Pebax/a-MoS2/MIP-202混合基质膜的制备及CO2分离性能

doi:10.11949/0438-1157.20220628

摘要/Abstract

摘要：

为了获得高性能的CO₂/N₂分离膜，把空气中氧刻蚀的二硫化钼（a-MoS₂）和金属有机框架材料MIP-202通过机械力化学反应制备的双功能填料作为分散相，聚醚嵌段酰胺（Pebax-1657）作为连续相，采用溶液浇铸法制备了Pebax/a-MoS₂/MIP-202混合基质膜。采用FT-IR表征了填料的化学结构，借助ATR-FTIR、SEM、TG和力学性能测试表征了混合基质膜的化学结构、微观形貌结构、热稳定性和物理力学性能。研究了水含量、双功能填料配比、含量、膜两侧压差和操作温度对膜气体分离性能的影响，并考察了模拟烟道气（CO₂/N₂体积比15/85）条件下混合基质膜的长时间运行稳定性。结果表明：在温度为25℃、膜两侧压差为0.1 MPa的操作条件下，a-MoS₂与MIP-202质量比为5∶5和双功能填料含量为6%（质量）时，膜的气体分离性能达到最优，CO₂渗透性和CO₂/N₂选择性分别为380 Barrer和124.7，超过了2019年McKeown等提出的上限值。连续测试360 h后，混合基质膜的性能没有明显降低，其平均CO₂渗透性和CO₂/N₂选择性分别为358 Barrer和120.1。这主要是由于a-MoS₂和MIP-202协同提高了膜的气体分离性能。

关键词: 混合基质膜, 二硫化钼, MIP-202, 协同效应, CO₂分离

Abstract:

To obtain high-performance CO₂/N₂ separation membranes, a dual-functional filler prepared by mechanochemistry reaction of oxygen-etched molybdenum disulfide (a-MoS₂) and metal-organic framework material MIP-202 was used as the dispersed phase, and polyether block amide (Pebax-1657) was served as a continuous phase, and Pebax/a-MoS₂/MIP-202 mixed matrix membranes (MMMs) were prepared by solution casting. The chemical structure of filler was characterized by FT-IR. The chemical structure, microscopic structure, thermal stability and physical mechanical properties of MMMs were characterized by ATR-FTIR, SEM, TG and mechanical property testing. The effects of water content, dual-functional filler ratio, dual-functional filler content, feed pressure and operating temperature on the gas separation performance of the membranes were studied, and the long-time stability of MMMs under simulated flue gas (CO₂/N₂ volume ratio 15/85) conditions was investigated. The results showed that the best CO₂ permeability of MMMs was 380 Barrer with a CO₂/N₂ selectivity of 124.7 at 25℃ and 0.1 MPa, surpassing the upper bound proposed by McKeown et al in 2019, when the mass ratio of a-MoS₂ to MIP-202 was 5∶5 and the dual-functional filler content was 6%(mass). The separation performance of MMMs was not significantly degraded over 360 h testing, with an average CO₂ permeability of 358 Barrer and CO₂/N₂ selectivity of 120.1. This is mainly due to the synergistic improvement of the gas separation performance of the membrane by a-MoS₂ and MIP-202.

Key words: mixed matrix membranes, molybdenum disulfide, MIP-202, synergistic effect, CO₂ separation

中图分类号:

TQ 028.8

靳卓, 王永洪, 张新儒, 白雪, 李晋平. Pebax/a-MoS₂/MIP-202混合基质膜的制备及CO₂分离性能[J]. 化工学报, 2022, 73(10): 4527-4538.

Zhuo JIN, Yonghong WANG, Xinru ZHANG, Xue BAI, Jinping LI. Preparation of Pebax/a-MoS₂/MIP-202 mixed matrix membranes for CO₂ separation[J]. CIESC Journal, 2022, 73(10): 4527-4538.

图/表 12

图1 Pebax/a-MoS2/MIP-202混合基质膜的制备

Fig.1 Fabrication of Pebax/a-MoS2/MIP-202 MMMs

图2 a-MoS2/MIP-202的FT-IR表征

Fig.2 FT-IR characterization of a-MoS2/MIP-202

图3 膜的表征

Fig.3 Characterization of the membranes

表1 膜的热重表征参数

Table 1 Thermogravimetric characteristic parameters of the membranes

Membranes	Loading/%(mass)	Decomposition step/℃	T_max/℃	T_onset/℃	T_d5/℃	T_d10/℃
Pebax	0	353—462	419	353	360	380
Pebax/a-MoS₂/MIP-202 MMMs	2	353—455	415	353	357	375
	6	345—448	413	345	352	368
	8	338—448	411	338	345	367

图4 水含量对膜气体分离性能的影响

Fig.4 Effect of water content on the gas separation performance of the membranes

图5 a-MoS2与MIP-202的配比(a)和含量(b)对膜气体分离性能的影响

Fig.5 Effect of the mass ratio of a-MoS2 to MIP-202 (a) and loading (b) on the gas separation performance of the membranes

图6 膜两侧压差对膜气体分离性能的影响

Fig.6 Effect of pressure difference on the gas separation performance of the membranes

图7 温度对膜气体分离性能的影响

Fig.7 Effect of temperature on the gas separation performance of the membranes

图8 纯气和混合气测试条件下膜的气体分离性能

Fig.8 Gas separation performance of the membranes as determined by pure gas and mixed gas testing

图9 添加不同填料混合基质膜的气体分离性能

Fig.9 Gas separation performance of the MMMs with different fillers

图10 Pebax/a-MoS2/MIP-202-6混合基质膜的稳定性及与文献报道的混合基质膜对比

Fig.10 The stability of Pebax/a-MoS2/MIP-202-6 MMMs and comparison with reported MMMs in the literature

图11 Pebax/a-MoS2/MIP-202-6混合基质膜气体分离性能的增量及与上限对比

Fig.11 Enhancement of gas separation performance of Pebax/a-MoS2/MIP-202-6 MMMs and comparison with upper bound

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Pebax/a-MoS₂/MIP-202混合基质膜的制备及CO₂分离性能

Preparation of Pebax/a-MoS₂/MIP-202 mixed matrix membranes for CO₂ separation

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