Al_2O_3和SiC微滤膜的疏水改性及其油固分离性能研究
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摘要
以正辛基三乙氧基硅烷和乙醇分别作为改性剂和溶剂,采用接枝聚合法对平均孔径为500 nm的Al_2O_3膜和SiC膜进行疏水改性,考察了改性剂浓度、改性液温度和改性时间对膜表面疏水效果的影响,并对比了疏水改性前后两种陶瓷膜的表面性质及疏水改性后的油固分离性能,进行了反冲实验和稳定性测试。结果表明,两种陶瓷膜材料在改性剂浓度为0.2 mol·L~(-1),改性液温度为40℃,改性时间为12 h时,疏水改性效果最好,得到的疏水Al_2O_3膜和SiC膜的水接触角分别为134°±1°和140°±1°,经改性后的SiC膜的疏水效果优于Al_2O_3膜。在油固分离实验中,疏水Al_2O_3膜和SiC膜均对固体炭黑有良好的截留性能,但疏水改性对SiC膜的油品通量提升更为显著,两种膜的稳态通量分别为1134 L·m~(-2)·h~(-1)和1408 L·m~(-2)·h~(-1)。反冲操作对疏水SiC膜的通量恢复更有利。
The Al_2O_3 film and the SiC film with an average pore diameter of 500 nm were hydrophobically modified by n-octyltriethoxysilane and ethanol as modifiers and solvents,respectively.The concentration and modification of the modifer were investigated by graft polymerization.The wettability and oil-solid separation performance of the modified Al_2O_3 and SiC MF membranes were investigated.The backflushing operation and long-term stability test for the modified membranes were conducted.Under the optimal modification conditions with grafting agent concentration of 0.2 mol·L~(-1),grafting temperature of 40℃and grafting time of 12 h,the water contact angles(WCAs)of the modified Al_2O_3 and SiC membranes were as high as 134°±1°and 140°±1°,respectively.It was found that the hydrophobic SiC membrane showed higher hydrophobicity than that of the Al_2O_3 membrane.For oil-solid separation experiments,both modified membranes exhibited excellent rejection to impurities in oil phase.However,the hydrophobic modification had a more significant effect on the flux of SiC membrane.The fluxes of hydrophobic Al_2O_3 and SiC MF membranes were 1134 L·m~(-2)·h~(-1)and 1408 L·m~(-2)·h~(-1),respectively,with transmembrane pressure of 0.25 MPa.Backflushing operation was beneficial to the flux recovery of ceramic membrane,especially hydrophobic SiC membrane.
The Al_2O_3 film and the SiC film with an average pore diameter of 500 nm were hydrophobically modified by n-octyltriethoxysilane and ethanol as modifiers and solvents,respectively.The concentration and modification of the modifer were investigated by graft polymerization.The wettability and oil-solid separation performance of the modified Al_2O_3 and SiC MF membranes were investigated.The backflushing operation and long-term stability test for the modified membranes were conducted.Under the optimal modification conditions with grafting agent concentration of 0.2 mol·L~(-1),grafting temperature of 40℃and grafting time of 12 h,the water contact angles(WCAs)of the modified Al_2O_3 and SiC membranes were as high as 134°±1°and 140°±1°,respectively.It was found that the hydrophobic SiC membrane showed higher hydrophobicity than that of the Al_2O_3 membrane.For oil-solid separation experiments,both modified membranes exhibited excellent rejection to impurities in oil phase.However,the hydrophobic modification had a more significant effect on the flux of SiC membrane.The fluxes of hydrophobic Al_2O_3 and SiC MF membranes were 1134 L·m~(-2)·h~(-1)and 1408 L·m~(-2)·h~(-1),respectively,with transmembrane pressure of 0.25 MPa.Backflushing operation was beneficial to the flux recovery of ceramic membrane,especially hydrophobic SiC membrane.
引文
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[31]Ding D,Mao H Y,Chen X F,et al.Underwater superoleophobicunderoil superhydrophobic Janus ceramic membrane with its switchable separation in oil/water emulsions[J].Journal of Membrane Science,2018,565:303-310.
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[33]Gao N W,Ke W,Fan Y Q,et al.Evaluation of the oleophilicity of different alkoxysilane modified ceramic membranes through wetting dynamic measurements[J].Applied Surface Science,2013,283(14):863-870.
[34]孟庆伟,张峰,陈璐,等.离子筛吸附与陶瓷膜耦合用于盐湖卤水提锂[J].化工学报,2017,68(5):1899-1905.Meng Q W,Zhang F,Chen L,et al.Lithium recovery from qarham brine using adsorption-membrane separation hybrid system[J].CIESC Journal,2017,68(5):1899-1905.
[35]Cakl J,Bauer I,Dole?ek P,et al.Effects of backflushing conditions on permeate flux in membrane crossflow microfiltration of oil emulsion[J].Desalination,2000,127(2):189-198.
[2]Wei Y B,Qi H,Gong X,et al.Specially wettable membranes for oil-water separation[J].Advanced Materials Interfaces,2018,5(23):1800576.
[3]Chen X,Lim J F,Xu Y,et al.Operating conditions and feed composition on filtering emulsified oil using ceramic-hybrid membrane[J].Ceramics International,2016,42(15):17101-17109.
[4]张谨,李俊俊,纪晓声,等.利用混凝-超滤膜法研究乳化油水的分离过程[J].高校化学工程学报,2017,31(2):449-455.Zhang J,Li J J,Ji X S,et al.Study on oil separation from oil/water emulsion via coagulation and ultrafiltration[J].Journal of Chemical Engineering of Chinese Universities,2017,31(2):449-455.
[5]刘君腾,卿伟华,任钟旗,等.超疏水聚四氟乙烯丝网用于原油脱水的研究[J].高校化学工程学报,2012,26(4):563-568.Liu J T,Qing W H,Ren Z Q,et al.The study of crude oil dehydration using super-hydrophobic PTFE-coated wire mesh[J].Journal of Chemical Engineering of Chinese Universities,2012,26(4):563-568.
[6]Xu S,Ren L F,Zhou Q,et al.Facile ZIF-8 functionalized hierarchical micronanofiber membrane for high-efficiency separation of water-in-oil emulsions[J].Journal of Applied Polymer Science,2018,135(27):46462.
[7]Coutinho C D M,Chiu M C,Basso R C,et al.State of art of the application of membrane technology to vegetable oils:a review[J].Food Research International,2009,42(5/6):536-550.
[8]Padaki M,Murali R S,Abdullah M S,et al.Membrane technology enhancement in oil-water separation:a review[J].Desalination,2015,357(357):197-207.
[9]Khemakhem M,Khemakhem S,Amar R B.Emulsion separation using hydrophobic grafted ceramic membranes by[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2013,436(35):402-407.
[10]Ren C,Fang H,Gu J Q,et al.Preparation and characterization of hydrophobic alumina planar membranes for water desalination[J].Journal of the European Ceramic Society,2015,35(2):723-730.
[11]李云,胡浩威.润湿性对纳米多孔陶瓷膜输运性能的影响[J].化工学报,2017,68(9):3474-3481.Li Y,Hu H W.Effect of wettability on nanoporous ceramic membrane for condensate transport performance[J].CIESCJournal,2017,68(9):3474-3481.
[12]Kujawa J,Kujawski W.Functionalization of ceramic metal oxide powders and ceramic membranes by perfluroalkylsilanes and alkylsilanes possessing different reactive groups physicochemical and tribological properties[J].ACS Applied Materials&Interfaces,2016,8(11):7509-7521.
[13]Kujawa J,Cerneaux S,Kujawski W,et al.Hydrophobic ceramic membranes for water desalination[J].Applied Sciences,2017,7(4):402.
[14]Gao N W,Fan Y Q,Quan X J,et al.Modified ceramic membranes for low fouling separation of water-in-oil emulsions[J].Journal of Materials Science,2016,51(13):6379-6388.
[15]Ahmad N A,Leo C P,Ahmad A L.Superhydrophobic alumina membrane by steam impingement:minimum resistance in microfiltration[J].Separation and Purification Technology,2013,107(4):187-194.
[16]Zhang W B,Shi Z,Zhang F,et al.Superhydrophobic and superoleophilic PVDF membranes for effective separation of water-in-oil emulsions with high flux[J].Advanced Materials,2013,25(14):2071-2076.
[17]Bukhari S Z A,Ha J H,Lee J,et al.Effect of different heat treatments on oxidation-bonded SiC membrane for water filtration[J].Ceramics International,2018,44(12):14251-14257.
[18]代小元,沈凡,戴武斌,等.碳化硅陶瓷膜处理工业废水的工艺特性研究[J].武汉工程大学学报,2018,40(3):284-287.Dai X Y,Shen F,Dai W B,et al.Process characteristics of industrial wastewater treatment with silicon carbide ceramic membrane[J].Journal of Wuhan Institute of Technology,2018,40(3):284-287.
[19]De Wit P,Kappert E J,Lohaus T,et al.Highly permeable and mechanically robust silicon carbide hollow fiber membranes[J].Journal of Membrane Science,2015,475:480-487.
[20]王新.集成银丝SiC/PU复合加热膜的制备及性能分析[D].天津:天津工业大学,2014.Wang X.Preparation and performance analysis of integrated silver wire SiC/PU composite heating film[D].Tianjin:Tianjin Polytechnic University,2014.
[21]Jacob D S,Gedanken A.Effect of reaction parameters on the hydrolysis of tetramethyl orthosilicate and tetraethyl orthosilicate and their surface morphology in an ionic liquid[J].Journal of the American Ceramic Society,2010,91(9):3024-3030.
[22]陈奎,张天云,曹秀鸽,等.γ-(2,3-环氧丙烷)丙基三甲氧基硅烷水解研究[J].化工新型材料,2011,39(9):96-108.Chen K,Zhang T Y,Cao X G.et al.Hydrolysis study on organic silicon oxygen alkyl GPTMS[J].New Chemical Materials,2011,39(9):96-108.
[23]Ciobotaru I A,Major I,Vaireaun D I,et al.The determination of the optimum hydrolysis time for silane films deposition[J].Applied Surface Science,2016,371:275-280.
[24]Gaber A A,Ibrahim D M,Abd-Aimohsen F F,et al.Synthesis of alumina,titania,and alumina-titania hydrophobic membranes via sol-gel polymeric route[J].Journal of Analytical Science and Technology,2013,4(1):4-18.
[25]Fang H,Gao J F,Wang H T,et al.Hydrophobic porous alumina hollow fiber for water desalination via membrane distillation process[J].Journal of Membrane Science,2012,403/404(6):41-46.
[26]王煜琨,韦奇,张少康,等.碳氟基团修饰的多孔陶瓷膜润湿性、表面自由能及渗透性能的研究[J].膜科学与技术,2018,38(2):52-59.Wang Y K,Wei Q,Zhang S K,et al.Wettability,surface free energy and permeability of porous ceramic membranes silylated by fluorocarbon groups[J].Membrane Science and Technology,2018,38(2):52-59.
[27]Gao N W,Li M,Jing W H,et al.Improving the filtration performance of ZrO2membrane in non-polar organic solvents by surface hydrophobic modification[J].Journal of Membrane Science,2011,375(1/2):276-283.
[28]Ek S,Root A,Peussa M,et al.Determination of the hydroxyl group content in silica by thermogravimetry and a comparison with1H MAS NMR results[J].Thermochimica Acta,2001,379(1/2):201-212.
[29]Kujawa J,Cerneaux S,Kujawski W.Characterization of the surface modification process of Al2O3,TiO2and ZrO2powders by PFAS molecules[J].Colloids and Surfaces A:Physicochemical and Engineering Aspects,2014,447(5):14-22.
[30]Van Oss C J,Chaudhury M K,Good R J.Interfacial Lifshitz-van der Waals and polar interactions in macroscopic systems[J].Chemical Reviews,1988,88(6):927-941.
[31]Ding D,Mao H Y,Chen X F,et al.Underwater superoleophobicunderoil superhydrophobic Janus ceramic membrane with its switchable separation in oil/water emulsions[J].Journal of Membrane Science,2018,565:303-310.
[32]Wu J,Ling L,Xie J,et al.Surface modification of nanosilica with3-mercaptopropyl trimethoxysilane:experimental and theoretical study on the surface interaction[J].Chemical Physics Letters,2014,591:227-232.
[33]Gao N W,Ke W,Fan Y Q,et al.Evaluation of the oleophilicity of different alkoxysilane modified ceramic membranes through wetting dynamic measurements[J].Applied Surface Science,2013,283(14):863-870.
[34]孟庆伟,张峰,陈璐,等.离子筛吸附与陶瓷膜耦合用于盐湖卤水提锂[J].化工学报,2017,68(5):1899-1905.Meng Q W,Zhang F,Chen L,et al.Lithium recovery from qarham brine using adsorption-membrane separation hybrid system[J].CIESC Journal,2017,68(5):1899-1905.
[35]Cakl J,Bauer I,Dole?ek P,et al.Effects of backflushing conditions on permeate flux in membrane crossflow microfiltration of oil emulsion[J].Desalination,2000,127(2):189-198.