GO-TSC/聚酰亚胺混合基质膜的制备及气体分离性能研究

doi:10.19964/j.issn.1006-4990.2020-0658

摘要/Abstract

摘要：

使用氨基硫脲（TSC）对氧化石墨烯（GO）进行改性,制备GO-TSC层状复合材料。随后,将该复合材料加入到Matrimid^®5218（PI）基质中,制备用于二氧化碳分离的混合基质膜（MMMs）。通过TGA、SEM及气体分离性能测试考察了GO-TSC对膜热稳定性、结构和气体分离性能等的影响。SEM结果显示GO-TSC可均匀分散在聚合物基质上并与基质紧密结合;TGA结果显示混合基质膜在250 ℃以上仍保持稳定。与纯PI膜相比,MMMs显著增强了二氧化碳的渗透性。GO-TSC中所含的氨基与二氧化碳具有良好的亲和力,增加的碱性位点可以有效地转运二氧化碳。GO-TSC的层状结构增加了气体的传输路径,不利于大动态直径气体（甲烷、氮气）的通过,从而提高了分离性能。GO-TSC负载量为0.75%（质量分数）时混合基质膜的分离性能最佳。相比较纯PI膜,混合基质膜的二氧化碳渗透系数和二氧化碳/甲烷、二氧化碳/氮气分离系数分别提高了42.16%、95.79%和83.72%。

关键词: 氧化石墨烯, 聚酰亚胺, 混合基质膜, 气体分离

Abstract:

Graphene oxide（GO） was modified using thiosemicarbazide（TSC） for the fabrication of flat sheet GO-TSC cmpo-site.Subsequently,this composite was incorporated into the Matrimid^®5218（PI） matrix to fabricate mixed matrix membranes（MMMs） for CO₂ separation.Through TGA,SEM and gas separation performance tests,influence of GO-TSC on thermal sta-bility,structure and gas separation performance of the mixed matrix membrane was investigated.SEM showed that GO-TSC could be uniformly dispersed in the polymer matrix and tightly combined with the matrix;TGA result showed that decomposi-tion temperature of mixed matrix membranes was above 250 ℃.MMMs showed significantly enhanced CO₂ permeability com-pared with pure PI membrane.The amino group contained in GO-TSC had a good affinity with CO₂,and the increased amidogen sites could effectively transport CO₂.The GO-TSC lamellar structure increased the gas transmission path,which was not conducive to the passage of large dynamic diameter gases（CH₄,N₂）,thereby improving the separation performance.The MMMs doped with GO-TSC-0.75% showed optimal gas separation performance.Compared with pure PI membrane,the CO₂ permeability,CO₂/CH₄ selectivity and CO₂/N₂ selectivity of the MMMs were increased by 42.16%,95.79% and 83.72%,respectively.

Key words: graphene oxide, polyimide, mixed matrix membrane, gas separation

中图分类号:

TQ028.8

郭欣,衣华磊,袁玮良,郝蕴,段翠佳,陈赞. GO-TSC/聚酰亚胺混合基质膜的制备及气体分离性能研究[J]. 无机盐工业, 2021, 53(10): 74-80.

Guo Xin,Yi Hualei,Yuan Weiliang,Hao Yun,Duan Cuijia,Chen Zan. Study on preparation of GO-TSC/polyimide mixed matrix membrane and its gas separation performance[J]. Inorganic Chemicals Industry, 2021, 53(10): 74-80.

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参考文献 30

[1]	Scholes C A, Smith K H, Kentish S E, et al. CO₂ capture from pre-combustion processes-Strategies for membrane gas separation[J]. International Journal of Greenhouse Gas Control, 2010, 4(5):739-755. doi: 10.1016/j.ijggc.2010.04.001
[2]	Liu Y F, Wang Z, Yang H L, et al. 3-Phenylethynyl phthalimide end-capped imide oligomers and the cured polymers[J]. Journal of Polymer Science Part A:Polymer Chemistry, 2008, 46(12):4227-4235. doi: 10.1002/(ISSN)1099-0518
[3]	Zhao S, Wang Z, Qiao Z H, et al. Gas separation membrane with CO₂-facilitated transport highway constructed from amino carrier containing nanorods and macromolecules[J]. Journal of Materials Chemistry A, 2013, 1(2):246-249. doi: 10.1039/C2TA00247G
[4]	Kanehashi S, Chen G Q, Scholes C A, et al. Enhancing gas permea-bility in mixed matrix membranes through tuning the nanoparticle properties[J]. Journal of Membrane Science, 2015, 482(5):49-55. doi: 10.1016/j.memsci.2015.01.046
[5]	Yu J, Wang C Q, Xiang L, et al. Enhanced C₃H₆/C₃H₈ separation per-formance in poly(vinyl acetate) membrane blended with ZIF-8 nanocrystals[J]. Chemical Engineering Science, 2018, 179(6):1-12. doi: 10.1016/j.ces.2017.12.051
[6]	Li X Q, Ma L, Zhang H Y, et al. Synergistic effect of combining car-bon nanotubes and graphene oxide in mixed matrix membranes for efficient CO₂ separation[J]. Journal of Membrane Science, 2015, 479(1):1-10. doi: 10.1016/j.memsci.2015.01.014
[7]	Li X F, Zhang F, Jiang H Y, et al. Amine-functionalized GO as an active and reusable acid-base bifunctional catalyst for one-pot casc-ade reactions[J]. ACS Catalysis, 2013, 4(2):394-401. doi: 10.1021/cs400761r
[8]	陈德强, 白云翔, 张春芳, 等. Fe₃O₄ /PIM-1磁性混合基质膜的制备及其 O₂/N₂ 分离性能研究[J]. 膜科学与技术, 2017, 37(4):27-37.
[9]	Li Y F, Wang S F, He G, et al. Facilitated transport of small molec-ules and ions for energy-efficient membranes[J]. Chemical Society Reviews, 2015, 44(1):103-118. doi: 10.1039/C4CS00215F
[10]	Zhao Y, Wang F S, Winston H, et al. Steric hindrance effect on amine demonstrated in solid polymer membranes for CO₂ transpo-rt[J]. Journal of Membrane Science, 2012, 4(12):132-138.
[11]	Xin Q, Zhao L, Li C, et al. Enhancing the CO₂ separation perfor-mance of composite membranes by the incorporation of amino acid-functionalized graphene oxide[J]. Journal of Materials Chemistry A, 2015, 3(12):6629-6641. doi: 10.1039/C5TA00506J
[12]	Peng D D, Wang S F, Tian Z, et al. Facilitated transport membran-es by incorporating graphene nanosheets with high zinc ion loading for enhanced CO₂ separation[J]. Journal of Membrane Science, 2017, 522:351-362. doi: 10.1016/j.memsci.2016.09.040
[13]	Xin Q P, Ma F X, Zhang L, et al. Interface engineering of mixed matrix membrane via CO₂-philic polymer brush functionalized graphene oxide nanosheets for efficient gas separation[J]. Journal of Membrane Science, 2019, 586(9):23-33. doi: 10.1016/j.memsci.2019.05.050
[14]	Jia X L, Zhang Q, Zhao M Q, et al. Dramatic enhancements in toug-hness of polyimide nanocomposite via long-CNT-induced long-range creep[J]. Journal of Materials Chemistry, 2012, 22(14):45-58.
[15]	Zambare R, Song X, Bhuvana S, et al. Ultrafast dye removal using ionic liquid-graphene oxide sponge[J]. ACS Sustainable Chemistry& Engineering, 2017, 5(7):6026-6035.
[16]	Jia M M, Feng Y, Qiu J, et al. Amine-functionalized MOFs@GO as filler in mixed matrix membrane for selective CO₂ separation[J]. Separation and Purification Technology, 2019, 213(2):63-69. doi: 10.1016/j.seppur.2018.12.029
[17]	Wang C Y, Lan Y F, Yu W T, et al. Preparation of amino-function-alized graphene oxide/polyimide composite films with improved mechanical,thermal and hydrophobic properties[J]. Applied Sur-face Science, 2016, 362(2):11-19.
[18]	Bu J Q, Yuan L, Zhang N, et al, High-efficiency adsorption of me-thylene blue dye from wastewater by a thiosemicarbazide function-alized graphene oxide composite[J]. Diamond and Related Materi-als, 2020, 101(2):67-79.
[19]	Shang N Z, Feng C, Zhang H Y, et al, Suzuki-miyaura reaction ca-talyzed by graphene oxide supported palladium nanoparticles[J]. Catalysis Communications, 2013, 40(8):111-115. doi: 10.1016/j.catcom.2013.06.006
[20]	Huang D D, Xin Q P, Li Y Z, et al. Synergistic effects of zeolite imidazole framework@graphene oxide composites in humidified mixed matrix membranes on CO₂ separation[J]. RSC Advances, 2018, 7(8):6099-6109.
[21]	Liu Y, Peng D D, He G, et al, Enhanced CO₂ permeability of mem-branes by incorporating polyzwitterion@CNT composite particles into polyimide matrix[J]. ACS Applied Materials & Interfaces, 2014, 6(15):13051-13060.
[22]	Li X Q, Cheng Y D, Zhang H Y, et al. Efficient CO₂ capture by func-tionalized graphene oxide nanosheets as fillers to fabricate multi-permselective mixed matrix membranes[J]. ACS Applied Materi-als & Interfaces, 2015, 7(9):177-189.
[23]	Cui Y, Kundalwal S I, Kumar S. Gas barrier performance of grap-hene/polymer nanocomposites[J]. Carbon, 2016, 98(3):313-333. doi: 10.1016/j.carbon.2015.11.018
[24]	Ge B S, Wang T, Sun H X, et al. Preparation of mixed matrix mem-branes based on polyimide and aminated graphene oxide for CO₂ separation[J]. Polymers for Advanced Technologies, 2018, 29(4):1334-1343. doi: 10.1002/pat.v29.4
[25]	Khan A, Klaysom C, Gahlaut A, et al. Mixed matrix membranes co-mprising of Matrimid and-SO₃H functionalized mesoporous MCM-41 for gas separation[J]. Journal of Membrane Science, 2013, 47(4):73-79.
[26]	Li F, Li Y, Chung T S, et al. Facilitated transport by hybrid POSS^®-Matrimid^®-Zn²⁺ nanocomposite membranes for the separation of natural gas[J]. Journal of Membrane Science, 2010, 356(3):14-21. doi: 10.1016/j.memsci.2010.03.021
[27]	Wang S, Tian Z Z, Feng J, et al. Enhanced CO₂ separation proper-ties by incorporating poly(ethylene glycol)-containing polymeric submicrospheres into polyimide membrane[J]. Journal of Mem-brane Science, 2015, 473(1):310-317.
[28]	Zornoza B, Téllez C, Coronas J. Mixed matrix membranes compris-ing glassy polymers and dispersed mesoporous silica spheres for gas separation[J]. Journal of Membrane Science, 2011, 368(2):100-109. doi: 10.1016/j.memsci.2010.11.027
[29]	Zhang Y, Musselman I H, Ferraris J P, et al. Gas permeability pro-perties of Matrimid^® membranes containing the metal-organic fra-mework Cu-BPY-HFS[J]. Journal of Membrane Science, 2018, 313(5):170-181. doi: 10.1016/j.memsci.2008.01.005
[30]	Zhang Y, Balkus K J, Musselman I H, et al. Mixed-matrix membra-nes composed of Matrimid^® and mesoporous ZSM-5 nanoparticl-es[J]. Journal of Membrane Science, 2008, 325(1):28-39. doi: 10.1016/j.memsci.2008.04.063

混合基质膜	度数/（°）	间距/nm
PI	15.90	0.562
PI/GO-TSC-0.5%	16.17	0.553
PI/GO-TSC-0.75%	16.29	0.549
PI/GO-TSC-1%	16.35	0.547
PI/GO-TSC-1.25%	16.47	0.543
PI/GO-TSC-1.5%	16.61	0.538

填料	P （CO₂）/Barrer	α （CO₂/CH₄）	α （CO₂/N₂）	测试条件
SO₃H-MCM-41^[25]	11.20	40.50	37.40	0.4 MPa,35 ℃
POSS-Zn^2+[26]	4.00	57.60	30.76	1.0 MPa,35 ℃
PEGSS^[27]	10.42	49.62	47.36	0.1 MPa,40 ℃
C60^[28]	3.79	34.80	23.70	1.0 MPa,35 ℃
CU-BPY-HFS^[29]	10.40	27.40	33.40	0.39 MPa,35 ℃
MCM-48^[30]	9.35	33.39	31.16	0.25 MPa,35 ℃
GO-TSC	10.11	60.55	51.86	0.2 MPa,35 ℃

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