聚乙烯醇基高透湿高阻隔三元混合基质全热交换膜制备和性能

doi:10.16085/j.issn.1000-6613.2021-0516

化工进展 ›› 2022, Vol. 41 ›› Issue (2): 911-919.DOI: 10.16085/j.issn.1000-6613.2021-0516

聚乙烯醇基高透湿高阻隔三元混合基质全热交换膜制备和性能

苌现¹(), 杨文杰¹, 李士洋¹, 张秀敏¹, 吴涛², 薛立新¹^,²()

^1.浙江工业大学化工学院膜分离与水科学技术中心，浙江杭州 310014
^2.浙江工业大学膜分离与水处理协同创新中心湖州研究院，浙江湖州 313000

收稿日期:2021-03-15 修回日期:2021-06-10 出版日期:2022-02-05 发布日期:2022-02-23
通讯作者: 薛立新
作者简介:苌现（1992—），男，硕士研究生，研究方向为膜科学与技术。E-mail：1093304586@qq.com。
基金资助:
国家自然科学基金(21975222);湖州市科技项目(2019ZD2035)

Polyvinyl alcohol (PVA) based ternary mixed matrix total heat exchange membranes (THEM) comprising montmorillonite (MMT) and CaCl₂: preparation and characterization

CHANG Xian¹(), YANG Wenjie¹, LI Shiyang¹, ZHANG Xiumin¹, WU Tao², XUE Lixin¹^,²()

^1.Center for Membrane Separation and Water Science & Technology, College of Chemical Engineering, Zhejiang University of Technology, Hangzhou 310014, Zhejiang, China
^2.Colaborative Imovation Center for Membrane Separation and Water Treatmert of Zhejiang University of Technology Huzhou Institute, Huzhou 313000, Zhejiang, China

Received:2021-03-15 Revised:2021-06-10 Online:2022-02-05 Published:2022-02-23
Contact: XUE Lixin

摘要/Abstract

摘要：

探讨了通过蒙脱土（MMT）和无水氯化钙（CaCl₂）共混掺杂改性，来打破透湿和阻气性之间的博弈（trade-off）效应，全面提升聚乙烯醇（PVA）全热交换膜性能的可行性。本文系统研究了氯化钙和蒙脱土的含量对膜的形态、接触角、热稳定性、力学性能、气体透过率和总换热效率的影响。实验数据表明，适量氯化钙的杂化可以引入水传导通道，提升膜的水蒸气透过率和焓交换效率，适量蒙脱土掺杂可以提升膜的高CO₂气体阻隔性能、改善其热稳定性和机械性能，同时提升粗糙度、提高湿度和焓交换效率；但是当无水氯化钙和蒙脱土含量过高时，膜的机械性能、透湿度和CO₂气体阻隔性能又会变差。综合考虑，PVA∶CaCl₂∶MMT的质量比为8∶1.6∶0.8的三元混合基质膜不仅具有高的透湿性和焓交换效率（68%），而且保持了聚乙烯醇膜的极高CO₂气体阻隔性，有望作为节能通风系统中全热交换膜的优化选项。

关键词: 聚乙烯醇, 无水氯化钙, 蒙脱土, 透湿, 阻气, 全热交换效率

Abstract:

The feasibility of breaking the trade-off between the heat exchange ratio and waste gas barrier property of polyvinyl alcohol (PVA) based total heat exchange membranes were investigated using montmorillonite (MMT) and CaCl₂ as co-additives. The morphology, water contact angle, thermal stability, mechanical properties, gas transmission permeability and total heat exchange efficiency of the ternary hybrid matrix membranes developed from solution-cast method were investigated at varied content of CaCl₂ and MMT. It was observed that addition of suitable amount of CaCl₂ hybrid can be introduced into the water conduction channel to improve the water vapor permeability and enthalpy exchange efficiency of the membrane. The addition of suitable amount of MMT could improve not only CO₂ gas barrier property, but also surface roughness, thermal stability and mechanical properties of the THEM. However, excess MMT or CaCl₂ content had both shown negative effects. Considering the requirements of low CO₂ gas transmission permeability, good water vapor and heat exchange efficiency and mechanical properties, the hybrid matrix membranes with the mass ratio of PVA∶CaCl₂∶MMT of 8∶1.6∶0.8 was most likely to be used as total heat exchange membranes with improved performance in energy-saving ventilation systems.

Key words: polyvinyl alcohol, calcium chloride, montmorillonite, moisture permeable, gas barrier, total heat exchange efficiency

中图分类号:

TU834

苌现, 杨文杰, 李士洋, 张秀敏, 吴涛, 薛立新. 聚乙烯醇基高透湿高阻隔三元混合基质全热交换膜制备和性能[J]. 化工进展, 2022, 41(2): 911-919.

CHANG Xian, YANG Wenjie, LI Shiyang, ZHANG Xiumin, WU Tao, XUE Lixin. Polyvinyl alcohol (PVA) based ternary mixed matrix total heat exchange membranes (THEM) comprising montmorillonite (MMT) and CaCl₂: preparation and characterization[J]. Chemical Industry and Engineering Progress, 2022, 41(2): 911-919.

图/表 18

表1 铸膜液的组成

样品	PVA∶CaCl₂∶MMT（质量比）	样品	PVA∶CaCl₂∶MMT（质量比）
PVA	8∶0∶0	PC₄	8∶1.6∶0
PM₁	8∶0∶0.4	PC₄M₁	8∶1.6∶0.4
PM₂	8∶0∶0.8	PC₄M₂	8∶1.6∶0.8
PM₄	8∶0∶1.6	PC₄M₃	8∶1.6∶1.2
PC₁	8∶0.4∶0	PC₄M₄	8∶1.6∶1.6
PC₂	8∶0.8∶0

图1 水蒸气透过试验示意图

图2 CO2透过试验示意图

图3 全热交换效率测试系统

图4 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜的表面[(a)~(d)]和断面[(a')~(d')]图

图5 聚乙烯醇膜、聚乙烯醇/蒙脱土杂化膜的表面[(a)~(d)]和断面[(a')~(d')]图

图6 聚乙烯醇/氯化钙/蒙脱土三元混合基质膜的表面[(a)~(d)]和断面[(a')~(d')]图

图7 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的原子力显微镜

表2 表面粗糙度数据（扫描尺寸=5μm×5μm）

样品	R_a	R_q
PVA	1.86	2.25
PC₄	4.04	4.88
PC₄M₁	5.18	6.38
PC₄M₂	13.8	17.7
PC₄M₃	33.2	41.8
PC₄M₄	72.7	57.3

图8 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的水接触角

图9 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的力学性能

图10 几种样品膜的TGA曲线

表3 不同温度下样品膜热分析的质量损失结果

样品	100℃/%	200℃/%	300℃/%	400℃/%	500℃/%	600℃/%
PVA	0.67	6.85	19.37	64.91	90.51	92.67
PM	0.87	6.91	24.40	72.60	87.01	88.82
PC	1.33	10.63	39.15	45.06	74.08	77.39
PCM	1.30	10.48	35.45	41.54	67.16	69.69

图11 纯聚乙烯醇膜、聚乙烯醇/蒙脱土杂化膜的水蒸气和二氧化碳透过量示意图

图12 纯聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜的水蒸气和二氧化碳透过量示意图

图13 纯聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的水蒸气和二氧化碳透过量示意图

表4 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的水蒸气和CO2透过量

样品	水蒸气透过量 /g?m^-2?（24h）^-1	二氧化碳透过量 /cm³?m^-2?（24h）^-1?（0.1MPa）^-1
PVA	575.62	4.172
PC₄	1313.90	24.530
PC₄M₁	1524.23	14.336
PC₄M₂	1753.64	6.594
PC₄M₃	1664.98	8.609
PC₄M₄	1446.03	21.698
商业纸膜	2237.83	6.3×10¹¹

表5 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的全热交换效率

样品	$η T / %$	$η M / %$	$η H / %$
PVA	85.71	25.44	46.41
PC₄	95.74	35.65	59.40
PC₄M₁	97.33	36.10	59.85
PC₄M₂	96.71	40.24	64.55
PC₄M₃	96.08	44.82	68.32
PC₄M₄	97.68	41.20	64.76
商业纸膜	97.52	54.70	72.47

表5 聚乙烯醇膜、聚乙烯醇/氯化钙杂化膜、聚乙烯醇/氯化钙/蒙脱土混合基质膜的全热交换效率

样品	$η T / %$	$η M / %$	$η H / %$
PVA	85.71	25.44	46.41
PC₄	95.74	35.65	59.40
PC₄M₁	97.33	36.10	59.85
PC₄M₂	96.71	40.24	64.55
PC₄M₃	96.08	44.82	68.32
PC₄M₄	97.68	41.20	64.76
商业纸膜	97.52	54.70	72.47

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聚乙烯醇基高透湿高阻隔三元混合基质全热交换膜制备和性能

Polyvinyl alcohol (PVA) based ternary mixed matrix total heat exchange membranes (THEM) comprising montmorillonite (MMT) and CaCl₂: preparation and characterization

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聚乙烯醇基高透湿高阻隔三元混合基质全热交换膜制备和性能

Polyvinyl alcohol (PVA) based ternary mixed matrix total heat exchange membranes (THEM) comprising montmorillonite (MMT) and CaCl2: preparation and characterization

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Polyvinyl alcohol (PVA) based ternary mixed matrix total heat exchange membranes (THEM) comprising montmorillonite (MMT) and CaCl₂: preparation and characterization