超亲水/水下超疏油膜的制备及油水分离性能
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摘要
工业生产和频繁的溢油事故产生大量的含油废水,其高效分离依然面临全球性的挑战。具有仿生浸润特性的膜可以选择性透过水或油,分离效率高且操作简单而广泛应用于油水分离。本文通过一步浸渍法将TiO_2纳米颗粒和聚乙烯吡咯烷酮(PVP)原位固化到不锈钢网上制备了具有微/纳米层级结构的超亲水/水下超疏油油水分离膜。重点考察了TiO_2/PVP涂覆液浓度(质量分数1%、3%、5%、7%、9%)对膜的浸润特性和油水分离性能的影响。实验结果表明,不同TiO_2/PVP浓度改性的膜具有超亲水/水下超疏油特性,水的接触角均为0°,在水中油的接触角达160°,油水分离效率大于99.5%。膜通量随浓度的增大先减小后增加,当质量分数为3%时膜通量最大为8422.5L/(m~2·h)。经过30次连续油水分离后,其分离效率仍大于99.5%,表明TiO_2/PVP-SS(stainlesssteel)膜有良好的耐久性和稳定性。因此,TiO_2/PVP-SS仿生特殊浸润膜材料在油水分离领域具有经济、高效、环境友好的潜在优势。
The rapid development of industry activities and the frequently oil leakage accidents have produced large amount of oily wastewater and high efficient separation is still a worldwide challenge. Bio-inspired membranes with special wettability have highly selectivity on oil or water and have been extensively used for oil/water separation because of the advantages of easy operation, high efficiency. A one-step fabrication of micro/nano scale hierarchical structure superhydrophilic and underwater superoleophobic oil/water separation membrane was developed through impregnation of TiO_2 nanoparticles and polyvinyl pyrrolidone(PVP)into stainless steel mesh. The effects of TiO_2/PVP concentration on wetting properties and oil-water separation performances were investigated. The results indicated that water contact angle of the modified membrane was 0°, underwater oil contact angle was 160°, and the oil-water separation efficiency was above 99.5% under varied coating concentrations. The flux of these as-prepared membranes undergone a trend of going up and drop down, the maximum flux of 8422.5 L/(m~2·h) was reached at the TiO_2/PVP concentration of 3%. The mesh still maintained separation efficiency above 99.5% after 30 separation cycles, indicating that the TiO_2/PVP-SS(stainless steel)modified membrane has good durability and stability. Therefore, the TiO_2/PVP modified bionic special wettability membrane has the potential advantages of economy, high efficiency and environmental friendliness in the oil-water separation.
The rapid development of industry activities and the frequently oil leakage accidents have produced large amount of oily wastewater and high efficient separation is still a worldwide challenge. Bio-inspired membranes with special wettability have highly selectivity on oil or water and have been extensively used for oil/water separation because of the advantages of easy operation, high efficiency. A one-step fabrication of micro/nano scale hierarchical structure superhydrophilic and underwater superoleophobic oil/water separation membrane was developed through impregnation of TiO_2 nanoparticles and polyvinyl pyrrolidone(PVP)into stainless steel mesh. The effects of TiO_2/PVP concentration on wetting properties and oil-water separation performances were investigated. The results indicated that water contact angle of the modified membrane was 0°, underwater oil contact angle was 160°, and the oil-water separation efficiency was above 99.5% under varied coating concentrations. The flux of these as-prepared membranes undergone a trend of going up and drop down, the maximum flux of 8422.5 L/(m~2·h) was reached at the TiO_2/PVP concentration of 3%. The mesh still maintained separation efficiency above 99.5% after 30 separation cycles, indicating that the TiO_2/PVP-SS(stainless steel)modified membrane has good durability and stability. Therefore, the TiO_2/PVP modified bionic special wettability membrane has the potential advantages of economy, high efficiency and environmental friendliness in the oil-water separation.
引文
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[22]薛众鑫,江雷.仿生水下超疏油表面[J].高分子学报,2012(10):1091-1101.XUE Zhongxin, JIANG Lei. Bioinspired underwater superoleophobic surfaces[J]. Acta Polymerica Sinica, 2012(10):1091-1101.
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[24]XUEZX,JIANGL.Bioinspiredunderwatersuperoleophobic surffaces[J]. Acta Polymerica Sinica, 2012, 12(10):1091-1101.
[25]YUYuanlie,CHENHua,LIUYun,et al.Selectiveseparation ofoil andwaterwithmeshmembranesbycapillarity[J].Advancesin Colloid and Interface Science, 2016(235):46-55.
[26]JINY,ZHAOZZ,XIANGHX,etal.Superhydrophilicsuperoleophobiccoatings[J].JournalofMaterialsChemistry,2012,22(7):2834-2837.
[2]LIU D, HE L, LEI W W, et al. Multifunctional polymer/porous boron nitridenanosheetmembranesforsuperiortrappingemulsifiedoils and organic molecules[J]. Advanced Materials Interfaces, 2015, 2(12):1500228.
[3]CAOY,LIUN,ZHANGW,etal.One-stepcoatingtoward multifunctionalapplications:oil/watermixturesandemulsions separationandcontaminantsadsorption[J].ACSAppliedMaterials&Interfaces, 2016, 8(5):3333-3339.
[4]XUEZX,WANGST,LINL,etal.Anovelsuperhydrophilicand underwatersuperoleophobichydrogel-coatedmeshforoil/water separation[J]. Advanced Materials, 2011, 23(37):4270-4273.
[5]XUEZX,CAOYZ,LIUN,etal.Specialwettablematerialsfor oil/water separation[J]. J. Mater. Chem. A, 2014, 2(8):2445-2460.
[6]WENZELRN.Resistanceofsolidsurfacestowettingbywater[J].Ind. Eng. Chem., 1936, 28(8):988-994.
[7]CASSIE A B D, BAXTER S. Wettability of porous surfaces[J]. Trans.Faraday. Soc., 1944, 40(1):546-551.
[8]LIANGWX,GUOZG.Stablesuperhydrophobicand superoleophilic soft porous materials for oil/water separation[J]. RSC Advances, 2013, 3(37):16469-16474.
[9]DONGY,LIJ,SHIL,etal.Underwatersuperoleophobicgraphene oxidecoatedmeshesfortheseparationofoilandwater[J].Chem.Commun(Camb), 2014, 50(42):5586-5589.
[10]WANGLF,YANGSY,WANGJ,etal.Fabricationof superhydrophobicTPUfilmforoil–waterseparationbasedon electrospinning route[J]. Materials Letters, 2011, 65(5):869-872.
[11]LI Jian, YAN Long, LI Haoyu, et al. A facile one-step spray-coating processforthefabricationofasuperhydrophobicattapulgitecoated meshforuseinoil/waterseparation[J].RSCAdv.,2015,5(66):53802-53808.
[12]LIX,WANGM,WANGC,etal.FacileimmobilizationofAg nanoclusteronnanofibrousmembraneforoil/waterseparation[J].ACS Applied Mater Interfaces, 2014, 6(17):15272-15282.
[13]张晟卯,吴红丽,张治军.二氧化钛聚乙烯吡咯烷酮纳米复合薄膜的制备与表征[J].化学研究, 2003, 14(1):1-3.ZHANGShengmao,WUHongli,ZHANGZhijun.Preparationand characterizationofTiO2/PVPnanocompositethinfilms[J].Chemical Research, 2003, 14(1):1-3.
[14]滕乐天,赵康,汤玉斐.静电纺丝制备TiO2纳米纤维的光催化性能[J].硅酸盐学报, 2012, 40(8):1215-1219.TENGLetian,ZHAOKang,TANGYufei.Photocatalyticacticityof TiO2nanofiberspreparedviaelectrospinningtechnology[J].Journal of the Chinese Ceramic Society, 2012, 40(8):1215-1219.
[15]朱海涛,曹洪美,张文静.不锈钢滤网的改性及其疏水亲油性能[J].青岛科技大学学报, 2016, 37(6):642-647.ZHUHT,CAOHM,ZHANGWJ.Modificationand hydrophobicity/olephilicityofstainlessfiltermesh[J].Journalof Qingdao University of Science and Technology, 2016, 37(6):642-647.
[16]靳健,刘沛清,林贵平,等.加入纳米颗粒的相变悬浮液黏性和热导率特性[J].航空学报, 2010, 31(2):244-248.JINJian,LIUPeiqing,LINGuiping,etal.Viscosityandthermal conductivitycharacteristicsofmicroencapsulatedphasechange materialsuspensionsaddedwithnano-particles[J].ActaAeronautice Et Astronautice Sinice, 2010, 31(2):244-248.
[17]徐继润,徐俊杰,邢军,等.易沉降悬浮液流变性测定时循环速度的理论分析[J].过滤与分析, 2009, 19(3):1-3.XUJirun,XUJunjie,XINGJun,etal.Theoreticalanalysisof circulationvelocityindeterminationofrheologicalpropertyof suspendedsuspension[J].JournalofFiltration&Separation,2009,19(3):1-3.
[18]斯芳芳,张靓,赵宁,等.超亲水表面制备方法及其应用[J].化学进展, 2011, 23(9):1831-1840.SIFangfang,ZHANGLiang,ZHAONing,etal.Superhydrophilic surfaces:preparation method and application[J].Progress in Chemistry,2011, 23(9):1831-1840.
[19]GUNATILAKEUB,BANDARAJ.Efficientremovalofoilfromoil contaminated water by superhydrophilic and underwater superoleophobic nano/microstructuredTi O2nanofiberscoatedmesh[J].Chemosphere,2017, 171:134-141.
[20]WANGST,ZHUY,XIAF,etal.Thepreparationofa superhydrophiliccarbonfilmfromasuperhydrophobiclotusleaf[J].Carbon, 2006, 44(9):1848-1850.
[21]WUJ,CHENJ,QASIMK,etal.Ahierarchicalmeshfilmwith superhydrophobicandsuperoleophilicpropertiesforoilandwater separation[J].JournalofChemicalTechnology&Biotechnology,2012, 87(3):427-430.
[22]薛众鑫,江雷.仿生水下超疏油表面[J].高分子学报,2012(10):1091-1101.XUE Zhongxin, JIANG Lei. Bioinspired underwater superoleophobic surfaces[J]. Acta Polymerica Sinica, 2012(10):1091-1101.
[23]SHIH,HEY,PANY,etal.Amodifiedmussel-inspiredmethodto fabricateTiO2decoratedsuperhydrophilicPVDFmembranefor oil/waterseparation[J].JournalofMembraneScience,2016,506:60-70.
[24]XUEZX,JIANGL.Bioinspiredunderwatersuperoleophobic surffaces[J]. Acta Polymerica Sinica, 2012, 12(10):1091-1101.
[25]YUYuanlie,CHENHua,LIUYun,et al.Selectiveseparation ofoil andwaterwithmeshmembranesbycapillarity[J].Advancesin Colloid and Interface Science, 2016(235):46-55.
[26]JINY,ZHAOZZ,XIANGHX,etal.Superhydrophilicsuperoleophobiccoatings[J].JournalofMaterialsChemistry,2012,22(7):2834-2837.