磺化CAU-1强化聚乙烯胺促进传递膜的CO2/N2分离性能

doi:10.11949/0438-1157.20250130

摘要/Abstract

摘要：

混合基质膜结合了聚合物和无机材料的优点，性能可超过聚合物膜，在气体分离方面具有广泛的应用前景。为了获得高性能的CO₂/N₂分离膜，利用丙烯基-1，3-磺酸内酯（BS）的环氧基团与CAU-1的伯胺基团开环反应制备磺化CAU-1（CAU-1@BS）。然后，将CAU-1@BS添加到聚乙烯胺（PVAm）中制备制膜液，将其涂覆在亲水性改性聚砜超滤膜上制备得到混合基质复合膜。借助XPS、FTIR和BET表征了CAU-1@BS的化学结构和孔隙结构，并通过SEM表征了膜的形貌结构。此外，还研究了混合基质复合膜的制备条件和测试条件对气体分离性能的影响。研究结果表明，当CAU-1@BS的含量为7%（质量分数）时，制备的混合基质复合膜表现出优异的分离性能，其CO₂渗透速率为505 GPU（1 GPU=3.38×10^-10 mol·m^-2·S^-1·Pa^-1），CO₂/N₂选择性为67，与纯PVAm膜（CO₂渗透速率为296 GPU；CO₂/N₂选择性为39）相比，分别提高了70.6%和71.8%。一方面，这是因为通过开环反应引入的磺酸基团不仅可以作为Lewis碱性位点与CO₂发生酸碱相互作用，而且能够吸附水分子从而增强CO₂在膜中的促进传递效果。另一方面，PVAm中的氨基与CAU-1@BS的多孔结构协同作用提高膜的气体分离性能。此外，在以CO₂/N₂混合气为原料气的条件下，制备的混合基质复合膜在长达360 h的时间内保持了良好的稳定性，其平均CO₂渗透速率和CO₂/N₂选择性分别为527 GPU和70，这表明该膜具有较好的应用前景。

关键词: 混合基质复合膜, 二氧化碳捕集, 分离, 磺化CAU-1, 传递过程

Abstract:

Mixed matrix membranes combine the advantages of polymers with inorganic materials, which can outperform polymer membranes and have a wide range of applications in gas separation. To obtain high-performance CO₂/N₂ separation membranes, sulfonated CAU-1 (CAU-1@BS) was prepared by the ring-opening reaction of the epoxy group of prop-1-ene-1,3-sultone (BS) with the primary amine group of CAU-1. Then, CAU-1@BS was added to polyvinylamine (PVAm) to prepare a casting solution, which was coated on a hydrophilic modified polysulfone ultrafiltration membrane to obtain a mixed matrix composite membrane. The chemical structure and pore structure of CAU-1@BS were characterized by XPS, FTIR and BET, and the morphological structure of the membrane was characterized by SEM. Furthermore, the effects of preparation and test conditions of mixed matrix composite membranes on gas separation were investigated. The results showed that as-prepared mixed matrix composite membranes exhibited excellent separation performance with a CO₂ permeance of 505 GPU and a CO₂/N₂ selectivity of 67, when the content of CAU-1@BS was 7% (mass). Their values were improved by 70.6% and 71.8%, respectively, compared with those of pristine PVAm membranes (CO₂ permeance: 296 GPU; CO₂/N₂ selectivity: 39). On the one hand, this is due to the fact that the sulfonic acid groups introduced through the ring-opening reaction not only act as Lewis basic sites for acid-base interactions with CO₂, but also adsorb water molecules to enhance the facilitated transport of CO₂ in the membrane. On the other hand, the gas separation performance of the membrane was improved by the synergic effect of the amine groups and porous structure of CAU-1@BS. In addition, under the condition of using CO₂/N₂ mixed gas as feed gas, the prepared mixed matrix composite membrane maintained good stability for up to 360 h, and its average CO₂ permeance and CO₂/N₂ selectivity were 527 GPU and 70, respectively, which shows that the membrane has good application prospects.

Key words: mixed matrix composite membranes, CO₂ capture, separation, sulfonated CAU-1, transport processes

中图分类号:

TQ 028.8

王士成, 张新儒, 王永洪, 李晋平. 磺化CAU-1强化聚乙烯胺促进传递膜的CO₂/N₂分离性能[J]. 化工学报, 2025, 76(10): 5176-5189.

Shicheng WANG, Xinru ZHANG, Yonghong WANG, Jinping LI. Enhancing the CO₂/N₂ separation performance of PVAm facilitated transport membrane by sulfonated CAU-1[J]. CIESC Journal, 2025, 76(10): 5176-5189.

图/表 14

图1 PVAm/CAU-1@BS膜的制备示意图

Fig.1 Depicting preparation of PVAm/CAU-1@BS

图2 CAU-1和CAU-1@BS的结构表征

Fig.2 Structural characterization of CAU-1 and CAU-1@BS

表1 材料的孔结构参数

Table 1 Porous structure parameters of materials

Samples

BET surface area/

(m²·g^-1)

Total pore volume/

(cm³·g^-1)

H-K micropore volume /

(cm³·g^-1)

Average pore diameter/nm

图3 CAU-1和CAU-1@BS的XPS全谱图及元素高分辨率谱图

Fig.3 XPS full spectrum and elemental high-resolution spectra of CAU-1 and CAU-1@BS

图4 CAU-1和CAU-1@BS的扫描电镜图以及对应的粒径分布

Fig.4 SEM images of CAU-1 and CAU-1@BS and corresponding particle size distributions

图5 膜的结构表征

Fig.5 Structural characterization of the membranes

图6 纯PVAm膜和MMCMs的表面和截面SEM图

Fig.6 Surface and cross-sectional SEM images of the pristine PVAm membrane and MMCMs

图7 (a) CAU-1与BS的质量比和(b) CAU-1@BS的含量对膜气体分离性能的影响；湿涂层厚度对膜(c) CO2渗透速率和(d) CO2/N2选择性的影响

Fig.7 Effect of (a) the mass ratio of CAU-1to BS and (b) CAU-1@BS loading on the gas separation performance of the membranes; Effect of the wet coating thickness on (c) CO2 permeance and (d) CO2/N2 selectivity of membranes

图8 纯PVAm膜和PVAm/CAU-1@BS的(a) CO2渗透速率和(b) CO2/N2选择性与进料气压力的关系

Fig.8 Dependence of (a) CO2 permeance and (b) CO2/N2 selectivity of the pristine PVAm membrane and PVAm/CAU-1@BS on feed gas pressure

图9 纯PVAm膜和PVAm/CAU-1@BS的(a) CO2渗透率和(b) CO2/N2选择性与操作温度的关系

Fig.9 Dependence of (a) CO2 permeance and (b) CO2/N2 selectivity of the pristine PVAm membrane and PVAm/CAU-1@BS membrane as functions of operating temperature

图10 使用混合气体和纯气体测试纯PVAm膜和PVAm/CAU-1@BS的分离性能

Fig.10 Separation performance of the pristine PVAm membrane and PVAm/CAU-1@BS tested using a gas mixture and a pure gas

图11 (a)添加了不同填料的MMCMs的气体分离性能；添加了不同填料的Pebax基质膜的(b)扩散系数和(c)溶解度系数

Fig.11 (a) Gas separation performances of MMCMs loaded with different fillers; (b) Diffusion coefficients and (c) solubility coefficients of Pebax-based membranes with different fillers added

图12 (a) PVAm/CAU-1@BS-7膜的稳定性及(b)与先前报道的膜对比

Fig.12 (a) The stability of PVAm/CAU-1@BS-7 membranes and (b) comparison with previously reported membranes

图13 (a) PVAm/CAU-1@BS与其他已报道的基于PVAm的MMCMs的性能增加百分数及其(b)上限对比

Fig.13 (a) Percentage increase in performance of PVAm/CAU-1@BS versus other reported PVAm-based MMCMs and (b) their upper bound

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磺化CAU-1强化聚乙烯胺促进传递膜的CO₂/N₂分离性能

Enhancing the CO₂/N₂ separation performance of PVAm facilitated transport membrane by sulfonated CAU-1

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