MOFs基丙烯/丙烷高效分离混合基质膜研究进展

doi:10.16085/j.issn.1000-6613.2022-1187

摘要/Abstract

摘要：

丙烯是三大合成材料的基本原料之一，在国民经济中占有十分重要的地位，但其生产过程存在分离与纯化能耗较高的问题。将功能纳米填料引入聚合物基质制备的混合基质膜具有良好的渗透选择性，有望大幅降低丙烯分离与纯化所需的能耗，是膜分离领域的研究热点。本文综述了聚合物结构对丙烯/丙烷膜分离性能的影响规律，总结了混合基质膜丙烯/丙烷分离性能的重要影响因素。然后，分别从聚合物基质和MOFs填料入手，介绍了MOFs基丙烯/丙烷高效分离混合基质膜的研究现状，并从改善界面相容性、调控膜填料结构和调控膜基质结构三个方面，详细讨论了混合基质膜分离性能的优化方法。最后，针对混合基质膜丙烯/丙烷分离过程中存在的问题，对丙烯、丙烷分子在混合基质膜中传递机制进行了深入的分析，并对丙烯/丙烷分离混合基质膜的设计制备和应用研究进行了展望。

关键词: 膜分离, 丙烯/丙烷分离, 金属有机骨架, 混合基质膜

Abstract:

Propylene, as one of the basic raw materials of the three major synthetic materials, has a vital position in the national economy, but the energy consumption required for separation and purification in its production process is extremely high. Mixed matrix membrane is prepared by introducing functional nanofillers into polymer matrix and can show excellent separation ability for propylene and propane. It is believed that such membranes can substantially reduce the energy consumption of propylene purification, and has become a hotspot in the field of gas separation. In this study, the effects of polymer structure on the separation performance of propylene/propane membrane are reviewed, and the important factors affecting the separation performance of propylene/propane in mixed matrix membranes is summarized. Then, the progress in propylene/propane separation mixed matrix membranes (MMMs) is reviewed based on the point view of polymer matrix and MOFs filler. The optimization method of MMMs is discussed in detail from three aspects: improving interface compatibility, regulating membrane packing structure and regulating membrane matrix structure. Finally, in view of the problems existing in the process of mixed matrix membranes for propylene/propane separation, the transport mechanism of propylene and propane molecules in mixed matrix membranes is analyzed. The future research on MMMs for propylene/propane separation is also proposed.

Key words: membrane separation, propylene/propane separation, metal organic frameworks(MOFs), mixed matrix membrane

中图分类号:

TQ028.8

常晓青, 彭东来, 李东洋, 张延武, 王景, 张亚涛. MOFs基丙烯/丙烷高效分离混合基质膜研究进展[J]. 化工进展, 2023, 42(4): 1961-1973.

CHANG Xiaoqing, PENG Donglai, LI Dongyang, ZHANG Yanwu, WANG Jing, ZHANG Yatao. Recent progress on mixed matrix membrane for efficient C₃H₆/C₃H₈ separation[J]. Chemical Industry and Engineering Progress, 2023, 42(4): 1961-1973.

图/表 11

参考文献 75

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聚合物	测试温度/℃	原料侧压力/atm	自由体积分数FFV/%	丙烯渗透通量/Barrer	选择性C₃H₆/C₃H₈	参考文献
Matrimid^®	35	2.0	—	0.10	10.0	[29]
6FDA-mPD	35	3.8	15.6	0.13	10.0	[30]
6FDA–IPDA	35	3.8	16.8	0.58	15.0	[30]
6FDA-6FpDA	35	3.8	19.0	0.89	16.0	[30]
6FDA-DDBT	50	2.0	16.9	0.76	27.0	[7]
6FDA-TrMPD	50	2.0	18.2	30	11.0	[7]
6FDA-TeMPD	50	2.0	18.2	37	7.0	[7]
PIM-PI-OH (250℃)	35	2.0	—	3.50	30.0	[31]
PIM	30	1.0	22.0	1051	7.5	[32]
KAUST-PI-1	35	2.0	—	817	16	[33]

聚合物	测试温度/℃	原料侧压力/atm	自由体积分数FFV/%	丙烯渗透通量/Barrer	选择性C₃H₆/C₃H₈	参考文献
Matrimid^®	35	2.0	—	0.10	10.0	[29]
6FDA-mPD	35	3.8	15.6	0.13	10.0	[30]
6FDA–IPDA	35	3.8	16.8	0.58	15.0	[30]
6FDA-6FpDA	35	3.8	19.0	0.89	16.0	[30]
6FDA-DDBT	50	2.0	16.9	0.76	27.0	[7]
6FDA-TrMPD	50	2.0	18.2	30	11.0	[7]
6FDA-TeMPD	50	2.0	18.2	37	7.0	[7]
PIM-PI-OH (250℃)	35	2.0	—	3.50	30.0	[31]
PIM	30	1.0	22.0	1051	7.5	[32]
KAUST-PI-1	35	2.0	—	817	16	[33]

样品	扩散系数/10⁹cm²·s^-1		扩散选择性	溶解系数(标准状况) /0.0075cm³·cm^-3·Pa^-1		溶解选择性	渗透通量/Barrer		选择性
样品	丙烯	丙烷	丙烯/丙烷	丙烯	丙烷	丙烯/丙烷	丙烯	丙烷	丙烯/丙烷
PI	5.29±0.14	0.51±0.01	10.40±0.10	3.17±0.06	2.87±0.13	1.10±0.03	16.63±0.14	1.47±0.05	11.30±0.30
PZ67-20	7.72±0.06	0.31±0.01	24.80±0.20	4.40±0.09	3.66±0.11	1.20±0.01	34.14±0.04	1.14±0.01	29.90±0.20
PZ8-20	8.09±0.08	0.43±0.04	18.70±1.60	4.67±0.14	4.18±0.30	1.10±0.04	37.73±0.56	1.82±0.06	20.70±0.40

样品	扩散系数/10⁹cm²·s^-1		扩散选择性	溶解系数(标准状况) /0.0075cm³·cm^-3·Pa^-1		溶解选择性	渗透通量/Barrer		选择性
样品	丙烯	丙烷	丙烯/丙烷	丙烯	丙烷	丙烯/丙烷	丙烯	丙烷	丙烯/丙烷
PI	5.29±0.14	0.51±0.01	10.40±0.10	3.17±0.06	2.87±0.13	1.10±0.03	16.63±0.14	1.47±0.05	11.30±0.30
PZ67-20	7.72±0.06	0.31±0.01	24.80±0.20	4.40±0.09	3.66±0.11	1.20±0.01	34.14±0.04	1.14±0.01	29.90±0.20
PZ8-20	8.09±0.08	0.43±0.04	18.70±1.60	4.67±0.14	4.18±0.30	1.10±0.04	37.73±0.56	1.82±0.06	20.70±0.40

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