PVSA/PVAm共混复合膜的制备及其CO_2分离性能的研究
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摘要
分离CO2的固定载体膜同时具备良好的稳定性和渗透选择性能，是一类很有
发展前景的新型分离膜。聚合物共混改性是开发具有崭新性能膜材料的重要途
径。
本文利用我们实验室已开发出的固定载体膜材料—聚N-乙烯基-γ-氨基丁
酸钠(PVSA)和聚乙烯基胺（PVAm）研制出PVSA/PVAm共混膜材料，并以聚醚
砜(PES)超滤膜为支撑体制成共混复合膜。采用现代分析测试手段红外、X射线
衍射（XRD）、材料拉伸测试及环境扫描电子显微镜（ESEM）对PVSA和共混聚
合物的微观结构、共混聚合物的拉伸性能和共混复合膜的形貌特征进行了研究。
结果表明，通过聚合物共混的方法，膜材料的力学性能得到了改善；两种聚合物
相容性良好，电镜显示共混复合膜表层致密光滑，与支撑层紧密结合。以CO2/CH4
体系为研究对象，考察了共混复合膜的透过选择性能，系统研究了各种因素如耦
合效应、PVSA/PVAm配比、铸膜环境温度及湿度对膜结构和性能的影响。以CO2、
CH4、N2、O2为研究对象，系统地探讨了该共混复合膜对不同气体体系的分离性
能。研究结果表明，以该共混聚合物为表层，PES超滤膜为支撑层制得的
PVSA/PVAm共混复合膜综合性能优越。在PVSA wt%＝33.3%，压力为 1.04atm
时，PVSA/PVAm共混复合膜的CO2渗透速率和CO2/CH4理想分离因子分别为
6.48×10-6 cm3 (STP)cm-2 s-1 cmHg-1和 217。用 50%CO2和 50%CH4组成的混合气进
行测试时，在CO2分压为 0.518atm的情况下，CO2的渗透速率达到了 5.56×
10-6cm3(STP) cm-2 s-1 cmHg-1，CO2/CH4的分离因子为 49.7。不同气体通过该共混
复合膜的快慢顺序为CO2＞O2＞CH4＞N2，理想分离因子大小为αCO2/N2＞α
CO2/CH4＞αCO2/O2。
本论文还采用丙烯酰胺与马来酸酐进行共聚并水解得到聚合物马来酸钠－
丙稀酰胺（MAS-Am），采用该共聚物为表层，PES超滤膜为支撑层制得复合膜，
初步探讨了该复合膜对CO2/CH4体系的渗透选择性。结果表明，相对PVSA/PVAm
共混复合膜而言，该膜的CO2渗透速率以及CO2/CH4的分离因子较低。在纯气测
试中，当压力为 1.04atm时，该复合膜CO2的渗透速率为 1.04×10－6 cm3(STP) cm-2
s-1 cmHg-1，CO2/CH4理想分离因子为 66。当用 50%CO2和 50%CH4组成的混合气
进行测试时，CO2分压为 0.56atm时，CO2渗透速率为 5.58×10－7 cm3(STP) cm-2 s-1
cmHg-1，CO2/CH4分离因子为 43.6。
Fixed carrier membranes for CO2 separation are promising membranes, which
have the advantages of both stability and good permselectivity. Polymer blending is a
useful method which can result in a new product with properties not found in single
polymers.
Poly(N-vinyl-γ-sodium aminobutyrate)(PVSA) and polyvinyamine(PVAm)
are two fixed carrier membrane materials developed by our research group. In this
work, fixed carrier blend materials—PVSA/PVAm were prepared by using PVSA and
PVAm successfully. Composite membranes were developed with the blend material
PVSA/PVAm as active layers and polyethersulfone ultrafiltration membrane as
support. Tensile elongation measurement was used to test the mechanics of blend
materials. FTIR(Fourier Transform Infrared Spectroscopy), XRD(X-ray diffractions)
and ESEM (Environmental Scanning Electron Microscope) were employed to
characterize the structure of PVSA and blend materials PVSA/PVAm and the
morphology of the PVSA/PVAm blend composite membranes. The results show that
the mechanical properties of the blend polymer are better than that of the two single
polymers, the active layers of the composite membranes are smooth and dense.
The permselectivities of the blend composite membranes were measured with
pure CO2 and CH4 gas as well as binary mixture of CO2 and CH4. The effects of many
kinds of factors such as “coupling effects”, PVSA/PVAm ratio, cross-linking and
casting temperature and relative humidity on performances of the PVSA/PVAm blend
composite membranes were discussed in detail. The permselectivity of the blend
membranes for CO2/N2 and CO2/O2 were also measured. The PVSA/PVAm blend
composite membranes present excellent comprehensive performances, which are
better than single PVSA and PVAm composite membranes. For pure feed gases, at
pressure of 1.04 atm，PVSA wt%=33.3%, the PVSA/PVAm blend composite
membrane displays a CO2 permeation rate of 6.48×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and
CO2/CH4 ideal separation factor of 217. For mixed feed gas composed of 50% CO2
and 50% CH4, at CO2 partial pressure of 0.518 atm，PVSA wt%=33.3%, the
PVSA/PVAm blend composite membrane displays a CO2 permeation rate of
5.56×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and CO2/CH4 ideal separation factor of 49.7. The
permeation rate sequence of different gases is CO2＞O2＞CH4＞N2, and the ideal
selectivity sequence of different gas systems is α CO2/N2＞αCO2/CH4＞αCO2/O2.
II
Copolymer poly( maleic acid sodium-co-acrylamide) (MAS-Am) was
synthesized by using maleic anhydride and acrylamide. The composite membrane
MAS-Am/PES were developed with this material as active layer and polyethersulfone
ultrafiltration membrane as support. And the permselectivities of the composite
membrane were also measured with pure CO2 and CH4 gas as well as binary mixture
of CO2 and CH4. For pure feed gases, at pressure of 1.04 atm，MAS-Am composite
membrane displays a CO2 permeation rate of 1.05×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and
CO2/CH4 ideal separation factor of 66. For mixed feed gas composed of 50% CO2 and
50% CH4, at CO2 partial pressure of 0.56 atm, the MAS-Am composite membrane
displays a CO2 permeation rate of 5.58×10-7 cm3 (STP)cm-2 s-1 cmHg-1 and CO2/CH4
ideal separation factor of 43.6.
发展前景的新型分离膜。聚合物共混改性是开发具有崭新性能膜材料的重要途
径。
本文利用我们实验室已开发出的固定载体膜材料—聚N-乙烯基-γ-氨基丁
酸钠(PVSA)和聚乙烯基胺（PVAm）研制出PVSA/PVAm共混膜材料，并以聚醚
砜(PES)超滤膜为支撑体制成共混复合膜。采用现代分析测试手段红外、X射线
衍射（XRD）、材料拉伸测试及环境扫描电子显微镜（ESEM）对PVSA和共混聚
合物的微观结构、共混聚合物的拉伸性能和共混复合膜的形貌特征进行了研究。
结果表明，通过聚合物共混的方法，膜材料的力学性能得到了改善；两种聚合物
相容性良好，电镜显示共混复合膜表层致密光滑，与支撑层紧密结合。以CO2/CH4
体系为研究对象，考察了共混复合膜的透过选择性能，系统研究了各种因素如耦
合效应、PVSA/PVAm配比、铸膜环境温度及湿度对膜结构和性能的影响。以CO2、
CH4、N2、O2为研究对象，系统地探讨了该共混复合膜对不同气体体系的分离性
能。研究结果表明，以该共混聚合物为表层，PES超滤膜为支撑层制得的
PVSA/PVAm共混复合膜综合性能优越。在PVSA wt%＝33.3%，压力为 1.04atm
时，PVSA/PVAm共混复合膜的CO2渗透速率和CO2/CH4理想分离因子分别为
6.48×10-6 cm3 (STP)cm-2 s-1 cmHg-1和 217。用 50%CO2和 50%CH4组成的混合气进
行测试时，在CO2分压为 0.518atm的情况下，CO2的渗透速率达到了 5.56×
10-6cm3(STP) cm-2 s-1 cmHg-1，CO2/CH4的分离因子为 49.7。不同气体通过该共混
复合膜的快慢顺序为CO2＞O2＞CH4＞N2，理想分离因子大小为αCO2/N2＞α
CO2/CH4＞αCO2/O2。
本论文还采用丙烯酰胺与马来酸酐进行共聚并水解得到聚合物马来酸钠－
丙稀酰胺（MAS-Am），采用该共聚物为表层，PES超滤膜为支撑层制得复合膜，
初步探讨了该复合膜对CO2/CH4体系的渗透选择性。结果表明，相对PVSA/PVAm
共混复合膜而言，该膜的CO2渗透速率以及CO2/CH4的分离因子较低。在纯气测
试中，当压力为 1.04atm时，该复合膜CO2的渗透速率为 1.04×10－6 cm3(STP) cm-2
s-1 cmHg-1，CO2/CH4理想分离因子为 66。当用 50%CO2和 50%CH4组成的混合气
进行测试时，CO2分压为 0.56atm时，CO2渗透速率为 5.58×10－7 cm3(STP) cm-2 s-1
cmHg-1，CO2/CH4分离因子为 43.6。
Fixed carrier membranes for CO2 separation are promising membranes, which
have the advantages of both stability and good permselectivity. Polymer blending is a
useful method which can result in a new product with properties not found in single
polymers.
Poly(N-vinyl-γ-sodium aminobutyrate)(PVSA) and polyvinyamine(PVAm)
are two fixed carrier membrane materials developed by our research group. In this
work, fixed carrier blend materials—PVSA/PVAm were prepared by using PVSA and
PVAm successfully. Composite membranes were developed with the blend material
PVSA/PVAm as active layers and polyethersulfone ultrafiltration membrane as
support. Tensile elongation measurement was used to test the mechanics of blend
materials. FTIR(Fourier Transform Infrared Spectroscopy), XRD(X-ray diffractions)
and ESEM (Environmental Scanning Electron Microscope) were employed to
characterize the structure of PVSA and blend materials PVSA/PVAm and the
morphology of the PVSA/PVAm blend composite membranes. The results show that
the mechanical properties of the blend polymer are better than that of the two single
polymers, the active layers of the composite membranes are smooth and dense.
The permselectivities of the blend composite membranes were measured with
pure CO2 and CH4 gas as well as binary mixture of CO2 and CH4. The effects of many
kinds of factors such as “coupling effects”, PVSA/PVAm ratio, cross-linking and
casting temperature and relative humidity on performances of the PVSA/PVAm blend
composite membranes were discussed in detail. The permselectivity of the blend
membranes for CO2/N2 and CO2/O2 were also measured. The PVSA/PVAm blend
composite membranes present excellent comprehensive performances, which are
better than single PVSA and PVAm composite membranes. For pure feed gases, at
pressure of 1.04 atm，PVSA wt%=33.3%, the PVSA/PVAm blend composite
membrane displays a CO2 permeation rate of 6.48×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and
CO2/CH4 ideal separation factor of 217. For mixed feed gas composed of 50% CO2
and 50% CH4, at CO2 partial pressure of 0.518 atm，PVSA wt%=33.3%, the
PVSA/PVAm blend composite membrane displays a CO2 permeation rate of
5.56×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and CO2/CH4 ideal separation factor of 49.7. The
permeation rate sequence of different gases is CO2＞O2＞CH4＞N2, and the ideal
selectivity sequence of different gas systems is α CO2/N2＞αCO2/CH4＞αCO2/O2.
II
Copolymer poly( maleic acid sodium-co-acrylamide) (MAS-Am) was
synthesized by using maleic anhydride and acrylamide. The composite membrane
MAS-Am/PES were developed with this material as active layer and polyethersulfone
ultrafiltration membrane as support. And the permselectivities of the composite
membrane were also measured with pure CO2 and CH4 gas as well as binary mixture
of CO2 and CH4. For pure feed gases, at pressure of 1.04 atm，MAS-Am composite
membrane displays a CO2 permeation rate of 1.05×10-6 cm3 (STP)cm-2 s-1 cmHg-1 and
CO2/CH4 ideal separation factor of 66. For mixed feed gas composed of 50% CO2 and
50% CH4, at CO2 partial pressure of 0.56 atm, the MAS-Am composite membrane
displays a CO2 permeation rate of 5.58×10-7 cm3 (STP)cm-2 s-1 cmHg-1 and CO2/CH4
ideal separation factor of 43.6.
引文
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