三醋酸纤维素/壳聚糖反渗透膜的制备及性能研究
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摘要
以壳聚糖(CS)为抗菌剂和三醋酸纤维素(CTA)为基膜材料,通过液-液共混和相转化成膜技术制备了三醋酸纤维素/壳聚糖共混反渗透膜(CTA/CS-RO),以改善醋酸纤维素反渗透膜的抗菌性能.采用傅里叶红外光谱、X-射线光电子能谱、扫描电子显微镜、水接触角、X-射线衍射光谱等对其结构和性能进行表征.结果表明,CTA/CS-RO中CS与CTA之间存在氢键作用,并且CS随着双扩散过程向膜表面迁移;膜厚度随着CS含量的递增而减小,横断面结构由指状孔转变成海绵状.CS的添加有利于共混膜亲水性、水通量和力学性能的提高.当CS含量为0.75%~1.00%时,膜样品在保持较高的盐截留率(R>90%)的同时其断裂伸长率和结晶度没有显著变化.动态接触抗菌测试结果表明,CTA/CS-RO对大肠杆菌和金黄色葡萄球菌均具有抑菌作用.特别地,当CS含量为0.75%~1.00%时,膜样品对大肠杆菌和金黄色葡萄球菌的抑菌率分别为65%~72.5%和16%~51%.综合分析,CTA/CS共混反渗透膜制备过程中CS的加入量保持在0.75%~1.00%时膜的综合性能最优.
Compared with conventional reverse osmosis membrane(RO) materials, cellulose acetate(CA)reverse osmosis membranes have attracted considerable attention due to their unique chlorine resistance. However,β-glucose units in the cellulose backbone of CA molecule are vulnerable to erosion and degradation by aquatic microorganisms. To improve the antibacterial performance of cellulose triacetate reverse osmosis membrane,cellulose triacetate/chitosan blend reverse osmosis membrane(CTA/CS-RO) were designed and prepared with CS as the antibacterial agent by phase inversion. The homogeneous CTA solutions containning 20 g·L-1 CS in formic acid were casted with casting knife of 250 μm thickness and the asymmetrical CTA/CS-RO membranes were obtained after solvent evaporation, immersion precipitation process. The mass fractions of CS to CTA were selected to be 0.25%, 0.50%. 0.75%, 1.00% and 1.25%, respectively. The structure and performances of the obtained CTA/CS-RO membranes were characterized by various methods such as Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, water contact angle and X-ray diffraction spectroscopy. The red shift of the characteristic peak of C― O― C in FTIR spectra indicated the presence of hydrogen bonding between CTA and CS. The characteristic peak of N1 s in XPS spectra indicated the migration of CS to the membrane surface during phase inversion. The SEM images showed that membrane thickness decreased with increasing CS concentration. The addition of CS improved the hydrophilicity, water flux and mechanical properties of CTA/CS-ROs. When the mass fraction of CS to CTA was within 0.75%-1.00%,CTA/CS-ROs showed high salt rejection(R > 90%) without siginificant changes in elongation at break and crystallinity. The dynamic contact antibacterial test results indicated that CTA/CS-ROs showed inhibitory effect on E. coli and S. aureus, which was improved by increasing the content of CS. When the mass fraction of CS to CTA was within 0.75%-1.00%, CTA/CS-ROs possessed higher inhibition rate against E. coli(65%-72.5%)than S. aureus(16%-51%) due to the electrostatic attraction between the positive CS and gram negative E. coli.
Compared with conventional reverse osmosis membrane(RO) materials, cellulose acetate(CA)reverse osmosis membranes have attracted considerable attention due to their unique chlorine resistance. However,β-glucose units in the cellulose backbone of CA molecule are vulnerable to erosion and degradation by aquatic microorganisms. To improve the antibacterial performance of cellulose triacetate reverse osmosis membrane,cellulose triacetate/chitosan blend reverse osmosis membrane(CTA/CS-RO) were designed and prepared with CS as the antibacterial agent by phase inversion. The homogeneous CTA solutions containning 20 g·L-1 CS in formic acid were casted with casting knife of 250 μm thickness and the asymmetrical CTA/CS-RO membranes were obtained after solvent evaporation, immersion precipitation process. The mass fractions of CS to CTA were selected to be 0.25%, 0.50%. 0.75%, 1.00% and 1.25%, respectively. The structure and performances of the obtained CTA/CS-RO membranes were characterized by various methods such as Fourier transform infrared spectroscopy, X-ray photoelectron spectroscopy, scanning electron microscopy, water contact angle and X-ray diffraction spectroscopy. The red shift of the characteristic peak of C― O― C in FTIR spectra indicated the presence of hydrogen bonding between CTA and CS. The characteristic peak of N1 s in XPS spectra indicated the migration of CS to the membrane surface during phase inversion. The SEM images showed that membrane thickness decreased with increasing CS concentration. The addition of CS improved the hydrophilicity, water flux and mechanical properties of CTA/CS-ROs. When the mass fraction of CS to CTA was within 0.75%-1.00%,CTA/CS-ROs showed high salt rejection(R > 90%) without siginificant changes in elongation at break and crystallinity. The dynamic contact antibacterial test results indicated that CTA/CS-ROs showed inhibitory effect on E. coli and S. aureus, which was improved by increasing the content of CS. When the mass fraction of CS to CTA was within 0.75%-1.00%, CTA/CS-ROs possessed higher inhibition rate against E. coli(65%-72.5%)than S. aureus(16%-51%) due to the electrostatic attraction between the positive CS and gram negative E. coli.
引文
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4Matin A,Khan Z,Zaidi S M J,Boyce M C.Desalination,2011,281:1-16
5Idris A,Ismail A F,Noorhayati M,Shilton S J.J Membr Sci,2003,213:45-54
6Loeb S,Sourirajan S.Sea Water Demineralization by Means of an Osmotic Membrane.Washington,D.C.:AmericanChemical Society,1963.117-132
7Li N N,Fane A G,Ho W S W,Matsuura T.Advanced Memebrane Technology and Applications.Hoboken:John Wiley&Sons,Inc.,2008.21-43
8Guibal E,Cambe S,Bayle S,Taulemesse J M,Vincent T.J Colloid Interf Sci,2013,393:411-420
9Liu C,Bai R.J Membr Sci,2006,284:313-322
10Alves N M,Mano J F.Int J Biol Macromol,2008,43:401-414
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14Nara S,T.Komiya T.Starch-St?rke,1983,35:407-410
15Kondo T.Cellulose,1997,4:281-292
16Klemm D,Heublein B,Fink H P,Bohn A.Angew Chem Int Ed,2005,44:3358-3393
17Xing Qiyi(邢其毅),Pei Weiwei(裴伟伟),Xu Ruiqiu(徐瑞秋),Pei Jian(裴坚).Basic Organic Chemistry,3rd ed(基础有机化学(第三版)上册).Beijing(北京):Higher Education Press(高等教育出版社),2005.187-188
18Celebi H,Kurt A.Carbohydr Polym,2015,133:284-293
19Geng C Z,Hu X,Yang G H,Zhang Q,Chen F,Fu Q.Chinese J Polym Sci,2015,33:61-69
20Ionita M,Crica L E,Voicu S I,Pandele A M,Iovu H.Polym Adv Technol,2016,27:350-357
21Saljoughi E,Sadrzadeh M,Mohammadi T.J Membr Sci,2009,326:627-634
22Morsy A,Ebrahim S,Kenawy E R,Abdel-Fattah T,Kandil S.Water Sci Technol:Water Supply,2016,16:1046-1056
23Ghaee A,Shariaty-Niassar M,Barzin J,Matsuura T,Fauzi Ismail A.Desalin Water Treat,2015,57:14453-14460
24Wu Qingyun(吴青芸),Pan Yehan(潘叶寒),Jin Weizhong(金伟中),Xu Jiamin(徐佳敏),Lao Kankan(劳侃侃),Gu Lin(顾林).Acta Polymerica Sinica(高分子学报),2017,(5):132-138
25Ding Mingyu(丁明玉).Modern Separation Methods and Techniques(现代分离方法与技术).Beijing(北京):ChemicalIndustry Press(化学工业出版社),2012.36-42
26Song Jianhui(宋建会),Zhou Feng(周凤),Wang Xiang(王湘),Ren Yi(任毅),Zhang Xiaohong(张晓红),Guo Mingming(郭鸣明),Qiao Jinliang(乔金樑).Acta Polymerica Sinica(高分子学报),2017,(4):676-682
27Anjali D D,Smitha B,Sridhar S,Aminabhavi T M.J Membr Sci,2005,262:91-99
28Nolte M C M,Simon P F W,del Toro M A,Gerstandt K,Calmano W.Sep Sci Technol,2011,46:395-403
29Braun J L,Kadla J F.J Carbohydr Chemy,2013,32:120-138
30Cai Z J,Jin H J,Kim J.Proc SPIE,2009,7291:72910U1-6
31Abdel-Naby A S,Al-Ghamdi A A.Int J Biol Macromol,2014,68:21-27
32An Shulin(安树林).Practical Course in Membrane Science and Technology(膜科学技术实用教程).Beijing(北京):Chemical Industry Press(化学工业出版社),2005.54-258
33Roy D,Knapp J S,Guthrie J T,Perrir S.Biomacromolecules,2008,9:91-99
34Yang S P,Fu S Y,Li X Y,Zhou Y M,Zhan H Y.Bioresources,2010,5:1114-1125
2Waheed S,Ahmad A,Khan S M,Gul S E,Jamil T,Islam A,Hussain T.Desalination,2014,351:59-69
3Sabad E G,Waheed S,Ahmad A,Khan S M,Hussain M,Jamil T,Zuber M.J Taiwan Inst Chem Eng,2015,57:129-138
4Matin A,Khan Z,Zaidi S M J,Boyce M C.Desalination,2011,281:1-16
5Idris A,Ismail A F,Noorhayati M,Shilton S J.J Membr Sci,2003,213:45-54
6Loeb S,Sourirajan S.Sea Water Demineralization by Means of an Osmotic Membrane.Washington,D.C.:AmericanChemical Society,1963.117-132
7Li N N,Fane A G,Ho W S W,Matsuura T.Advanced Memebrane Technology and Applications.Hoboken:John Wiley&Sons,Inc.,2008.21-43
8Guibal E,Cambe S,Bayle S,Taulemesse J M,Vincent T.J Colloid Interf Sci,2013,393:411-420
9Liu C,Bai R.J Membr Sci,2006,284:313-322
10Alves N M,Mano J F.Int J Biol Macromol,2008,43:401-414
11Mulder Marcel,Li Lin(李琳).Basic Principles of Membrane Technology,2nd ed(膜技术基本原理(第2版)).Beijing(北京):Tsinghua University Press(清华大学出版社),1999.193-195
12Xu Youyi(徐又一),Xu Zhikang(徐志康).Polymer Membrane Materials(高分子膜材料).Beijing(北京):ChemicalIndustry Press(化学工业出版社),2005.6-300
13Vinodhini P A,Sangeetha K,TGomathi,Sudha P N,Venkatesan J,Anil S.Int J Biol Macromol,2017,DOI:10.1016/j.ijbiomac.2017.03.122
14Nara S,T.Komiya T.Starch-St?rke,1983,35:407-410
15Kondo T.Cellulose,1997,4:281-292
16Klemm D,Heublein B,Fink H P,Bohn A.Angew Chem Int Ed,2005,44:3358-3393
17Xing Qiyi(邢其毅),Pei Weiwei(裴伟伟),Xu Ruiqiu(徐瑞秋),Pei Jian(裴坚).Basic Organic Chemistry,3rd ed(基础有机化学(第三版)上册).Beijing(北京):Higher Education Press(高等教育出版社),2005.187-188
18Celebi H,Kurt A.Carbohydr Polym,2015,133:284-293
19Geng C Z,Hu X,Yang G H,Zhang Q,Chen F,Fu Q.Chinese J Polym Sci,2015,33:61-69
20Ionita M,Crica L E,Voicu S I,Pandele A M,Iovu H.Polym Adv Technol,2016,27:350-357
21Saljoughi E,Sadrzadeh M,Mohammadi T.J Membr Sci,2009,326:627-634
22Morsy A,Ebrahim S,Kenawy E R,Abdel-Fattah T,Kandil S.Water Sci Technol:Water Supply,2016,16:1046-1056
23Ghaee A,Shariaty-Niassar M,Barzin J,Matsuura T,Fauzi Ismail A.Desalin Water Treat,2015,57:14453-14460
24Wu Qingyun(吴青芸),Pan Yehan(潘叶寒),Jin Weizhong(金伟中),Xu Jiamin(徐佳敏),Lao Kankan(劳侃侃),Gu Lin(顾林).Acta Polymerica Sinica(高分子学报),2017,(5):132-138
25Ding Mingyu(丁明玉).Modern Separation Methods and Techniques(现代分离方法与技术).Beijing(北京):ChemicalIndustry Press(化学工业出版社),2012.36-42
26Song Jianhui(宋建会),Zhou Feng(周凤),Wang Xiang(王湘),Ren Yi(任毅),Zhang Xiaohong(张晓红),Guo Mingming(郭鸣明),Qiao Jinliang(乔金樑).Acta Polymerica Sinica(高分子学报),2017,(4):676-682
27Anjali D D,Smitha B,Sridhar S,Aminabhavi T M.J Membr Sci,2005,262:91-99
28Nolte M C M,Simon P F W,del Toro M A,Gerstandt K,Calmano W.Sep Sci Technol,2011,46:395-403
29Braun J L,Kadla J F.J Carbohydr Chemy,2013,32:120-138
30Cai Z J,Jin H J,Kim J.Proc SPIE,2009,7291:72910U1-6
31Abdel-Naby A S,Al-Ghamdi A A.Int J Biol Macromol,2014,68:21-27
32An Shulin(安树林).Practical Course in Membrane Science and Technology(膜科学技术实用教程).Beijing(北京):Chemical Industry Press(化学工业出版社),2005.54-258
33Roy D,Knapp J S,Guthrie J T,Perrir S.Biomacromolecules,2008,9:91-99
34Yang S P,Fu S Y,Li X Y,Zhou Y M,Zhan H Y.Bioresources,2010,5:1114-1125