PEBA/氮硫共掺杂多孔碳球混合基质膜的制备及CO2分离性能研究

doi:10.11949/0438-1157.20210563

摘要/Abstract

摘要：

为了获得高性能的混合基质膜，有效捕集烟道气中的CO₂，设计了对CO₂有优异的扩散选择性和吸附选择性的氮硫共掺杂多孔碳球添加剂，实现了烟道气中CO₂/N₂的高效分离。选用表面含氧基团丰富的葡萄糖作为碳源，硫脲作为氮源和硫源，通过水热法制备了氮硫共掺杂碳球（NSC），并用KOH活化，获得了具有多孔结构的氮硫共掺杂碳球（NSPC），再加入聚醚嵌段酰胺（PEBA）中制备出PEBA/NSPC混合基质膜。采用FTIR、XRD和BET表征了材料的化学结构和孔结构，借助力学性能表征了膜的两相界面相容性。系统研究了PEBA/NSPC混合基质膜中葡萄糖与硫脲的质量比、NSC和KOH的质量比、NSPC的添加量、操作压力、操作温度，以及模拟烟道气条件对膜CO₂渗透性、CO₂/N₂选择性的影响。结果表明：NSPC材料成功实现了氮、硫元素的共掺杂，而且具有较好的孔结构。在操作温度25℃、操作压力0.2 MPa的条件下，混合基质膜中NSPC添加量为3%（质量）时气体分离性能最优，CO₂渗透系数和CO₂/N₂选择性分别为589 Barrer和64，相比纯PEBA膜分别提高了244%和139%。这是因为多孔碳球的微孔结构显著提高了CO₂的扩散选择性，同时氮、硫元素的掺杂因为酸碱相互作用和良好亲和性有效提高了CO₂的吸附选择性。稳定性实验表明，PEBA/NSPC混合基质膜在360 h连续运行过程中气体分离性能稳定，具有较好的工业应用前景。

关键词: 混合基质膜, 活性炭, CO₂捕集, 烟道气, 聚醚嵌段酰胺

Abstract:

In order to obtain high-performance mixed matrix membrane to effectively capture CO₂in flue gas, this paper designed a N,S co-doped porous carbon sphere with excellent diffusion and adsorption selectivity for CO₂as an additive to achieve the efficient separation of CO₂/N₂ from flue gas. Glucose with rich oxygen groups as the carbon source and thiourea as nitrogen and sulfur source are selected to prepare the nitrogen and sulfur co-doped carbons (NSC) by hydrothermal method. The porous structure of NSPC is produced by the activation of NSC with KOH. FTIR, XRD and BET tests indicate the successful synthesis of NSPC, which has high specific surface area and microporosity. The optimal ratio of glucose to thiourea, the optimal ratio of NSC to KOH in the synthesis of NSPC, the effect of NSPC content, feed pressure, test temperature on the performance of the membrane are studied. It proves that the nitrogen, sulfur-containing CO₂ affinity sites and micropores in NSPC have beneficial effects on the gas separation performance of the membrane. The results show that when the NSPC content is 3%(mass), the performance of membrane is the best at 25℃ and 0.2 MPa. The CO₂ permeability is 589 Barrer, and the CO₂/N₂ selectivity is 64. The performance of the membrane in the mixed gas is slightly lower than that in the pure gas, and it can remain stable for 360 h, which has good industrial application prospects.

Key words: mixed matrix membrane, activated carbon, CO₂ capture, flue gas, PEBA

中图分类号:

TQ 028.8

周毅,王永洪,张新儒,李晋平. PEBA/氮硫共掺杂多孔碳球混合基质膜的制备及CO₂分离性能研究[J]. 化工学报, 2021, 72(10): 5237-5246.

Yi ZHOU,Yonghong WANG,Xinru ZHANG,Jinping LI. Preparation of PEBA/N, S co-doped porous carbon sphere mixed matrix membrane for CO₂ separation[J]. CIESC Journal, 2021, 72(10): 5237-5246.

图/表 12

图1 NSPC和PEBA/NSPC 混合基质膜的制备

Fig.1 Schematic representation of the fabrication of NSPC and PEBA/NSPC

图2 NSPC的表征结果

Fig.2 Characterization of NSPC

图3 PEBA和PEBA/NSPC-X MMMs的红外光谱图和力学性能

Fig.3 FTIR spectra and mechanical properties of the PEBA and PEBA/NSPC-X MMMs

图4 葡萄糖和硫脲的质量比对PEBA/NSPC混合基质膜的CO2渗透系数和CO2/N2选择性的影响

Fig.4 Effect of the mass ratio of glucose to thiourea on pure gas CO2 permeability and CO2/N2 selectivity of the PEBA/NSPC MMMs

图5 NSC与KOH的质量比对PEBA/NSPC混合基质膜分离性能的影响

Fig.5 Effect of the mass ratio of NSC to KOH on pure gas CO2 permeability and CO2/N2 selectivity of the PEBA/NSPC MMMs

图6 NSPC含量对PEBA/NSPC-X MMMs的CO2渗透系数和CO2/N2选择性的影响

Fig.6 Effect of NSPC loading on pure gas CO2 permeability and CO2/N2 selectivity of the PEBA/NSPC-X MMMs

图7 操作压力对纯PEBA膜和PEBA/NSPC-X MMMs CO2渗透性和CO2/N2选择性的影响

Fig.7 Effect of feed pressure on the CO2 permeability and CO2/N2 selectivity of pure PEBA and the PEBA/NSPC-X MMMs

图8 温度对膜性能的影响

Fig.8 Effect of temperature on the performance of membranes

图9 纯气和混合气测试条件下膜的CO2渗透性和CO2/N2选择性

Fig.9 CO2 permeability and CO2/N2 selectivity of as-prepared membranes as determined by pure-gas and mixed-gas testing

图10 不同填料对混合基质膜气体分离性能的影响[添加量为3%(质量)]

Fig.10 Gas separation performance of the MMMs with different fillers at the loading of 3%(mass)

图11 PEBA/NSPC-3混合基质膜的稳定性

Fig.11 The stability of PEBA/NSPC-3

图12 PEBA/NSPC-3混合基质膜性能与文献结果对比

Fig.12 The comparison of separation performance between PEBA/NSPC-3 MMMs and reported MMMs

参考文献 32

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PEBA/氮硫共掺杂多孔碳球混合基质膜的制备及CO₂分离性能研究

Preparation of PEBA/N, S co-doped porous carbon sphere mixed matrix membrane for CO₂ separation

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