P84共聚聚酰亚胺-聚乙烯吡咯烷酮/聚丙烯腈复合膜的制备及其渗透汽化分离甲醇/四氢呋喃
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摘要
通过聚乙烯吡咯烷酮(PVP)与P84共聚聚酰亚胺(P84)共混,以聚丙烯腈(PAN)超滤膜为支撑层,制备了不同PVP含量的P84-PVP/PAN复合膜。采用傅里叶红外光谱(FTIR)、X射线衍射(XRD)、扫描电镜(SEM)、差示扫描量热仪(DSC)和接触角(CA)测量等方法对复合膜进行表征。FTIR分析表明,PVP与P84为物理共混。DSC结果显示共混物存在单一玻璃化转变温度,具有良好相容性。此外,水接触角测试显示PVP引入提高了膜亲水性。XRD结果表明,随着PVP含量的增加,共混物分子链平均间距增大,膜内自由体积增大。考察了PVP含量、操作温度及料液浓度对渗透汽化分离甲醇/四氢呋喃性能的影响。结果表明,随着共混物中PVP质量分数增加至20%,膜渗透通量逐渐增大,分离因子先增加(PVP质量分数≤10%)而后迅速降低。当PVP质量分数为10%、进料温度为20℃时,复合膜对于质量分数30%甲醇/四氢呋喃有最优的分离性能,其渗透通量为259g/(m~2?h),分离因子为41。
Polyvinylpyrrolidon(PVP)-P84 copolyimide(P84)/polyacrylonitrile(PAN) composite membranes were prepared via blending of PVP into P84 matrix. Membranes were characterized by Fourier transform infrared(FTIR), X-ray diffraction(XRD), scanning electron microscopy(SEM), differential scanningcalorimeter(DSC) and contact angle(CA) metering. FTIR analysis indicated that PVP and P84 were physically blended. DSC results showed that the P84-PVP blends possessed a single glass-transitiontemperature, indicating a good miscibility of blend. The contact angle test demonstrated that thehydrophility of membranes was improved with the incorporation of PVP. XRD results indicated that dspacing in the P84-PVP blend was increased when the PVP loading amount was increased.The effect of PVP loading,operating temperature and feed composition on the pervaporation performance of the composite membranes was examined.When PVP content was enhanced to 20%,the total permeation flux was increased.Meanwhile,the separation factor was first increased with the PVP content≤10%,and then decreased quickly.The composite membrane with a PVP loading amount of 10%exhibited the best performance with a total flux of 259g/(m~2?h)and a separation factor of 41 using a feed of methanol(30%)/tetrahydrofuran at 20℃.
Polyvinylpyrrolidon(PVP)-P84 copolyimide(P84)/polyacrylonitrile(PAN) composite membranes were prepared via blending of PVP into P84 matrix. Membranes were characterized by Fourier transform infrared(FTIR), X-ray diffraction(XRD), scanning electron microscopy(SEM), differential scanningcalorimeter(DSC) and contact angle(CA) metering. FTIR analysis indicated that PVP and P84 were physically blended. DSC results showed that the P84-PVP blends possessed a single glass-transitiontemperature, indicating a good miscibility of blend. The contact angle test demonstrated that thehydrophility of membranes was improved with the incorporation of PVP. XRD results indicated that dspacing in the P84-PVP blend was increased when the PVP loading amount was increased.The effect of PVP loading,operating temperature and feed composition on the pervaporation performance of the composite membranes was examined.When PVP content was enhanced to 20%,the total permeation flux was increased.Meanwhile,the separation factor was first increased with the PVP content≤10%,and then decreased quickly.The composite membrane with a PVP loading amount of 10%exhibited the best performance with a total flux of 259g/(m~2?h)and a separation factor of 41 using a feed of methanol(30%)/tetrahydrofuran at 20℃.
引文
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[16]徐荣,邹琳,张琪,等.有机硅烷交联PDMS/陶瓷复合膜的制备及渗透汽化汽油脱硫性能[J].化工进展, 2016, 35(10):3331-3336.XU Rong, ZOU Lin, ZHANG Qi, et al. Fabrication of aminosilanecrosslinked PDMS/ceramic composite membranes for pervaporativedesulfurization of gasoline[J]. Chemical Industry and EngineeringProgress, 2016, 35(10):3331-3336.
[17] SHAO L, LAU C H, CHUNG T S. A novel strategy for surfacemodification of polyimide membranes by vapor-phase ethylenediamine(EDA)for hydrogen purification[J]. International Journal of HydrogenEnergy, 2009, 34(20):8716-8722.
[18] WU H, FANG X, ZHANG X, et al. Cellulose acetate-poly(N-vinyl-2-pyrrolidone)blend membrane for pervaporation separation of methanol/MTBE mixtures[J]. Separation and Purification Technology, 2008, 64(2):183-191.
[19] YONG W F, CHUNG T S. Miscible blends of carboxylated polymers ofintrinsic microporosity(cPIM-1)and Matrimid[J]. Polymer, 2015, 59:290-297.
[20] SOLOUKIPOUR S, SALJOUGHI E, MOUSAVI S M, et al. PEBA/PVDF blend pervaporation membranes:preparation and performance[J]. Polymers for Advanced Technologies, 2017, 28(1):113-123.
[21] HIRAYAMA Y, YOSHIGANA T, KUSUKI Y, et al. Relation of gaspermeability with structure of aromatic polyimides I[J]. Journal ofMembrane Science, 1996, 111(2):169-182.
[22] TEOH M M, CHUNG T S, WANG K Y, et al. Exploring Torlon/P84 co-polyamide-imide blended hollow fibers and their chemical cross-linking modifications for pervaporation dehydration of isopropanol[J].Separation and Purification Technology, 2008, 61(3):404-413.
[23] ZERESHKI S, FIGOLI A, MADAENI S S, et al. Effect of polymercomposition in PEEKWC/PVP blends on pervaporation separation ofethanol/cyclohexane mixture[J]. Separation&Purification Technology,2010, 75(3):257-265.
[24] ZHANG S, ZOU Y, WEI T, et al. Pervaporation dehydration of binaryand ternary mixtures of n-butyl acetate, n-butanol and water usingPVA-CS blended membranes[J]. Separation and PurificationTechnology, 2017, 173:314-322.
[25] WIJMANS J G, BAKER R W. The solution-diffusion model:a review[J]. Journal of Membrane Science, 1995, 107(1/2):1-21.
[26] XU Y, CHEN C, LI J. Experimental study on physical properties andpervaporation performances of polyimide membranes[J]. ChemicalEngineering Science, 2007, 62(9):2466-2473.
[27] JADAV G L, ASWAL V K, BHATT H, et al. Influence of filmthickness on the structure and properties of PDMS membrane[J].Journal of Membrane Science, 2012, 415/416(10):624-634.
[28] GAO C, ZHANG M, JIANG Z, et al. Preparation of a highly water-selective membrane for dehydration of acetone by incorporatingpotassium montmorillonite to construct ionized water channel[J].Chemical Engineering Science, 2015, 135:461-471.
[29] LI Q, LIU Q, ZHAO J, et al. High efficient water/ethanol separation by amixed matrix membrane incorporating MOF filler with high wateradsorption capacity[J]. JournalofMembrane Science, 2017, 544:68-78.
[2] ONG Y K, SHI G M, LE N L, et al. Recent membrane development forpervaporation processes[J]. Progress in Polymer Science, 2016, 57:1-31.
[3] ZHOU K, ZHANG Q G, HAN G L, et al. Pervaporation of waterethanoland methanol-MTBE mixtures using poly(vinyl alcohol)/celluloseacetate blended membranes[J]. Journal of Membrane Science, 2013,448(24):93-101.
[4] LU J, NGUYEN Q, ZHOU J, et al. Poly(vinyl alcohol)/poly(vinylpyrrolidone)interpenetrating polymer network:synthesis andpervaporation properties[J]. Journal of Applied Polymer Science, 2003,89(10):2808-2814.
[5] WANG Y, YANG L, LUO G, et al. Preparation of cellulose acetatemembrane filled with metal oxide particles for the pervaporationseparation of methanol/methyl tert-butyl ether mixtures[J]. ChemicalEngineering Journal, 2009, 146(1):6-10.
[6] KIM S G, LIM G T, JEGAL J, et al. Pervaporation separation of MTBE(methyl tert-butyl ether)and methanol mixtures through polyioncomplex composite membranes consisting of sodium alginate/chitosan[J]. Journal of Membrane Science, 2000, 174(1):1-15.
[7] LUIS P, DEGREVE J, BRUGGEN B V D. Separation of methanol-n-butyl acetate mixtures by pervaporation:potential of 10 commercialmembranes[J]. Journal of Membrane Science, 2013, 429(4):1-12.
[8]盛鲁杰,任吉中,李新学,等. P84(BTDA-TDI/MDI)中空纤维膜的制备与分离性能研究[J].膜科学与技术, 2017, 37(4):8-14.SHENG Lujie, REN Jizhong, LI Xinxue, et al. Preparation of P84(BTDA-TDI/MDI)polyimide hollow fiber membranes and theirperformance[J]. Membrane Science and Technology, 2017, 37(4):8-14.
[9] SHI B, WU Y, LIU J. Vapor permeation separation of MeOH/MTBEthrough polyimide poly(ether-sulfone)hollow-fibermembranes[J]. Desalination, 2004, 161(1):59-66.
[10] QIAO X, CHUNG T S. Fundamental characteristics of sorption,swelling, and permeation of P84 co-polyimide membranes forpervaporation dehydration of alcohols[J]. Industrial&EngineeringChemistry Research, 2005, 44(23):8938-8943.
[11] SALEHIAN P, YONG W F, CHUNG T S. Development of highperformance carboxylated PIM-1/P84 blend membranes forpervaporation dehydration of isopropanol and CO2/CH4separation[J].Journal of Membrane Science, 2016, 518:110-119.
[12] WEI Q, ZHANG Y, WANG Y, et al. Measurement and modeling of the effect of composition ratios on the properties of poly(vinyl alcohol)/poly(vinyl pyrrolidone)membranes[J]. Materials&Design, 2016, 103:249-258.
[13] KANAGARAJ P, NAGENDRAN A, RANA D, et al. Effects ofpolyvinylpyrrolidone on the permeation and fouling-resistanceproperties of polyetherimide ultrafiltration membranes[J]. Industrial&Engineering Chemistry Research, 2015, 54(17):4832-4838.
[14] ZHANG Q G, HU W W, ZHU A M, et al. UV-crosslinked chitosan/polyvinylpyrrolidone blended membranes for pervaporation[J]. RSCAdvances, 2013, 3(6):1855-1861.
[15] HAN G L, GONG Y, ZHANG Q G, et al. Polyarylethersulfone withcardo/poly(vinyl pyrrolidone)blend membrane for pervaporation ofmethanol/methyl tert-butyl ether mixtures[J]. Journal of MembraneScience, 2013, 448(24):55-61.
[16]徐荣,邹琳,张琪,等.有机硅烷交联PDMS/陶瓷复合膜的制备及渗透汽化汽油脱硫性能[J].化工进展, 2016, 35(10):3331-3336.XU Rong, ZOU Lin, ZHANG Qi, et al. Fabrication of aminosilanecrosslinked PDMS/ceramic composite membranes for pervaporativedesulfurization of gasoline[J]. Chemical Industry and EngineeringProgress, 2016, 35(10):3331-3336.
[17] SHAO L, LAU C H, CHUNG T S. A novel strategy for surfacemodification of polyimide membranes by vapor-phase ethylenediamine(EDA)for hydrogen purification[J]. International Journal of HydrogenEnergy, 2009, 34(20):8716-8722.
[18] WU H, FANG X, ZHANG X, et al. Cellulose acetate-poly(N-vinyl-2-pyrrolidone)blend membrane for pervaporation separation of methanol/MTBE mixtures[J]. Separation and Purification Technology, 2008, 64(2):183-191.
[19] YONG W F, CHUNG T S. Miscible blends of carboxylated polymers ofintrinsic microporosity(cPIM-1)and Matrimid[J]. Polymer, 2015, 59:290-297.
[20] SOLOUKIPOUR S, SALJOUGHI E, MOUSAVI S M, et al. PEBA/PVDF blend pervaporation membranes:preparation and performance[J]. Polymers for Advanced Technologies, 2017, 28(1):113-123.
[21] HIRAYAMA Y, YOSHIGANA T, KUSUKI Y, et al. Relation of gaspermeability with structure of aromatic polyimides I[J]. Journal ofMembrane Science, 1996, 111(2):169-182.
[22] TEOH M M, CHUNG T S, WANG K Y, et al. Exploring Torlon/P84 co-polyamide-imide blended hollow fibers and their chemical cross-linking modifications for pervaporation dehydration of isopropanol[J].Separation and Purification Technology, 2008, 61(3):404-413.
[23] ZERESHKI S, FIGOLI A, MADAENI S S, et al. Effect of polymercomposition in PEEKWC/PVP blends on pervaporation separation ofethanol/cyclohexane mixture[J]. Separation&Purification Technology,2010, 75(3):257-265.
[24] ZHANG S, ZOU Y, WEI T, et al. Pervaporation dehydration of binaryand ternary mixtures of n-butyl acetate, n-butanol and water usingPVA-CS blended membranes[J]. Separation and PurificationTechnology, 2017, 173:314-322.
[25] WIJMANS J G, BAKER R W. The solution-diffusion model:a review[J]. Journal of Membrane Science, 1995, 107(1/2):1-21.
[26] XU Y, CHEN C, LI J. Experimental study on physical properties andpervaporation performances of polyimide membranes[J]. ChemicalEngineering Science, 2007, 62(9):2466-2473.
[27] JADAV G L, ASWAL V K, BHATT H, et al. Influence of filmthickness on the structure and properties of PDMS membrane[J].Journal of Membrane Science, 2012, 415/416(10):624-634.
[28] GAO C, ZHANG M, JIANG Z, et al. Preparation of a highly water-selective membrane for dehydration of acetone by incorporatingpotassium montmorillonite to construct ionized water channel[J].Chemical Engineering Science, 2015, 135:461-471.
[29] LI Q, LIU Q, ZHAO J, et al. High efficient water/ethanol separation by amixed matrix membrane incorporating MOF filler with high wateradsorption capacity[J]. JournalofMembrane Science, 2017, 544:68-78.