部分嵌入式静电自组装改性聚酰胺反渗透膜?
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摘要
针对聚酰胺反渗透膜(RO)抗阳离子表面活性剂污染能力差的难点,提出改变反渗透膜表面荷电性方法,以聚乙烯亚胺(PEI)的乙醇溶液为电解质溶液,利用部分嵌入式静电自组装法对聚酰胺反渗透膜进行改性。采用场发射扫描电子显微镜(FE-SEM)、X射线光电子能谱(XPS)、接触角和固体表面Zeta电位对改性反渗透膜的结构和性能进行表征。结果表明,FE-SEM图像显示膜表面形态没有发生变化;XPS元素分峰和含量分析证明了PEI成功组装在反渗透膜上;接触角验证了改性后膜的亲水性增加,Zeta电位证实了改性后膜的荷负电性减小。改性后膜通量和脱盐性能均增加,抗污染性能得到显著改善,并具有耐酸碱稳定性(pH 2～11)。
In order to improve anti-cationic surfactant pollution performance of polyamide reverse osmosis(RO) membranes, a partially embedded electrostatic self-assembly method was used with polyethyleneimine(PEI)-ethanol solution as the polyelectrolyte solution to modified RO membrane surface.The RO membranes were characterized by field emission scanning electron microscopy(FE-SEM), X-ray photoelectron spectroscopy(XPS), contact angle and solid surface Zeta potential. The FE-SEM results show that the surface morphology of the modified membranes is not changed. XPS elemental and content analysis prove that PEI is successfully assembled on membrane surface, while contact angle results verify that the modified membrane shows increased hydrophilicity. Furthermore, zeta potential results confirm the charge-negativity of the modified membrane decreases. The modified membranes have higher flux and salt rejection, better antifouling to cationic surfactants and good stability in acid and base conditions(pH2～11).
In order to improve anti-cationic surfactant pollution performance of polyamide reverse osmosis(RO) membranes, a partially embedded electrostatic self-assembly method was used with polyethyleneimine(PEI)-ethanol solution as the polyelectrolyte solution to modified RO membrane surface.The RO membranes were characterized by field emission scanning electron microscopy(FE-SEM), X-ray photoelectron spectroscopy(XPS), contact angle and solid surface Zeta potential. The FE-SEM results show that the surface morphology of the modified membranes is not changed. XPS elemental and content analysis prove that PEI is successfully assembled on membrane surface, while contact angle results verify that the modified membrane shows increased hydrophilicity. Furthermore, zeta potential results confirm the charge-negativity of the modified membrane decreases. The modified membranes have higher flux and salt rejection, better antifouling to cationic surfactants and good stability in acid and base conditions(pH2～11).
引文
[1]CHEN D D,WU M D,LI B C,et al.Layer-by layer-assembled healable antifouling films[J].Advanced Materials,2015,27(39):5882-5888.
[2]李艳,王程,杜国强.静电自组装制备海泡石负载纳米TiO2复合光催化材料研究[J].高校化学工程学报,2011,25(5):871-876.LI Y,WANG C,DU G Q.Preparation and photocatalytic activity of sepiolite supported sano TiO2 cmposite photocatalysts prepared by electrostatic self assembly method[J].Journal of Chemical Engineering of Chinese Universities,2011,25(5):871-876.
[3]卢金荣,陈国华,吴大军.静电自组装功能性纳米复合膜的研究进展[J].材料导报,2004,18(3):57-60.LU J R,CHEN G H,WU D J.Progress in study of functional nanocomposite films formed via electrostatics self-assembly[J].Materials Review,2004,18(3):57-60.
[4]SUN J,YI Z,ZHAO X T,et al.CO2 separation membranes with high permeability and CO2/N2 selectivity prepared by electrostatic self-assembly of polyethylenimine on reverse osmosis membranes[J].RSC Advances,2017,7(24):14678-14687.
[5]刘美玲,刘军,王琴,等.聚电解质静电沉积改性制备高性能反渗透膜[J].化工学报,2018,69(2):830-839.LIU M L,LIU J,WANG Q,et al.Surface modification of reverse osmosis membrane by electrostatic deposition of polyelectrolyte for performance improvement[J].CIESC Journal,2018,69(2):830-839.
[6]ROUSE J H,LILLEHEI P T.Electrostatic assembly of polymer/single walled carbon nanotube multilayer films[J].Nano Letters,2003,3(1):59-62.
[7]KRASEMANN L,TIEKE B.Composite membranes with ultrathin separation layer prepared by self-assembly of polyelectrolytes[J].Materials Science and Engineering C,1999,8/9:513-518.
[8]翟青霞,黄英,李玉青.静电自组装膜研究进展[J].材料开发与应用,2010,25(2):86-92.ZHAI Q X,HUANG Y,LI Y Q.Development of electrostatic self-assembly nano-composite thin films[J].Development and Application of Materials,2010,25(2):86-92.
[9]LOWACK K,HELM C A.Molecular mechanisms controlling the self-assembly process of polyelectrolyte multilayer[J].Macromolecules,1998,31(3):823-833.
[10]SHULTZ S,BASS M,SEMIAT R.Modification of polyamide membranes by hydrophobic molecular plugs for improved boron rejection[J].Journal of Membrane Science,2018,546:165-172.
[11]ZHAO Y Y,YUAN Q P.Effect of membrane pretreatment on performance of solvent resistant nanofiltration membranes in methanol solutions[J].Journal of Membrane Science,2006,280(1/2):195-201.
[12]FREGER V.Swelling and morphology of the skin layer of polyamide composite membrane:an atomic force microscopy study[J].Environment Science and Technology,2004,38(11):3168-3175.
[13]RANDOVáA,BARTOVSKáL,HOVORKA?.New approach for descriotion for description of sorption and swelling phenomena in liquid+polymer membrane systems[J].Separation and Purification Technology,2017,179:475-485.
[14]骆广生,夏芳,戴猷元.溶胀对膜萃取传质性能的影响[J].水处理技术,1999,25(1):9-13.LUO G S,XIA F,DAI Y Y.Effect of swelling on mass transfer performance in membrane extraction[J].Technology of Water Treatment,1999,25(1):9-13.
[15]DRáZEVI?E,KO?UTI?K,FREGER V.Permeability and selectivity of reverse osmosis membranes:correlation to swelling revisited[J].Water Research,2014,49:444-452.[16 LIN L,LOPEZ R,RAMON G A,et al.Investigating the void structure of the polyamide active layers of thin-film composite membranes[J].Journal of Membrane Science,2016,497:365-376.
[17]JAHAN Z,NIAZI M B K,GREGERSEN?W.Mechanical,thermal and swelling properties of cellulose nanocrystals/PVAnanocomposites membranes[J].Journal of Membrane Science,2018,57:113-124.
[18]梅苏宁,杨建明,张前,等.聚乙烯亚胺在新领域的应用研究进展[J].化工新型材料,2017,45(10):35-37.MEI S N,YANG J M,ZHANG Q,et al.Research progress on application of polyethyleneimine in the new field[J].New Chemical Materials,2017,45(10):35-37.
[19]谷金钰,李昊,许文盛,等.聚多巴胺-聚乙烯亚胺改性反渗透膜制备与表征[J].人民长江,2017,48(16):31-42.GU J Y,LI H,XU W S,et al.Fabrication and characterization of a reverse osmosis membrane modified by polydopaminepolyethylenimine[J].Yangze River,2017,48(16):31-42.
[20]卜芳.阳离子表面活性剂聚集过程的热力学研究[D].大连:大连理工大学,2009.BU F.Thermodynamic investigation on the aggregation behavior of cationic surfactants[D].Dalian:Dalian University of Technology,2009.
[21]许骏.抗污染耐氯芳香聚酰胺复合反渗透膜制备及其性能研究[D].天津:天津大学,2013.XU J.Preparation and performances of anti-fouling and chlorine resistant aromatic polyamide composite reverse osmosis membranes[D].Tianjin:Tianjin University,2013.
[22]杨丽彬,孙本惠,徐叶新,等.聚酰亚胺膜在不同醇/水体系中的溶胀特性[J].膜科学与技术,2008,28(2):44-47.YANG L B,SUN B H,XU Y X,et al.Swelling characteristics of polyimide membrane in different aqueous alcohol solution[J].Membrane Science and Technology,2008,28(2):44-47.
[23]LOUIE J S,PINNAU I,REINHARD M.Effects of surface coating process conditions on the water permeation and salt rehection and salt rejection properties of composite polyamide reverse osmosis membranes[J].Journal of Membrane Science,2011,367(1/2):249-255.
[24]NIKKOLA J,LIU X,LI Y,et al.Surface modification of thin film composite RO membrane for enhanced anti-biofouling performance[J].Journal of Membrane Science,2013,444:192-200.
[25]LIU M H,CHEN Q,WANG L Z,et al.Improving fouling resistance and chlorine stability of aromatic polyamide thin-film composite RO membrane by surface grafting of polyvinyl alcohol(PVA)[J].Desalination,2015,367:11-20.
[26]EU J H,WANG Z,WANG Y,et al.Polyvinylamine-grafted polyamide reverse osmosis membrane with improved antifouling property[J].Journal of Membrane Science,2015,495:1-13.
[27]KARAN S,JIANG Z,LIVINGSTON A G.Sub-10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation[J].Science,2015,348(6241):1347-1351.
[28]MA L,ZHUANG H L,WEi S,et al.Enhanced Li-S batteries using amine-functionalized carbon nanotubes in the cathode[J].ACSNano,2015,10(1):1050-1059.
[29]TIAN X,WANG W,WANG Y,et al.Polyethylenimine functionalized halloysite nanotubes for efficient removal and fixation of Cr(VI)[J].Microporous and Mesoporous Materials,2015,207:46-52.
[30]ZHANG C,SU J,ZHU H,et al.The removal of heavy metal ions from aqueous solutions by amine functionalized cellulose pretreated with microwave-H2O2[J].RSC Advances,2017,7(54):34182-34191.
[31]LOUETTE P,BODINO F,PIREAUX J J.Poly(ethylene imine)(PEI)XPS reference core level and energy loss spectra[J].Surface Science Spectra,2005,12(1):54-58.
[32]XU J,WANG Z,WANG J X,et al.Positively charged aromatic polyamide reverse osmosis membrane with high anti-fouling property prepared by polyethylenimine grafting[J].Desalination,2015,365:398-406.
[33]KANG G D,CAO Y M.Development of antifouling reverse osmosis membranes for water treatment:a review[J].Water Research,2012,46(3):584-600.
[34]WANG Y,WANG Z,HAN X L,et al.Improved flux and anti-biofouling performances of reverse osmosis membrane via surface layer-by-layer assembly[J].Journal of Membrane Science,2017,539:403-411.
[35]GOOSEN M F A,SABLANI S S,AL-HINAI H,et al.Fouling of reverse osmosis and ultrafiltration membranes:a critical review[J].Separation Science and Technology,2004,39(10):2261-2297.
[36]LEE S,ANG W S,ELIMELECH M.Fouling of reverse osmosis membranes by hydrophilic organic matter:implications for water reuse[J].Desalination,2006,187(1-333):313-321.
[2]李艳,王程,杜国强.静电自组装制备海泡石负载纳米TiO2复合光催化材料研究[J].高校化学工程学报,2011,25(5):871-876.LI Y,WANG C,DU G Q.Preparation and photocatalytic activity of sepiolite supported sano TiO2 cmposite photocatalysts prepared by electrostatic self assembly method[J].Journal of Chemical Engineering of Chinese Universities,2011,25(5):871-876.
[3]卢金荣,陈国华,吴大军.静电自组装功能性纳米复合膜的研究进展[J].材料导报,2004,18(3):57-60.LU J R,CHEN G H,WU D J.Progress in study of functional nanocomposite films formed via electrostatics self-assembly[J].Materials Review,2004,18(3):57-60.
[4]SUN J,YI Z,ZHAO X T,et al.CO2 separation membranes with high permeability and CO2/N2 selectivity prepared by electrostatic self-assembly of polyethylenimine on reverse osmosis membranes[J].RSC Advances,2017,7(24):14678-14687.
[5]刘美玲,刘军,王琴,等.聚电解质静电沉积改性制备高性能反渗透膜[J].化工学报,2018,69(2):830-839.LIU M L,LIU J,WANG Q,et al.Surface modification of reverse osmosis membrane by electrostatic deposition of polyelectrolyte for performance improvement[J].CIESC Journal,2018,69(2):830-839.
[6]ROUSE J H,LILLEHEI P T.Electrostatic assembly of polymer/single walled carbon nanotube multilayer films[J].Nano Letters,2003,3(1):59-62.
[7]KRASEMANN L,TIEKE B.Composite membranes with ultrathin separation layer prepared by self-assembly of polyelectrolytes[J].Materials Science and Engineering C,1999,8/9:513-518.
[8]翟青霞,黄英,李玉青.静电自组装膜研究进展[J].材料开发与应用,2010,25(2):86-92.ZHAI Q X,HUANG Y,LI Y Q.Development of electrostatic self-assembly nano-composite thin films[J].Development and Application of Materials,2010,25(2):86-92.
[9]LOWACK K,HELM C A.Molecular mechanisms controlling the self-assembly process of polyelectrolyte multilayer[J].Macromolecules,1998,31(3):823-833.
[10]SHULTZ S,BASS M,SEMIAT R.Modification of polyamide membranes by hydrophobic molecular plugs for improved boron rejection[J].Journal of Membrane Science,2018,546:165-172.
[11]ZHAO Y Y,YUAN Q P.Effect of membrane pretreatment on performance of solvent resistant nanofiltration membranes in methanol solutions[J].Journal of Membrane Science,2006,280(1/2):195-201.
[12]FREGER V.Swelling and morphology of the skin layer of polyamide composite membrane:an atomic force microscopy study[J].Environment Science and Technology,2004,38(11):3168-3175.
[13]RANDOVáA,BARTOVSKáL,HOVORKA?.New approach for descriotion for description of sorption and swelling phenomena in liquid+polymer membrane systems[J].Separation and Purification Technology,2017,179:475-485.
[14]骆广生,夏芳,戴猷元.溶胀对膜萃取传质性能的影响[J].水处理技术,1999,25(1):9-13.LUO G S,XIA F,DAI Y Y.Effect of swelling on mass transfer performance in membrane extraction[J].Technology of Water Treatment,1999,25(1):9-13.
[15]DRáZEVI?E,KO?UTI?K,FREGER V.Permeability and selectivity of reverse osmosis membranes:correlation to swelling revisited[J].Water Research,2014,49:444-452.[16 LIN L,LOPEZ R,RAMON G A,et al.Investigating the void structure of the polyamide active layers of thin-film composite membranes[J].Journal of Membrane Science,2016,497:365-376.
[17]JAHAN Z,NIAZI M B K,GREGERSEN?W.Mechanical,thermal and swelling properties of cellulose nanocrystals/PVAnanocomposites membranes[J].Journal of Membrane Science,2018,57:113-124.
[18]梅苏宁,杨建明,张前,等.聚乙烯亚胺在新领域的应用研究进展[J].化工新型材料,2017,45(10):35-37.MEI S N,YANG J M,ZHANG Q,et al.Research progress on application of polyethyleneimine in the new field[J].New Chemical Materials,2017,45(10):35-37.
[19]谷金钰,李昊,许文盛,等.聚多巴胺-聚乙烯亚胺改性反渗透膜制备与表征[J].人民长江,2017,48(16):31-42.GU J Y,LI H,XU W S,et al.Fabrication and characterization of a reverse osmosis membrane modified by polydopaminepolyethylenimine[J].Yangze River,2017,48(16):31-42.
[20]卜芳.阳离子表面活性剂聚集过程的热力学研究[D].大连:大连理工大学,2009.BU F.Thermodynamic investigation on the aggregation behavior of cationic surfactants[D].Dalian:Dalian University of Technology,2009.
[21]许骏.抗污染耐氯芳香聚酰胺复合反渗透膜制备及其性能研究[D].天津:天津大学,2013.XU J.Preparation and performances of anti-fouling and chlorine resistant aromatic polyamide composite reverse osmosis membranes[D].Tianjin:Tianjin University,2013.
[22]杨丽彬,孙本惠,徐叶新,等.聚酰亚胺膜在不同醇/水体系中的溶胀特性[J].膜科学与技术,2008,28(2):44-47.YANG L B,SUN B H,XU Y X,et al.Swelling characteristics of polyimide membrane in different aqueous alcohol solution[J].Membrane Science and Technology,2008,28(2):44-47.
[23]LOUIE J S,PINNAU I,REINHARD M.Effects of surface coating process conditions on the water permeation and salt rehection and salt rejection properties of composite polyamide reverse osmosis membranes[J].Journal of Membrane Science,2011,367(1/2):249-255.
[24]NIKKOLA J,LIU X,LI Y,et al.Surface modification of thin film composite RO membrane for enhanced anti-biofouling performance[J].Journal of Membrane Science,2013,444:192-200.
[25]LIU M H,CHEN Q,WANG L Z,et al.Improving fouling resistance and chlorine stability of aromatic polyamide thin-film composite RO membrane by surface grafting of polyvinyl alcohol(PVA)[J].Desalination,2015,367:11-20.
[26]EU J H,WANG Z,WANG Y,et al.Polyvinylamine-grafted polyamide reverse osmosis membrane with improved antifouling property[J].Journal of Membrane Science,2015,495:1-13.
[27]KARAN S,JIANG Z,LIVINGSTON A G.Sub-10 nm polyamide nanofilms with ultrafast solvent transport for molecular separation[J].Science,2015,348(6241):1347-1351.
[28]MA L,ZHUANG H L,WEi S,et al.Enhanced Li-S batteries using amine-functionalized carbon nanotubes in the cathode[J].ACSNano,2015,10(1):1050-1059.
[29]TIAN X,WANG W,WANG Y,et al.Polyethylenimine functionalized halloysite nanotubes for efficient removal and fixation of Cr(VI)[J].Microporous and Mesoporous Materials,2015,207:46-52.
[30]ZHANG C,SU J,ZHU H,et al.The removal of heavy metal ions from aqueous solutions by amine functionalized cellulose pretreated with microwave-H2O2[J].RSC Advances,2017,7(54):34182-34191.
[31]LOUETTE P,BODINO F,PIREAUX J J.Poly(ethylene imine)(PEI)XPS reference core level and energy loss spectra[J].Surface Science Spectra,2005,12(1):54-58.
[32]XU J,WANG Z,WANG J X,et al.Positively charged aromatic polyamide reverse osmosis membrane with high anti-fouling property prepared by polyethylenimine grafting[J].Desalination,2015,365:398-406.
[33]KANG G D,CAO Y M.Development of antifouling reverse osmosis membranes for water treatment:a review[J].Water Research,2012,46(3):584-600.
[34]WANG Y,WANG Z,HAN X L,et al.Improved flux and anti-biofouling performances of reverse osmosis membrane via surface layer-by-layer assembly[J].Journal of Membrane Science,2017,539:403-411.
[35]GOOSEN M F A,SABLANI S S,AL-HINAI H,et al.Fouling of reverse osmosis and ultrafiltration membranes:a critical review[J].Separation Science and Technology,2004,39(10):2261-2297.
[36]LEE S,ANG W S,ELIMELECH M.Fouling of reverse osmosis membranes by hydrophilic organic matter:implications for water reuse[J].Desalination,2006,187(1-333):313-321.