基于PI微球复合型全热交换膜的制备与性能

doi:10.16085/j.issn.1000-6613.2023-0101

摘要/Abstract

摘要：

聚酰亚胺（PI）是一类具备高热稳定性和化学稳定性的聚合物材料，已被广泛用于气体分离膜的制备。然而，当前将其作为新型有机填料的研究甚少，更没有应用在全热交换、新风系统领域的相关报道。因此，本文采用对苯二胺（pPDA）和3,3′,4,4′-二苯酮四甲酸二酐（BTDA）作为单体原料，通过溶剂热聚合法成功制备了具有片层结构的PI微球颗粒。通过界面聚合过程将所制备的PI微球引入聚酰胺（PA）分离层中，构建出一系列基于PI微球的PA复合型全热交换膜材料。深入探究了PI微球的添加方式（制膜工艺）和掺杂量对膜形貌、水接触角、表面粗糙度、CO₂及水蒸气透过率、全热交换效率等的影响规律。研究结果表明，采用将PI微球均匀分散于均苯三甲酰氯（TMC）油相溶液中的制膜方法可确保粒子的负载与界面聚合反应同步进行，有效避免了颗粒堆叠和界面缺陷的问题。所制备的PI-PA-IV-2复合膜具有优异的透湿阻气性能，水蒸气渗透率从原膜的1763.45g/(m²·24h)提升至1949.51g/(m²·24h)，CO₂透过率从21.04GPU降至3.64GPU。与此同时，该膜拥有与商业纸膜相当的热交换效率（97.47%）和焓交换效率（71.41%），为新型高效全热交换膜的制备提供了可行方案。

关键词: 聚酰亚胺, 分离, 膜, 界面, 阻气, 全热交换效率

Abstract:

Polyimide (PI) is a highly stable class of polymeric materials widely used in gas separation applications. However, research on new organic fillers for PI is limited with few reports on their application in total heat exchange and fresh air systems. In this study, the flower-like PI microspheres with a lamellar structure were synthesized using 1,4-phenylenediamine (pPDA) and benzophenone-3,3′,4,4′-tetracarboxylic dianhydride (BTDA) as monomers via a solvothermal process polymerization. By introducing PI microspheres into the polyamide (PA) separation layer via interfacial polymerization (IP), a series of PI-PA composite total heat exchange membranes were successfully fabricated. The effects of the addition method and amount of PI microspheres on membrane morphology, water contact angle, surface roughness, CO₂ and water vapor permeability, and total heat exchange efficiency were thoroughly investigated. The homogeneous dispersion of PI microspheres in trimesoyl chloride (TMC) oil phase ensured simultaneous PI loading and interfacial polymerization, effectively avoiding particle stacking and interfacial defects. The optimized PI-PA-Ⅳ-2 composite film demonstrated outstanding moisture permeability and gas resistance with CO₂ permeability decreasing from 21.04GPU to 3.64GPU and water vapor permeability increasing from 1763.45g/(m²·24h) to 1949.51g/(m²·24h). Moreover, this membrane exhibited comparable heat exchange efficiency (97.47%) and enthalpy exchange efficiency (71.41%) to commercial paper membranes, highlighting its potential as a valuable approach for the high-efficiency total heat exchange membranes.

Key words: polyimide, separation, membranes, interface, gas barrier, total heat exchange efficiency

中图分类号:

TQ028

罗伶萍, 王慧敏, 朱泰忠, 张良, 刘梦娇, 黄菲, 薛立新. 基于PI微球复合型全热交换膜的制备与性能[J]. 化工进展, 2023, 42(12): 6478-6489.

LUO Lingping, WANG Huimin, ZHU Taizhong, ZHANG Liang, LIU Mengjiao, HUANG Fei, XUE Lixin. Preparation and properties of composite total heat exchange membranes based on polyimide microspheres[J]. Chemical Industry and Engineering Progress, 2023, 42(12): 6478-6489.

图/表 18

图1 聚酰亚胺微球制备流程图

图2 界面聚合制备PI-PA复合膜工艺流程

图3 CO2渗透测试装置图1—气瓶；2—流量计；3—流量调节阀；4—压力表；5—恒温箱；6—膜池；7—膜；8—皂膜流量计PCO2=VPtS (1)

图4 全热交换测试系统

图5 聚酰亚胺微球的形貌

图6 聚酰亚胺微球的FTIR图

图7 聚酰亚胺微球的XRD图

图8 聚酰亚胺微球、PA/PSf膜和PI-PA/PSf膜的XRD图

图9 聚酰亚胺微球在不同制膜工艺下的形貌

图10 不同工艺流程制备的PI-PA复合膜CO2和水蒸气渗透性

图11 添加不同含量微球的PI-PA复合膜SEM图

图12 添加不同含量微球的PI-PA复合膜SLM图（单位：μm）

表1 添加不同含量微球的PI-PA复合膜粗糙度

添加量/mg	粗糙度/ $μ$ m
0	0.48
2	0.47
5	0.56
8	0.79

表1 添加不同含量微球的PI-PA复合膜粗糙度

添加量/mg	粗糙度/ $μ$ m
0	0.48
2	0.47
5	0.56
8	0.79

图13 PA原始膜轮廓线

图14 添加不同含量微球的PI-PA复合膜接触角

图15 微球含量对PI-PA复合膜的CO2和水蒸气渗透性

表2 膜的热交换效率、焓交换效率及透湿阻气性

膜类型	热交换效率/%	焓交换效率/%	二氧化碳渗透率/GPU	水蒸气渗透率/g·m^-2·(24h)^-1
商业纸膜	97.52	72.47	9.5×10⁶	2237.83
PA	95.59	71.43	21.04	1763.45
PI-PA-Ⅳ-2	97.47	71.41	3.64	1949.51

图16 复合膜与商业纸膜的全热性能及透湿阻气性能对比图

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