摘要
现阶段在膜应用过程中最大问题是膜污染问题，国内外的研究往往都是通过对膜本体材料的选择，膜表面的改性、膜应用工艺的优化等方面进行研究减缓膜污染的问题，很少针对膜的纵向深层结构来研究膜污染问题。膜纵向结构有对称性结构(均质结构)与非对称性结构(皮层结构)。目前已知聚偏氟乙烯中空纤维亲水性膜是抗污染性较强的一种膜材料。本文首先通过用不同浓度的溶剂(DMAc)对聚偏氟乙烯外压中空纤维亲水性超滤膜外表面浸泡处理，使膜外皮层孔结构处于不同状态，表征表面孔结构变化。然后通过改变纺丝制膜工艺制得泡点压力与通量相当但表面孔结构不同的两种中空纤维膜，一种中空纤维膜外表面光滑，膜孔颈在膜表面，定义为A型孔结构膜，另一种中空纤维膜表面相对粗糙，膜孔颈位于膜外表面层下，定义为V型孔结构膜。通过用这两种不同孔结构的亲水性超滤膜过滤卵清蛋白、淀粉、二氧化硅、柴油等四种典型体系，考察膜通量衰减情况，研究膜孔结构与膜耐污染性能关系；然后改变不同的过滤工艺条件研究膜通量的衰减情况，进一步研究膜孔结构和其抗污染性能的关系，研究表明：V型孔结构膜较A型孔结构膜耐污染。接着对污染程度相当的两种孔结构膜，在一定的压力下反洗一定时间；对应不同的污染体系，采用不同的化学药剂清洗，研究通量恢复情况，研究表明：V型孔结构膜较A型孔结构膜易清洗。为了进一步的提高膜的耐污染性能，对两种结构的膜表面进行涂覆改性，通过过滤卵清蛋白和柴油两种典型易污染体系研究膜表面耐污染情况，发现涂覆改性后的中空纤维复合膜耐污染性有了明显的提高，主要原因是膜表面引入了亲水性基团提高了膜的亲水性。
As we know, today, the difficult problems are fouling of membrane during the application of membrane. Many ways, such as, the elect of membrane material, membrane surface-modified, the optimization design of membrane application technological conditions, have ever been studied in domestic and abroad; but few people do research on pore structure of membrane. Membrane pore structure includes symmetrical pore and asymmetrical pore. Now we know PVDF is a kind of material that has the greater anti-fouling property. In this article, two kinds of PVDF UF membrane with different outer surface pore structure but equivalent bubble point pressure and water flux were prepared by changing spinning condition, the one whose necks of pores lie on the surface of the membrane is smooth, this pore structure is named A model pore; the other one whose necks of pores are under membrane surface is relative rough this pore structure is named V model pore. Then, attenuation curve of membrane flux is studied through filtering representative different solution systems and changing different filtration conditions, and further illuminate the relation between membrane pore structure and anti-fouling. The results show that V model pore of membrane has better anti-fouling property. In succession, membrane that has dissimilar exterior configuration but the same fouling is washed reversely by water, and then different contaminative system is cleaned out by different chemical medicine, further reversion conditions of flux is researched. As a result, V model pore of is cleaned out easily. For the sake of improving anti-fouling property further, PVDF hollow fiber composition membrane is prepared by coating PVA on the surface of membrane. The results that the performance of anti-fouling is improved by coating PVA are demonstrated through filtering ovalbumin system and diesel oil system.
引文
[1] Cheryan M. In: Untrafiltration and Microfiltration Handbook[M]. Chap. 6. Technomic Lancaster, PA, 1998.
[2] 张国俊，刘忠州．膜过程中超滤膜污染机制的研究及其防治技术进展[J]．膜科学与技术，2004，3(6)：1-4．
[3] 戴海平．中空纤维超滤膜污染行为的研究[J]．天津纺织工学院学报，1997，7(1)：35-38．
[4] 张原．超滤膜污染的机理和控制[J]．净水技术，2001，20(4)：11-13．
[5] 黎雁，吕晓龙．聚偏氟乙烯多孔膜的改性研究进展[J]．天津工业大学报，2001，10(5)：74-78．
[6] 吕晓龙．聚偏氟乙烯中空纤维膜的改性研究[J]．天津工业大学学报，2004，3(4)：24-27．
[7] 陈池，吕晓龙．PAMPS／PVDF中空纤维凝胶复合膜的制备及其性能研究[J]．天津工业大学学报，2005，4(1)：10-12．
[8] 王湛．膜分离技术基础[M]．化学工业出版社，2000，210-211．
[9] 王湛．膜分离技术基础[M]．化学工业出版社，2000，248-261．
[10] 许振良，陈贵娥．高孔隙率聚偏氟乙烯中空纤维超滤膜的研究[J]．2001，21(4)：39-43．
[11] 刘忠洲．微滤、超滤过程中的污染与清洗[J]．水处理技术，1997，3(4)：187-193．
[12] 吕晓龙．聚偏氟乙烯中空纤维微孔膜的应用及清洗方法[J]．膜科学与技术，2000，20(5)：5-9．
[13] 李爱勤．非对称聚偏氟乙烯渗透汽化膜的制备与性能研究[J]．郑州轻工业学院学报(自然科学版)，2004，7(4)：25-27．
[14] 华耀祖．超滤技术与应用[M]．化学工业出版社，2003，74-96．
[15] 李旭祥．分离膜制备及应用[M]．化学工业出版社，2003，18-21．
[16] 方正．聚偏氟乙烯树脂[J]．上海化工，2000，25(12)：23-24．
[17] 祝振鑫．用鸡蛋清中的卵清蛋白测定常用超滤膜的切割分子量[J]．膜科学与技术，1999，19(5)：44-50．
[18] 王晓丽，傅学起．大豆分离蛋白污染的聚砜膜清洗实验研究[J]．安全与环境学报．2004，(4)：25-27．
[19] Stevens L. Egg white proteins [J]. Comp Biochem Physiol, B: Comp Biochem, 1991, 100B (1):1-9.
[20] Fane A G, Fell CJD, Suki A. The effect PH and ionic environment on the ultrafil tration of protein solutions with retentive membranes [J]. J Membr Sci, 1983, 16:195-210.
[21] Fane A G, Fell CJD. Waters. AG. Ultrafiltration of protein solutions through partially permeable membrane: The effect of adsorption and solution environment [J].J Membr Sci, 1983. 16: 211～224.
[22] 李阳初，李发永等．外压刊营式膜组件的改进及其应用[J]．石油大学学报(自然科学版)，1993，17(74)．
[23] Choi H. Zhang K. Dionysiou D D. et al. Influence of cross—flow velocity on membrane performance during filtration of biological suspension[J]. J Membr Sci, 2005, 248(1-2): 189-199.
[24] Inc J. Rao P. Shirazes S. Effect of operating parameters on permeate flux decline caused by cake formation—a model study[J]. Desalination, 2005, 171 (1-2) : 95-105.
[25] 周治海．膜分离技术在玉米淀粉精加工中应用[J]．粮食与油脂．2002(5)：29-32．
[26] 李锡均，冯少玲．玉米深加工综合利用的前景[J]．包装与食品机械．2001，19(6)：37-39．
[27] 王海修，赵宏等．薄膜分离技术在玉米湿磨工艺中的应用[J]．吉林粮食高等专科学校学报．2005，20(2)：1-5
[28] Shankar Raman Chellam. Particle Back-Transport and Permeate flux Behavior in Cross flow Membrane Filters [J].Environ Science Technology. 1997, (31):819-824.
[29] Blake N J, Cumming I W. Streat Prediction of Steady State Cross flow filtration using a Force Balance Model [J]. J Membr Sci, 1992. 68: 205-216.
[30] 蔺爱国．膜分离技术在油田含油污水处理中的应用研究进展[J]．工业水处理，2006，26(1)．
[31] 宋航．静态吸附法评估膜对油的亲和性[J]．水处理技术，2003，29(3)140-142．
[32] 操建华，朱宝库，徐又一．外置式中空纤维膜-生物反应器处理污水的研究[J]．膜科学与技术，2006，26(4)：48-51，56．
[33] 邱运仁，张启修．超滤过程膜污染控制技术研究进展[J]．现代化工．2002，22(2)：18-23．
[34] 唐广军，孙本惠．聚偏氟乙烯膜的亲水性改性研究进展[J]．化工进展．2004，23(5)：480-485．
[35] 孟波，谭小耀，杨乃涛，张主砚．聚乙烯二甲基硅氧烷与聚偏氟乙烯复合分离膜的性能[J]．东北大学学报(自然科学版)．2004，25(8)：808-811．
[36] 万朝阳，陈翠仙．戊二醛交联PVA／PAN复合膜滲透气化性能的实验研究[J]．北京化工大学学报．2000，27(1)：4-7．
[37] Shekar B C, Veeravazhuthi V, Sakthivel S, et al. Growth, structure, dielectric and AC conduction properties of solution grown PVA films [J]. Thin Solid Films, 1999, 348: 122-125.
[38] 卞晓锴，施柳青等．聚乙烯醇复合膜的制备[J]．膜科学与技术，2004，24(4)：12-14．
[39] 马世虎，吕晓龙，李先锋等，PVDF中空纤维复合膜的制备及其性能研究[J]．天津工业大学学报，2005，24(3)：5-8．
[40] 庄银凤，朱仲祺，陈留伟等．聚乙烯醇一戊二醛水凝胶的脱水行为[J]．化学研究，1999，10(3)：17-20．
[41] 庄银凤，朱仲祺，王艳焰等．对聚乙烯醇一戊二醛凝胶体系的初步研究[J]．油田化学，1996，13(3)：264—265．
[42] N. A. Ochoa, M. Masuelli and J. Marchese, Effect of hydrophilicity on fouling of an emulsified oil wastewater with PVDF/PMMA membranes[J]. J Membr Sci, 2003,226(1-2):203-211.
[43] Robert Field, Song Hangl and Tom Arnot, The influence of surfactant on water flux through microfiltration membranes[J]. J Membr Sci, 1994,86(3):291-304.
[44] Landau and A. S. Jonson, Adsorptive fouling of modified and unmodified commercial polymeric ultrafiltration membranes[J]. J Membr Sci, 1999, 160(1):65-76.
[45] 黄征青，郭兴蓬等．耐污染聚乙烯醇超滤膜的研究现状[J]．膜科学与技术，2005(8)：56-60．
[46] 倪秀元．水一乙醇渗透蒸发膜分离技术研究及直用[J]．上海华东理工大学档案馆．1993．
[47] 吴秋林，吴照和．PVA—PE复合亲水分相膜的研制[J]．膜科学与技术，1995，(4)：29-32．
[48] Yutaka Sakurada, Ichiro. Polyvinyl Alcohol Fibers[M]. New York: Marcel Dekker Inc, 1985,86.
[49] Chetri P, Islam N, Dass N. Development of a novel catalyst for solution of poly (vinyl alcohol) in nonaquecus medium[J]. J Poly Sci, 1996, 34:1613-1615.
[50] 严瑞喧，陈振兴，宋宗文，等．水溶性聚合物[M]．北京：化学工业出版社，1988．25-74．
[51] Thrmas M, Escoubanne M. Preparation of pyrogen—free solution for medical use. Fur Pat Appl, 312104. 1989.03-19.
[52] 水田彦，发热性物质去除方法．日本，公开特许公报，平 1-196294．1989-08-18．
[53] 中华人民共和国卫生部药典委员会编．细菌内毒素检查法．见：中华人民共和国药典：二部，附录Ⅺ E．北京：化学工业出版社，1995．
[54] 黄清泉，夏振民．药品细菌內毒素检查的实验设计[J]．中国药学杂质，1997，32(2)：2．
[55] Zhang Guo-sheng (张国胜), GU He-ping, et al (谷和平等). Treatment of cool rolling emulsion with inorganic ceramic membranes (无机陶瓷膜处理冷轧乳化液废水) [J]. J Chem Eeng of Chinese Univ(高校化学工程学报), 1998, 12(a): 288-292.
[56] Miller D R. Pappas N A. Diffusional effects during albumin adsorption on highly swollen poly(vinyl alcohol) by drugless Euro Polym J, 1988, 24: 611-615.
[57] Li R H. Barbari T A. Performance of poly(vinyl alcohol)thin-gel composite ultra filtration membranes[J]. J Membrane Sci, 1995, 105; 71～78.
[58] Kong J, Li K. Oil removal from oil-in-water emulsions using PVDF membranes [J]. Sep Purif Technol, 1999, 16: 83-93.
[59] Ma H, Bowman C N, Davis R H. Membrane fouling reduction by backpulsing and surface modification [J]. J Membr Sci, 2000, 173: 191-200.
[60] Faibish R S, Cohen Y. Fouling and rejection behavior of ceramic and polymer-modified ceramic membranes for ultrafiltration of oil-in-water emulsions and microemulsions [J].Colloids and Surfaces A:Physicochemical and Engineering Aspects, 2001,191: 27-40.
[61] Tansel B, Regula J, Shalewitz R. Treatment of fuel oil and crude oil contaminated waters by ultrafiltration membranes [J].Desalination, 1995, 102: 301-311.
[62] 刘有智，高松平，张俊祥．用陶瓷超滤膜对含有超细固体颗粒的乳化悬浮液的净化处理[J]．化工进展．2003(1)：60-65．
[63] 王怀林，王忆川，姜建胜，云金明，王建华．陶瓷微滤膜用于油田采出水处理的研究[J]．膜科学与技术．1998，18(2)：59-64．
[64] 吴秋林，许效红，吴照和，刘青山．多孔亲水膜一油水分散体系界面现象研究[J]．膜科学与技术．1995，15(9)：61-67．
[65] 王枢，褚良银，陈文梅，顾雪林，李艳，王广会．有机／无机复合型抗污染油水分离膜研究[J]．高校化学工程学报．2005，19(1)：11-16．
[66] 李娜，刘忠州，续曙光．耐污染膜—聚乙烯醇膜的研究进展[J]．膜科学与技术．1999，19(3)：1-7．
[67] Elimdech M, Zhu Xia hua, Childress A E, el al. Role of membrane surface morphology in colloidal fouling of cellulose and composite aromatic polyamide RO membranes [J]. J Membrane Sci, 1997,127:101～109,129.