SGO改性复合纳滤膜的制备及分盐性能
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摘要
近年来,水资源短缺,水源污染严重,国家对水处理末端的资源化利用提出了更高的要求,分盐过程也受到越来越多的关注.纳滤膜表面通常带有电荷,可以选择性地透过不同价态的离子.基于纳滤膜表面电荷特性不同,为很好地实现盐的分离,将制备的带有磺酸基团的氧化石墨烯引入到纳滤膜材料中,采用界面聚合法,制备了SGO改性复合纳滤膜. Zeta电位分析表明所制备的复合纳滤膜表面的电荷比不添加SGO的纳滤膜更负;红外光谱分析中酯基基团特征峰的出现表明磺酸基团参与了聚合反应; SEM结构表面,膜表面出现了明显的图灵结构,在0. 2 MPa压力下,纯水通量可达45. 85 L·(m~2·h)-1,对Na2SO4截留率为98. 23%,对Na Cl截留率为24. 93%,10 h运行可以很好地实现对SO_4~(2-)、Cl~-的有效分离,可实现盐的资源化回收.
In recent years,water resources are in short supply and seriously polluted. Increasingly more attention has been paid to the process of salt separation. The surface of the nanofiltration( NF) membrane is usually charged and can selectively allow the permeation of different ions. Based on the different charges on the NF membrane surface,in order to achieve a good separation of salt,the prepared graphene oxide with the sulfonic acid group was introduced into NF membrane material. Additionally,the SGO modified composite NF membrane was prepared by interfacial polymerization. Zeta potential analysis showed that the charge on the surface of the prepared NF membrane was more negative than that of the NF membrane without SGO. The peak of the ester group in the FT-IR analysis indicated that the sulfonate group was involved in the polymerization reaction. A Turing structure present on the surface of the membrane was evident through SEM pictures of the membrane surface. At a pressure of 0. 2 MPa,the pure water flux can reach 45. 85 L·( m~2·h)-1. The rejection of Na_2SO_4 was 98. 23%,while that of NaCl was 24. 93%. The 10 h operation can effectively separate SO_4~(2-) and Cl~-,which realized the salt recycling.
In recent years,water resources are in short supply and seriously polluted. Increasingly more attention has been paid to the process of salt separation. The surface of the nanofiltration( NF) membrane is usually charged and can selectively allow the permeation of different ions. Based on the different charges on the NF membrane surface,in order to achieve a good separation of salt,the prepared graphene oxide with the sulfonic acid group was introduced into NF membrane material. Additionally,the SGO modified composite NF membrane was prepared by interfacial polymerization. Zeta potential analysis showed that the charge on the surface of the prepared NF membrane was more negative than that of the NF membrane without SGO. The peak of the ester group in the FT-IR analysis indicated that the sulfonate group was involved in the polymerization reaction. A Turing structure present on the surface of the membrane was evident through SEM pictures of the membrane surface. At a pressure of 0. 2 MPa,the pure water flux can reach 45. 85 L·( m~2·h)-1. The rejection of Na_2SO_4 was 98. 23%,while that of NaCl was 24. 93%. The 10 h operation can effectively separate SO_4~(2-) and Cl~-,which realized the salt recycling.
引文
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[19]王利颖,石洁,王凯伦,等.碳纳米管改性PVDF中空纤维超滤膜处理二级出水抗污染性能研究[J].环境科学,2017,38(1):220-228.Wang L Y,Shi J,Wang K L,et al. Effect of PVDF hollow fiber ultrafiltration membranes modification with carbonnanotube on membrane fouling control during ultrafiltration of sewage effluent[J]. Environmental Science,2017,38(1):220-228.
[20] Liu G P,Jin W Q. Graphene oxide membrane for molecular separation:challenges and opportunities[J]. Science China Materials,2018,61(8):1021-1026.
[21]王茜,郭晓燕,邵怀启,等.石墨烯及氧化石墨烯对分离膜改性的方法、效能和作用机理[J].化学进展,2015,27(10):1470-1480.Wang X,Guo X Y,Shao H Q,et al. Methods,performances and mechanisms of separation membrane modified by graphene and graphene oxide[J]. Progress in Chemistry,2015,27(10):1470-1480.
[22] Xie Q L, Zhang S S, Xiao Z Y, et al. Preparation and characterization of novel alkali-resistant nanofiltration membranes with enhanced permeation and antifouling properties:the effects of functionalized graphene nanosheets[J]. RSC Advances,2017,7(30):18755-18764.
[23] Hu R R,He Y J,Zhang C M,et al. Graphene oxide-embedded polyamide nanofiltration membranes for selective ion separation[J]. Journal of Materials Chemistry A,2017,5(48):25632-25640.
[24]林菊香,董菁,陈丹青,等.基于对氨基苯磺酸重氮盐功能化制备亲水性磺化石墨烯的研究[J].中国科学:化学,2016,46(8):791-799.Lin J X,Dong J,Chen D Q,et al. Synthesis of hydrophilic sulfonated graphene based on diazonium salt of 4-aminobenzenesulfonic acid functionalized graphene[J]. Scientia Sinica Chimica,2016,46(8):791-799.
[25]郭长春.氧化石墨烯(GO)与磺化氧化石墨烯(SGO)的制备及其修饰电极电化学研究[D].青岛:青岛大学,2012.
[26] Bano S,Mahmood A,Kim S J,et al. Graphene oxide modified polyamide nanofiltration membrane with improved flux and antifouling properties[J]. Journal of Materials Chemistry A,2015,3(5):2065-2071.
[27] Rolere S,Liengprayoon S,Vaysse L,et al. Investigating natural rubber composition with Fourier Transform Infrared(FT-IR)spectroscopy:a rapid and non-destructive method to determine both protein and lipid contents simultaneously[J]. Polymer Testing,2015,43:83-93.
[28] Tan Z,Chen S F,Peng X S,et al. Polyamide membranes with nanoscale Turing structures for water purification[J]. Science,2018,360(6388):518-521.
[29]袁俊生,焦亮,刘杰.利用纳滤膜软化浓海水研究[J].水处理技术,2012,38(11):81-83,89.Yuan J S,Jiao L,Liu J. Softening of concentrated seawater by nanofiltration membrane[J]. Technology of Water Treatment,2012,38(11):81-83,89.
[2]田晓媛.纳滤/反渗透膜技术处理高盐废水及高浓度重金属废水的研究[D].湘潭:湘潭大学,2014.
[3] Eriksson P, Kyburz M, Pergande W. NF membrane characteristics and evaluation for sea water processing applications[J]. Desalination,2005,184(1-3):281-294.
[4]方建慧,姜华,刘继全,等.纳滤膜在海水淡化中的应用研究[J].膜科学与技术,2006,26(1):50-54.Fang J H,Jiang H,Liu J Q. et al. Study on desalination performance of seawater with nanofiltration membrane[J].Membrane Science and Technology,2006,26(1):50-54.
[5] Luo J Q,Wan Y H. Effects of p H and salt on nanofiltration—a critical review[J]. Journal of Membrane Science,2013,438:18-28.
[6]赵彦彦,袁其朋.有机相纳滤分离过程中浓度、电荷、溶剂对溶质截留行为的影响[J].膜科学与技术,2006,26(5):31-36.Zhao Y Y,Yuan Q P. Effects of concentration,molecular charge and solvents on solute rejection with solvent-resistance nanofiltration membranes in non-aqueous system[J]. Membrane science and Technology,2006,26(5):31-36.
[7] Peng X S,Jin J,Nakamura Y,et al. Ultrafast permeation of water through protein-based membranes[J]. Nature Nanotechnology,2009,4(6):353-357.
[8]魏源送,王健行,岳增刚,等.纳滤膜技术在废水深度处理中的膜污染及控制研究进展[J].环境科学学报,2017,37(1):1-10.Wei Y S,Wang J X,Yue Z G,et al. Fouling and control of nanofiltration membrane in the advanced treatment of wastewater:an overview[J]. Acta Scientiae Circumstantiae,2017,37(1):1-10.
[9]龙小庆,王占生.活性炭-纳滤膜工艺去除饮用水中总有机碳和Ames致突变物[J].环境科学,2001,22(1):75-77.Long X Q,Wang Z S. Removal of TOC and Ames mutagens from drinking water using AC-NF process[J]. Environmental Science,2001,22(1):75-77.
[10] Nan Q, Li P, Cao B. Fabrication of positively charged nanofiltration membrane via the layer-by-layer assembly of graphene oxide and polyethylenimine for desalination[J].Applied Surface Science,2016,387:521-528.
[11] Li Y F,Su Y L,Zhao X T,et al. Preparation of antifouling nanofiltration membrane via interfacial polymerization of fluorinated polyamine and trimesoyl chloride[J]. Industrial&Engineering Chemistry Research, 2015, 54(33):8302-8310.
[12]邱实,吴礼光,张林,等.纳滤分离机理[J].水处理技术,2009,35(1):15-19.Qiu S,Wu L G,Zhang L,et al. Separation mechanisms of nanofiltration[J]. Technology of Water Treatment,2009,35(1):15-19.
[13]黄裕,张晗,董秉直.纳滤膜去除卡马西平的影响因素研究[J].环境科学,2011,32(3):705-710.Huang Y,Zhang H,Dong B Z. Researches on factors affecting the removal of carbamazepine by nanofiltration membranes[J].Environmental Science,2011,32(3):705-710.
[14]陈利,沈江南,林龙,等.纳滤分离机理及应用于高含盐溶液脱盐的进展[J].过滤与分离,2009,19(4):9-12.Chen L,Shen J N,Lin L,et al. Separation mechanism of nanofiltration and its application in desalination of high-salt concentration solution[J]. Journal of Filtration&Separation,2009,19(4):9-12.
[15]曹晓兵,李涛,周律,等.染整废水深度处理纳滤工艺膜污染成因分析[J].环境科学,2012,33(1):117-123.Cao X B,Li T,Zhou L,et al. Analysis of membrane fouling genesis in nanofiltration process for advanced treatment of dyeing and finishing wastewater[J]. Environmental Science,2012,33(1):117-123.
[16]文鹏.氧化石墨烯改性聚酰胺复合纳滤膜的制备及其性能表征[D].天津:天津工业大学,2017.
[17] Sasidhar V,Ruckenstein E. Anomalous effects during electrolyte osmosis across charged porous membranes[J]. Journal of Colloid and Interface Science,1982,85(2):332-362.
[18] Smit J A M. Reverse osmosis in charged membranes:analytical predictions from the space-charge model[J]. Journal of Colloid and Interface Science,1989,132(2):413-424.
[19]王利颖,石洁,王凯伦,等.碳纳米管改性PVDF中空纤维超滤膜处理二级出水抗污染性能研究[J].环境科学,2017,38(1):220-228.Wang L Y,Shi J,Wang K L,et al. Effect of PVDF hollow fiber ultrafiltration membranes modification with carbonnanotube on membrane fouling control during ultrafiltration of sewage effluent[J]. Environmental Science,2017,38(1):220-228.
[20] Liu G P,Jin W Q. Graphene oxide membrane for molecular separation:challenges and opportunities[J]. Science China Materials,2018,61(8):1021-1026.
[21]王茜,郭晓燕,邵怀启,等.石墨烯及氧化石墨烯对分离膜改性的方法、效能和作用机理[J].化学进展,2015,27(10):1470-1480.Wang X,Guo X Y,Shao H Q,et al. Methods,performances and mechanisms of separation membrane modified by graphene and graphene oxide[J]. Progress in Chemistry,2015,27(10):1470-1480.
[22] Xie Q L, Zhang S S, Xiao Z Y, et al. Preparation and characterization of novel alkali-resistant nanofiltration membranes with enhanced permeation and antifouling properties:the effects of functionalized graphene nanosheets[J]. RSC Advances,2017,7(30):18755-18764.
[23] Hu R R,He Y J,Zhang C M,et al. Graphene oxide-embedded polyamide nanofiltration membranes for selective ion separation[J]. Journal of Materials Chemistry A,2017,5(48):25632-25640.
[24]林菊香,董菁,陈丹青,等.基于对氨基苯磺酸重氮盐功能化制备亲水性磺化石墨烯的研究[J].中国科学:化学,2016,46(8):791-799.Lin J X,Dong J,Chen D Q,et al. Synthesis of hydrophilic sulfonated graphene based on diazonium salt of 4-aminobenzenesulfonic acid functionalized graphene[J]. Scientia Sinica Chimica,2016,46(8):791-799.
[25]郭长春.氧化石墨烯(GO)与磺化氧化石墨烯(SGO)的制备及其修饰电极电化学研究[D].青岛:青岛大学,2012.
[26] Bano S,Mahmood A,Kim S J,et al. Graphene oxide modified polyamide nanofiltration membrane with improved flux and antifouling properties[J]. Journal of Materials Chemistry A,2015,3(5):2065-2071.
[27] Rolere S,Liengprayoon S,Vaysse L,et al. Investigating natural rubber composition with Fourier Transform Infrared(FT-IR)spectroscopy:a rapid and non-destructive method to determine both protein and lipid contents simultaneously[J]. Polymer Testing,2015,43:83-93.
[28] Tan Z,Chen S F,Peng X S,et al. Polyamide membranes with nanoscale Turing structures for water purification[J]. Science,2018,360(6388):518-521.
[29]袁俊生,焦亮,刘杰.利用纳滤膜软化浓海水研究[J].水处理技术,2012,38(11):81-83,89.Yuan J S,Jiao L,Liu J. Softening of concentrated seawater by nanofiltration membrane[J]. Technology of Water Treatment,2012,38(11):81-83,89.