摘要
随着膜分离技术的迅速发展,中空纤维超滤膜被广泛应用在人们生活和生产的各个方面,如化工、环保、电子、轻工、纺织、石油、食品、医药、生物工程、能源工程等方面。随着中空纤维超滤膜的广泛应用,其性能也被人所关注,但是表征超滤膜性能的方法众多。标准化测量方法的研究对于提高国内超滤膜的产品质量和制造技术、促进产业健康发展和参与市场竞争具有重要意义。本文基于以上原因,对中空纤维超滤膜性能的表征方法进行对比研究。
本文研究了温度对膜的影响程度。中空纤维超滤膜的通量随温度的升高略有增加;对于不同的膜,温度对其通量影响程度不同。
采用密度法和干湿重量法对中空纤维超滤膜进行测试。密度法误差小于干湿重量法,因此,密度法更加稳定。
采用气体吸附脱附法、热测孔法、液体流速法、液体置换法、FESEM法对膜孔孔径及其分布进行测量。测量结果表明液体置换法测量平均孔径最大,气体吸附脱附法、FESEM法、热测孔法、液体流速法测量结果较为接近;气体吸附脱附法测得的孔径分布较宽,FESEM法、热测孔法、液体流速法、液体置换法测量结果较窄。
选用葡聚糖T10、T40,聚乙二醇6K、10K、20K,牛血清白蛋白,鸡卵清白蛋白表征中空纤维超滤膜截留性能。对相同分子量的标示物而言,蛋白质截留率最高,且复现性好,聚乙二醇次之,葡聚糖最差。蛋白质分子本身为球形分子复现性好,截留率高。聚砜材料对葡聚糖T10具有吸附作用,对膜的截留性能的表征也有一定的影响。
Hollow Fiber Ultrafiltration Membrane has been widely in all aspects of people’s life and production, such as chemical, environmental protection, electronic, light in- dustry, petroleum, food, pharmaceutical, bioengineering, energy engineering, etc. The performance of Hollow Fiber Ultrafiltration Membrane is concerned for the wide usa- ge of Hollow Fiber Ultrafiltration Membrane. Since there are many methods to chara- cterize the performance of Hollow Fiber Ultrafiltration Membrane, the paper comp- ares these methods.
The paper explores the changes of flux under different temperatures and the effects of temperature on the membrane.
Compared with two methods of porosity characterization, the deviation of density method is smaller than dry-wet method. In dry-wet method, sample must be immersed in ethanol for a certain period of time before measurement. Membrane may be swell- led making the aperture change because of the occlusion of liquid. Dry-wet method is easy to lead to large error because of more measurement data required. So the porosity got by density method is more in line with the actual.
Membrane pore size and distribution measured by gas adsorption-desorption me- thod, liquid displacement method and liquid velocity method is not close to the results measured by FESEM method. The result of DSC method is close to the FESEM me- thod. The surface of membrane is made wet before measurement, which does not in- fluence the structure of membrane pore. So DSC method is an ideal method to mea- sure the membrane pore.
Dextran T10 and T40, Polyethylene Glycol 6K, 10K, and 20k, Bovine Serum Albumin, chicken ovalbumin are used to characterize the retention performance of Hollow Fiber Ultrafiltration Membrane. To the marker of the same molecular weight, the retention rate of protein is highest with good reproducibility, followed by PEG, Dextran the worst. Protein molecule itself is spherical molecule with good repro- ducibility and high retention rate. So protein is suggested to characterize the retention performance of Hollow Fiber Ultrafiltration Membrane. Because of the adsorption of membrane material, membrane material has certain effect on the retention per- formance of membrane.
引文
[1]王学松,膜分离技术及其应用,北京:科学出版社,1994,1~6
[2]郑领英,王学松,膜技术,北京:化学工业出版社,2000,3
[3] Taleshi Matsuura, Progress in Membrane Science and Technology for Seawater Desalination-a Review, Desalination, 2001, 134,47~54
[4]何旭敏,何国梅,曾碧榕,膜分离技术的应用,厦门大学学报(自然科学版),2001,40(2):495~502
[5]陈一鸣,蔡慧茹,刘玉榕,膜分离技术的现状及其在染料化工的应用,化工装备技术,2002,22(1):6~12
[6]刑启华,膜分离技术的应用,化学教育,2000,6:22~24
[7] Strathman H,Proceedings of International Congress on Membrane and Membrane Process,1990,1, 1167~1168
[8]黄加乐,董声雄,我国膜技术的应用现状与前景,福建化工,2000:3~5
[9]程淑英,龚丽丽,膜分离技术应用现状及展望,化工技术经济,1999,17(2):15~18
[10]邓麦村,气体分离技术在我国的发展及展望,现代化工,1996,10:13~18
[11]朱智清,膜分离技术的发展及其工业应用,化工技术与开发,2003,32(1):20
[12]史玉东,康小红,胡新宇,膜分离技术在乳品工业中的应用,农产品加工,2009,160(1):1
[13]楼福乐,毛伟钢,陆晓峰等,超滤技术在制药工业中除热原的应用,膜科学与技术,1999,19(3):1
[14]谷大建,徐巍,膜分离技术的应用及研究进展,综述报告,2008,17(6):1~2
[15]刘茉娥,膜分离技术应用手册,北京:化学工业出版社,2001,2~4
[16]黄英,王利,水处理中膜分离技术的应用,工业水处理,2005,25(4):11
[17] Marcel Mulder,膜技术基本原理,北京:清华大学出版社,1999,48~49
[18]杨宗伟,分离膜材料和膜制备技术的研究进展,过滤与分离,2007,17(1):12~13
[19] Y. Liu, G.H. Koops, H. Strathmann,Characterization of morphology contr- oled polyethersulfone hollow fiber membranes by the addition of polyethylene glycol to the dope and bore liquid solution,Journal of Membrane Science, 223(2003),187~199
[20]张耀鹏,邵惠丽,沈新元等,用原子力显微镜研究纤维素膜表面形貌和孔径大小及分布,膜科学与技术,2002,22(2):13
[21]Bowen W R,Hilal N,Livet R W.d at Atomic force microscope studies of membranes:Fore measurement and imaging in electrolyte solutions.J Membr Sci,1997.126,77~89
[22]钱欣,程蓉,原子力显微镜在合成膜表征中的应用,膜科学与技术,2004,24(2):62~66
[23]李慧琴,张玉,用原子力显微镜研究聚乙烯醇分离膜的结构,水处理技术,2006,32(4):27~29
[24]李万超,赵义平,陈莉等,固含量对PVDF g PNIPAA m温敏膜性能和结构的影响,天津工业大学学报,2008,27(5):11~14
[25]P Shao,R Y M Huan g,X Feng,et .Gas-liquid displacement method for esti- mateing membrane pore-size distributions.AICHE Journal,2000,50(3),557~565
[26]吕晓龙,超滤膜孔径及其分布的测定方法:I.常用测定方法讨论,水处理技术,1995,21(3):137~141
[27]Deutsches Institute fur Normung,DIN 66133-1993,DIN, 1993
[28]邢健敏,李芬芳,梁逸曾,丙烯腈/丙烯酰胺/苯乙烯三元共聚超滤膜材料的制备和表征,华东理工大学学报,2006,32(2):209~216
[29]McGuire K S, Lawson K W, Lloyd D R.Pore size distribution determin- ation from liquid permeation through micro porous membranes.Journal of Membrane Science,1995,99,127~137
[30]W Piatkiewicz,S Rosin ski,D Lewin ska,et a1.Determination of pore size distribution in hollow fiber membranes.Journal of Membrane Science,1999,l53,91~102
[31]罗菊芬,莫剑雄,液液界面法测超滤膜孔径及孔径分布,水处理技术,1996,22(5):255~259
[32]段文松.王振中,超滤膜结构参数特性的分析研究,江苏环境科技,2007,20(2):9~11
[33]B.K. Chaturvedi, A.K. Ghosh, V. Ramachandhran, etc. , Preparation, charac- terization and performance of polyethersulfone ultrafiltration membranes. Desalination, 133 (2001) ,31~40.
[34] J. Ferna′ndez-Sempere, F. Ruiz-Bevia′and R.Salcedo-Diaz, Measureme- nts by holographic interferometry of concentration profiles in dead-end ultrafiltration of polyethylene glycol solutions. Membr. Sci., 229 (2004) ,187~197.
[35] I.M. Noel, R.E. Lebrun and C.R. Bouchard, Nanofiltration of NaC1 solutions using a SPPO membrane (BQ01) Part 1. Membrane characterization and separation mechanisms. Desalination,155 (2003), 229~242.
[36] I. Kim, K. Lee and T. Tak, Preparation and characterization of integrally ski- nned uncharged polyetherimide asymmetric nanofiltration membrane. Membr. Sci., 183 (2001), 235~247.
[37] I. Kim, H. Yun and K. Lee, Preparation of asymmetric polyacrylonitrile me- mbrane with small pore size by phase inversion and post-treatment process. Membr. Sci., 199 (2002) ,75~84.
[38] M. Khayet, C.Y. Feng, K.C. Khulbe and T. Matsuura, Study on the effect of a non-solvent additive on the morphology and performance of ultrafiltration hollow- fiber membranes. Desalination,148 (2002) ,321~327.
[39] H. Hicke, I. Lehmann, G. Malsch, M. Ulbricht and M. Becker, Preparation and characterization of a novel solvent-resistant and autoclavable polymer membrane. Membr. Sci., 198 (2002), 187~196.
[40] Q.K. Wang, T. Matsuura, C.Y. Feng, etc., The sepiolite membrane for ultrafiltration. Membr. Sci, 184 (2001) ,153~163.
[41] Z. Xu and F.A. Qusay , Polyethersulfone (PES) hollow fiber ultrafiltration membranes prepared by PES/non-solvent/NMP solution. Memb. Sci., 233 (2004) , 101~111.
[42] J.E. Yoo, J.H. Kim, Y. Kim etc. , Novel ultrafiltration membranes prepared from the new miscible blends of polysulfone with poly (1-vinylpyrrolidone- co-styrene) copolymers. Membr. Sci., 216 (2003) , 95~106.
[43] X. Lu, X. Bian and L. Shi, Preparation and characterization of NF composite membrane. Memb. Sci., 210 (2002) , 3~11.
[44] JISC,JIS K-3821,JIS,北京:中国标准出版社,1990
[45] American Society for Testing and Materials,ASTM F 316-2003,ASTM,北京:中国标准出版社,2003
[46] J. Xu, Z.-L. Xu, Poly(vinyl chloride) (PVC) hollow fiber ultrafiltration me- mbranes prepared from PVC/additives/solvent, J. Membr. Sci. 2002, 208, 203~212
[47]国家海洋局,HYT039-1995,中华人民共和国海洋行业标准,北京:中国标准出版社,1996-01-01
[48]许晓鹏,郑领英,用BET法测定反渗透与超过滤膜的皮层孔分布,膜科学与技术,1990,10(3):1~7
[49] J. Chen, J. Li, Z.-P. Zhao, D. Wang, C.-X. Chen, Nanofiltration membrane prepared from polyacrylonitrile ultrafiltration membrane by low-temperature plasma: 5. Grafting of styrene in vapor phase and its application, Surface & Coatings Tech- nology 2007, 201, 6789~6792
[50]M. Iza, S. Woerly, C. Danumah, S. Kaliaguine, M. Bousmina, Determin- ation of pore size distribution for mesoporous materials and polymeric gels by means of DSC measurement: thermoporometry, Polymer, 2005, 41, 5885~5893
[51]M.R. Landry, Thermoporometry by differential scanning calorimetry: exp- erimental considerations and applications, Thermochimica Acta, 2005, 433:27~50
[52]诸爱士,林贤诉,高兴,液—液置换法测试超滤膜孔径及其分布的研究,浙江科技学院学报,2004,16(4):239~243
[53]赵学辉,吕晓龙,中空纤维膜孔径及其分布的测定,水处理技术,2007,33(7):14~17
[54] Chong Zhou, Zhan Wang*, Yanli Liang, Jinmiao Yao, Study on the control of pore sizes of membranes using chemical methods Part II. Optimization factors for preparation of membranes, Desalination, 255(2008),123~138
[55]王磊,王旭东,段文松,刘莹,超滤膜结构参数的测定方法及透水通量与膜结构关系的模型,膜科学与技术,2006,26(5):55~59
[56]国家海洋局,HYT050-1999,中华人民共和国海洋行业标准,北京:中国标准出版社,1999-07-01
[57] American Society for Testing and Materials,ASTM E 1343-2001,ASTM,2001
[58]戴海平,张惠新,梁福海,孙方,用葡聚糖测定超滤膜切割分子量的简易方法,膜科学与技术,2005,25(4):1~3
[59]华耀祖,超滤技术与应用,北京:化学工业出版社,2004,77~104