高自由体积的PI聚合物为基相，采用原位聚合掺杂的方式制备了UiO-66/PI混合基质膜，经进一步热处理制备了高性能的热重排混合基质膜。利用TG、FT-IR、SEM和XRD等表征方法探究了混合基质膜的化学结构、微观形貌以及分子链间距离。结果表明：原位掺杂方式将UiO-66纳米颗粒均匀分散于聚合物基质中。经热处理后，UiO-66仍可保持其晶体结构，同时进一步增大了聚合物基质的分子链间距离。UiO-66的引入同时提高了热重排膜的气体渗透系数和对CO2/CH4、CO2/N2的选择性。与未掺杂的膜相比，掺杂含量为3 wt.%的热重排混合基质膜的CO2渗透系数可高达3316 Barrer，提高了1.74倍，同时CO2/N2和CO2/CH4的选择性分别由24.4和27.5提高到35.7和33.2。热处理恒温时间的延长可进一步提高膜的气体渗透通量，其中CO2渗透系数最高可达11950 Barrer，对应CO2/CH4选择性为19。所制备的UiO-66/PI热重排混合基质膜对CO2/CH4和CO2/N2的分离性能超越了2008 Robeson上限，在CO2分离与捕集领域展现出较好的应用前景。

UiO-66/PI mixed matrix membranes (MMMs) were prepared by in-situ polymerization using UiO-66 with high thermal stability as filler and PI with high free volume as polymeric matrix, which were further heated to obtain the high-performance thermally rearranged MMMs. The chemical structure, micro-morphology and interchain distance of the MMMs were investigated via
TG, FT-IR, SEM and XRD. Results showed that the UiO-66 nanoparticles were dispersed uniformly into the polymeric matrix by the in-situ doping method. After thermal treatment, the crystal structure of UiO-66 was still maintained and the interchain distance was further enlarged. The gas permeabilities and selectivities for CO2/CH4 and CO2/N2 of the MMMs were both improved due to the incorporation of UiO-66. Compared with the membrane without incorporating UiO-66, the CO2
permeability of the thermally rearranged MMMs with 3 wt% loading could be as high as 3316 Barrer, which was 1.74 times higher. Meanwhile, the selectivities of CO2/N2 and CO2/CH4 were increased from 24.4 and 27.5 to 35.7 and 33.2 respectively. In addition, the gas permeabilities of the membranes were further enhanced when the thermal treatment time was extended. When the thermal time was 5 h, the CO2 gas permeability was 11950 Barrer and the corresponding CO2/CH4 selectivity was 19. The separation performance for CO2/CH4 and CO2/N2 of the UiO-66/PI thermally rearranged MMMs prepared in this work was beyond the upper bound of 2008 Robeson, showing that these membranes exhibited a potential application prospect for CO2 separation and capture.

基金项目：
国家自然科学基金面上项目“借助于聚合物聚集态结构的调控制备高性能气体分离炭膜”（21878033），国家自然科学基金重点基金“用于脱碳提纯氢气的CO2优先渗透分离膜研究”（21436009）

作者简介：

UiO-66/PI mixed matrix membranes (MMMs) were prepared by in-situ polymerization using UiO-66 with high thermal stability as filler and PI with high free volume as polymeric matrix, which were further heated to obtain the high-performance thermally rearranged MMMs. The chemical structure, micro-morphology and interchain distance of the MMMs were investigated via
TG, FT-IR, SEM and XRD. Results showed that the UiO-66 nanoparticles were dispersed uniformly into the polymeric matrix by the in-situ doping method. After thermal treatment, the crystal structure of UiO-66 was still maintained and the interchain distance was further enlarged. The gas permeabilities and selectivities for CO2/CH4 and CO2/N2 of the MMMs were both improved due to the incorporation of UiO-66. Compared with the membrane without incorporating UiO-66, the CO2
permeability of the thermally rearranged MMMs with 3 wt% loading could be as high as 3316 Barrer, which was 1.74 times higher. Meanwhile, the selectivities of CO2/N2 and CO2/CH4 were increased from 24.4 and 27.5 to 35.7 and 33.2 respectively. In addition, the gas permeabilities of the membranes were further enhanced when the thermal treatment time was extended. When the thermal time was 5 h, the CO2 gas permeability was 11950 Barrer and the corresponding CO2/CH4 selectivity was 19. The separation performance for CO2/CH4 and CO2/N2 of the UiO-66/PI thermally rearranged MMMs prepared in this work was beyond the upper bound of 2008 Robeson, showing that these membranes exhibited a potential application prospect for CO2 separation and capture.

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