Al_2O_3陶瓷微滤膜的制备及表征方法研究
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摘要
本文主要建立了一套用于无机微滤膜性能测试与表征的检测装置与方法，研究了固态粒子烧结法制备无机微滤膜的工艺条件，以所建立装置测定膜的孔径大小与分布、孔隙率和通量，同时对膜的微观结构进行表征(SEM法)，得到了完整无缺陷、孔径大小和孔隙率等膜性能可调控的无机微滤膜。
首先结合实验室条件建立陶瓷微滤膜孔径大小及分布的测试装置与方法，通过Origin软件对数据进行加权处理，并将得到的结果与南京工业大学膜科学与技术研究所的处理结果相比较，结果表明建立的装置与数据处理方法准确可靠；改进国标法测试陶瓷孔隙率的装置和方法，比较抽真空法和煮沸法的区别，结果表明抽真空法更准确可靠；建立气体输送法测定膜通量装置；并于试验后发现鸡蛋清法测超率膜的截留率不宜用于微滤膜。
然后考察了固态粒子烧结法制备氧化铝微滤膜的工艺条件。实验表明，不同添加剂的粒度大小对膜性能有显著影响，添加剂粒度越细，所得膜孔径越小，分布越窄；通过调节致孔剂、烧结助剂的种类和用量，烧结温度、保温时间和升温速率等影响因素可以调控膜的性能。各种影响因素相互制约，尤其在致孔剂含量较高时(＞20％)，要严格控制烧结初期的升温速率，以确保制得无缺陷膜。因此在膜的制备时要根据不同膜的用途综合考虑各种影响因素。
实验制得的微滤膜最可几孔径0.26μm，孔隙率32.15％，0.2Mpa压力下水的通量为488.5L/(m~2·h)，所制得的膜既可用作微滤膜，也可用作超滤膜的载体。
In this dissertation, a suit of testing device and method were made use of characterizing inorganic membrane performance were set up. The preparation technics of alumina ceramic microfiltration membrane by solid-state-particles sintering method were investigated. The pore size distribution, porsity, flux of water and the microstructure were characterizated by testing device and SEM. Free-detect microfiltration which microstructure and performance parameters could be controlled were obtained.
Firstly, the device and method of testing pore size distribution were set up acording to the experimnet condition. The data were disposed through Origin software and the disposed result compared with which were dealed with by the research center of membrane science & technique of Nanjing Polytechnic University was credible. The device and method of testing ceramic porosity by Nation Standard were improved on. The results of vacuum method and ferv method had been carefully checked and compared and the former was exact. The device of testing water flux was set up, too. Research proved that the method which fresh egg albumin was used to measure rejection ration of ultrafiltration membrane could not be used in microfiltration membrane.
Secondly, the preparation of alumina microfiltration membrane by solid-state-particles sintering was studied . The result showed that the power size of different additive had great effect on membrane performance . If the power size of additive was smaller, the pore size distribution was more narrow. The membrane performance could be adjusted by changing the variety and dosage of pore-forming additive and sintering additive, sintering temperature, sintering time and increasing velocity of sintering temperature. Increasing velocity of sintering temperature in initial stage of sintering should be controlled accurately to ensure that free-detect microfiltration membrane was obtained, especially when pore-forming additive was much more (>20%). Therefore, all sorts of factors should be considered comprehensively according to the use of different membrane.
The characteristics of alumina microfiltration membranes obtained in this paper had met the need of microfiltration, which were: the most pore size 0.26 u m , porosity 32.15% , pure water permeability flux 488.5L/(m2 h) (under the pressure of 0.2Mpa). The membrane obtained could be used as microfiltration , and the support of ultrafiltration as well as.
首先结合实验室条件建立陶瓷微滤膜孔径大小及分布的测试装置与方法，通过Origin软件对数据进行加权处理，并将得到的结果与南京工业大学膜科学与技术研究所的处理结果相比较，结果表明建立的装置与数据处理方法准确可靠；改进国标法测试陶瓷孔隙率的装置和方法，比较抽真空法和煮沸法的区别，结果表明抽真空法更准确可靠；建立气体输送法测定膜通量装置；并于试验后发现鸡蛋清法测超率膜的截留率不宜用于微滤膜。
然后考察了固态粒子烧结法制备氧化铝微滤膜的工艺条件。实验表明，不同添加剂的粒度大小对膜性能有显著影响，添加剂粒度越细，所得膜孔径越小，分布越窄；通过调节致孔剂、烧结助剂的种类和用量，烧结温度、保温时间和升温速率等影响因素可以调控膜的性能。各种影响因素相互制约，尤其在致孔剂含量较高时(＞20％)，要严格控制烧结初期的升温速率，以确保制得无缺陷膜。因此在膜的制备时要根据不同膜的用途综合考虑各种影响因素。
实验制得的微滤膜最可几孔径0.26μm，孔隙率32.15％，0.2Mpa压力下水的通量为488.5L/(m~2·h)，所制得的膜既可用作微滤膜，也可用作超滤膜的载体。
In this dissertation, a suit of testing device and method were made use of characterizing inorganic membrane performance were set up. The preparation technics of alumina ceramic microfiltration membrane by solid-state-particles sintering method were investigated. The pore size distribution, porsity, flux of water and the microstructure were characterizated by testing device and SEM. Free-detect microfiltration which microstructure and performance parameters could be controlled were obtained.
Firstly, the device and method of testing pore size distribution were set up acording to the experimnet condition. The data were disposed through Origin software and the disposed result compared with which were dealed with by the research center of membrane science & technique of Nanjing Polytechnic University was credible. The device and method of testing ceramic porosity by Nation Standard were improved on. The results of vacuum method and ferv method had been carefully checked and compared and the former was exact. The device of testing water flux was set up, too. Research proved that the method which fresh egg albumin was used to measure rejection ration of ultrafiltration membrane could not be used in microfiltration membrane.
Secondly, the preparation of alumina microfiltration membrane by solid-state-particles sintering was studied . The result showed that the power size of different additive had great effect on membrane performance . If the power size of additive was smaller, the pore size distribution was more narrow. The membrane performance could be adjusted by changing the variety and dosage of pore-forming additive and sintering additive, sintering temperature, sintering time and increasing velocity of sintering temperature. Increasing velocity of sintering temperature in initial stage of sintering should be controlled accurately to ensure that free-detect microfiltration membrane was obtained, especially when pore-forming additive was much more (>20%). Therefore, all sorts of factors should be considered comprehensively according to the use of different membrane.
The characteristics of alumina microfiltration membranes obtained in this paper had met the need of microfiltration, which were: the most pore size 0.26 u m , porosity 32.15% , pure water permeability flux 488.5L/(m2 h) (under the pressure of 0.2Mpa). The membrane obtained could be used as microfiltration , and the support of ultrafiltration as well as.
引文
[1] P.M.Bungay et al. synthetic Membranes Science, Engineer and Application. D. Reidel Publishing Company. 1986
[2] D.R.Loyd. Material Science of Synthetic Membranes. [J] . Am. Chem. Soc, Washington DC. 1985
[3] A. Crull. Prospects for the inorganic membrane business. [J] . Key Engineering Materials, 1991,61/62:297～298
[4] 徐南平，时钧．陶瓷分离膜的发展历史与趋势．[J]．粉体技术．1997，3(3)：45
[5] Leenaars A. F. M. K. Keizer, A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:1. Microstructure investigations on non-supported membranes. [J]. Mater. Sci. 1984, 19:1077～1088
[6] Leenaars A. F. M., A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:2. The formation of supported membranes. [J]. Coll. Interface Sci. 1985, 105(1):27～40
[7] Leenaars A. F. M., A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:3. The permeability for pure liquids. [J]. Memb. Sci. 1985,24:245～260
[8] Leenaars A. F. M., A. J. Burggraaf. The preparation and charactreizatio of alumina membranes with ultrafine pores:4. Ultrafiltration and hyperfiltration experiments. [J]. Memb. Sci. 1985,24:261～270
[9] Anderson M.A, M.L. Gieselman, Q.Xu. Titania and alumina ceramic membranes. [J|. Memb. Sci.1988,39:243～258
[10] 徐南平，时钧．无机膜的发展现状．[J]．南京化工大学学报．1998， 20(4)：102～106
[11] Hsieh H.P., Bhave R.R., H.L.Fleming. Microporous alumina membranes. [J]. Memb. Sci. 1988(39):221～241
[12] 侯相林，高荫本，陈诵英等．微孔无机膜的制备与改性．[J]．膜科学与技术，1996，16(4)：7～8
[13] 黄肖容，黄仲涛．溶胶—凝胶法制备不对称氧化铝膜．[J]．无机材料学报，1998，13(4)：534
[14] A.Larbot, J.p.Fabre, C.Guizard, et al. Inorganic membranes obtained by sol-gel technique [J]. Membrane Science,39,203(1988)
[15] 黄肖容，黄仲涛．用快速凝胶法制备无机氧化铝膜．[J]．材料研究学报，1999，13(4)：372～375
[16] 黄仲涛，曾昭槐，钟邦克等编著．[M]．无机膜技术及其应用．中国石化出版社，1999，第一版
[17] Leeneers A F M, Burggraaf A J. The preparation and characterization of alumina membranes with ultrafine pores .[J]. Colloid and Interface Sci. 1985, 105:27-40
[18] 杨维慎，邬继成，刘世河等．无机陶瓷膜的制备及其在催化中的应用．[J]．自然科学进展—国家重点实验室通讯，1993，3(2)：181-185
[19] Itays K, Sugawara S, Arai K, et al. Preparation and characterization of microporous ceramic media. [J]. Chem. Eng. Jpn, 1984, 17514-520
[20] 王焕庭，刘杏芹，周勇等．多孔陶瓷支撑体膜材料的制备与性能表征．[J]． 膜科学与技术，1997，17(1)：47-52
[21] 王沛，徐南平，时钧．管式陶瓷膜的制备．[J]．膜科学与技术，1996，16(3)：52-57
[22] 黄肖容，黄仲涛．熔模离心法制备高纯氧化铝基质膜管．[J]．膜科学与技术，1996，16(2)：31～38
[23] Pavlovic T and Ignatiev A. Optical and micro structural properties of anodic ally oxdozed aluminum .[J]. Thin Solid Films, 1986, 138:97-109
[24] 杨邦朝，王文生．薄膜物理与技术．[M]．电子科技大学出版社，1994：123
[25] Jiaratananon R, Chanachai A. A study of fouling in the ultrafiltration of passion fruit juice. [J]. memb. Sci. 1996(111):39～48
[26] Chen A S Flynm J T, Cook R G, et al. Removal of oil, grease, and suspended solids from produced water with ceramic crossflow microfiltration. [J]. SPE Production Engineering, 1991 (6): 131～136
[27] Humphery J L, Goodboy K P, Cassday A L. Ceramic membranes for the treatment of waters produced by oil wells. Am Chem Soc 197th National
Meeting, Dallas, 1989
[28] Chen A S, Flynm J T, Cook R G, et al. Removal of oil, grease, and suspended solids from produced water with ceramic crossflow microfiltration. [J]. SPE Production Engineering. 1991 (6): 131～136
[29] Humphery J L, Goodboy K P, Casaday A L. Ceramic membranes for the treatment of waters produced by oil wells. Am Chem Soc 197th National Meeting. Dallas. 1989
[30] 王怀林，王忆川，姜建胜等．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
[31] Simms K M, Liu T H, Zaidi S A.Recent advances in the application of membrane technology to the treatment of produced water in Canada. [J]. Water Treat. 1995(10): 135～144
[32] 邢卫红，张伟．陶瓷膜脱除炼油厂焦化废水中焦粉．[J]．南京化工大学学报，1998，20(3)：10～13
[33] Gaston C. Textile size reclamation through ultrafiltration (product brochure), 1979
[34] Soma C, Rumeau M, Sergent C. Use of mineral membranes in the treatment of textile effluents. Proc 1~(st) Intl Conf on Inorg Membr. Montpellier: 1989,523～526
[35] Gryaznov V M, Karavanov A N, Khim-Farm Zh. 1979, 13, 74
[36] Gryaznov V M, Z. Phs. Chem. Neue Folge, 1986, 147, 761
[37] V. Violante, L. Bettinali, L. Bimbi, et al. Reattore a membrana ceramica catalitica per la separazione di idrogeno e/o suoi isotopida correnti fluide. Brevetto Italiano RM 92 A000086, 7-2-1992; US Patent N. 5366712, 22/11/1994.
[38] Nourbakhsh W, et al, Alche Symp. Ser. 1989, 85(268), 75
[39] V.T.Zaspalis, Catalytically active ceramic membranes, Ph.D. Thesis, Twente University, NL, 1990
[40] V.T. Zaspalis, W. van Praag, K. Keizer, et al. Reactions of methanol over catalytically active alumina membranes. [J] Appl. Catal., 74 [1] 204-22 (1991)
[41] 王湛．膜分离技术基础．[M]．北京 化学工业出版社 2000，267～282
[42] Pore size characteristics of membrane filters for use with aerospace fluids. [P] ASTM Designation F316-80.1980
[43] Ruth E.Baltus. Characterization of the pore area distribution in porous membranes using transport measurements. [J] . Journal of Membrane Science 123(1997) 165-184
[44] 黄培，徐南平，时钧等．液体排除法测定多孔陶瓷膜孔径分布．[J]．南京化工大学学报 1998，20(3)
[45] K. Venkataraman, W. T. Choate, E. R. Tore, et al. Characterization studies of ceramic membranes.A novel technique using a coulter porometer. [J]. Membrane Sci, 1998, 39:259～271
[46] K. Venkataraman, W. T. Choate, E. R. Torre et al. Characterization studies of ceramic membranes. A novel technique using a coulter porometer.[J]. Mem Sci, 1988, 39:259～271
[47] 黄培，刑卫红，徐南平等．气体泡压法测定无机微滤膜孔径分布研究． [J]．水处理技术．1996，22(2)：80～84
[48] 时钧、袁权等．膜技术手册．[M]．北京 化学工业出版社 2001，1
[49] 祝振鑫，张观顺，王德印等．测定超率膜切割分子量的一种简便方法． [J]．湿法冶金．1995，4：14-23
[50] 祝振鑫，吴立明，胡晓君等．用鸡蛋清中的卵清蛋白测定常用超率膜的切割分子量．[J]．膜科学与技术．1999，19(5)：46-50
[2] D.R.Loyd. Material Science of Synthetic Membranes. [J] . Am. Chem. Soc, Washington DC. 1985
[3] A. Crull. Prospects for the inorganic membrane business. [J] . Key Engineering Materials, 1991,61/62:297～298
[4] 徐南平，时钧．陶瓷分离膜的发展历史与趋势．[J]．粉体技术．1997，3(3)：45
[5] Leenaars A. F. M. K. Keizer, A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:1. Microstructure investigations on non-supported membranes. [J]. Mater. Sci. 1984, 19:1077～1088
[6] Leenaars A. F. M., A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:2. The formation of supported membranes. [J]. Coll. Interface Sci. 1985, 105(1):27～40
[7] Leenaars A. F. M., A. J. Burggraaf. The preparation and characterization of alumina membranes with ultrafine pores:3. The permeability for pure liquids. [J]. Memb. Sci. 1985,24:245～260
[8] Leenaars A. F. M., A. J. Burggraaf. The preparation and charactreizatio of alumina membranes with ultrafine pores:4. Ultrafiltration and hyperfiltration experiments. [J]. Memb. Sci. 1985,24:261～270
[9] Anderson M.A, M.L. Gieselman, Q.Xu. Titania and alumina ceramic membranes. [J|. Memb. Sci.1988,39:243～258
[10] 徐南平，时钧．无机膜的发展现状．[J]．南京化工大学学报．1998， 20(4)：102～106
[11] Hsieh H.P., Bhave R.R., H.L.Fleming. Microporous alumina membranes. [J]. Memb. Sci. 1988(39):221～241
[12] 侯相林，高荫本，陈诵英等．微孔无机膜的制备与改性．[J]．膜科学与技术，1996，16(4)：7～8
[13] 黄肖容，黄仲涛．溶胶—凝胶法制备不对称氧化铝膜．[J]．无机材料学报，1998，13(4)：534
[14] A.Larbot, J.p.Fabre, C.Guizard, et al. Inorganic membranes obtained by sol-gel technique [J]. Membrane Science,39,203(1988)
[15] 黄肖容，黄仲涛．用快速凝胶法制备无机氧化铝膜．[J]．材料研究学报，1999，13(4)：372～375
[16] 黄仲涛，曾昭槐，钟邦克等编著．[M]．无机膜技术及其应用．中国石化出版社，1999，第一版
[17] Leeneers A F M, Burggraaf A J. The preparation and characterization of alumina membranes with ultrafine pores .[J]. Colloid and Interface Sci. 1985, 105:27-40
[18] 杨维慎，邬继成，刘世河等．无机陶瓷膜的制备及其在催化中的应用．[J]．自然科学进展—国家重点实验室通讯，1993，3(2)：181-185
[19] Itays K, Sugawara S, Arai K, et al. Preparation and characterization of microporous ceramic media. [J]. Chem. Eng. Jpn, 1984, 17514-520
[20] 王焕庭，刘杏芹，周勇等．多孔陶瓷支撑体膜材料的制备与性能表征．[J]． 膜科学与技术，1997，17(1)：47-52
[21] 王沛，徐南平，时钧．管式陶瓷膜的制备．[J]．膜科学与技术，1996，16(3)：52-57
[22] 黄肖容，黄仲涛．熔模离心法制备高纯氧化铝基质膜管．[J]．膜科学与技术，1996，16(2)：31～38
[23] Pavlovic T and Ignatiev A. Optical and micro structural properties of anodic ally oxdozed aluminum .[J]. Thin Solid Films, 1986, 138:97-109
[24] 杨邦朝，王文生．薄膜物理与技术．[M]．电子科技大学出版社，1994：123
[25] Jiaratananon R, Chanachai A. A study of fouling in the ultrafiltration of passion fruit juice. [J]. memb. Sci. 1996(111):39～48
[26] Chen A S Flynm J T, Cook R G, et al. Removal of oil, grease, and suspended solids from produced water with ceramic crossflow microfiltration. [J]. SPE Production Engineering, 1991 (6): 131～136
[27] Humphery J L, Goodboy K P, Cassday A L. Ceramic membranes for the treatment of waters produced by oil wells. Am Chem Soc 197th National
Meeting, Dallas, 1989
[28] Chen A S, Flynm J T, Cook R G, et al. Removal of oil, grease, and suspended solids from produced water with ceramic crossflow microfiltration. [J]. SPE Production Engineering. 1991 (6): 131～136
[29] Humphery J L, Goodboy K P, Casaday A L. Ceramic membranes for the treatment of waters produced by oil wells. Am Chem Soc 197th National Meeting. Dallas. 1989
[30] 王怀林，王忆川，姜建胜等．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
[31] Simms K M, Liu T H, Zaidi S A.Recent advances in the application of membrane technology to the treatment of produced water in Canada. [J]. Water Treat. 1995(10): 135～144
[32] 邢卫红，张伟．陶瓷膜脱除炼油厂焦化废水中焦粉．[J]．南京化工大学学报，1998，20(3)：10～13
[33] Gaston C. Textile size reclamation through ultrafiltration (product brochure), 1979
[34] Soma C, Rumeau M, Sergent C. Use of mineral membranes in the treatment of textile effluents. Proc 1~(st) Intl Conf on Inorg Membr. Montpellier: 1989,523～526
[35] Gryaznov V M, Karavanov A N, Khim-Farm Zh. 1979, 13, 74
[36] Gryaznov V M, Z. Phs. Chem. Neue Folge, 1986, 147, 761
[37] V. Violante, L. Bettinali, L. Bimbi, et al. Reattore a membrana ceramica catalitica per la separazione di idrogeno e/o suoi isotopida correnti fluide. Brevetto Italiano RM 92 A000086, 7-2-1992; US Patent N. 5366712, 22/11/1994.
[38] Nourbakhsh W, et al, Alche Symp. Ser. 1989, 85(268), 75
[39] V.T.Zaspalis, Catalytically active ceramic membranes, Ph.D. Thesis, Twente University, NL, 1990
[40] V.T. Zaspalis, W. van Praag, K. Keizer, et al. Reactions of methanol over catalytically active alumina membranes. [J] Appl. Catal., 74 [1] 204-22 (1991)
[41] 王湛．膜分离技术基础．[M]．北京 化学工业出版社 2000，267～282
[42] Pore size characteristics of membrane filters for use with aerospace fluids. [P] ASTM Designation F316-80.1980
[43] Ruth E.Baltus. Characterization of the pore area distribution in porous membranes using transport measurements. [J] . Journal of Membrane Science 123(1997) 165-184
[44] 黄培，徐南平，时钧等．液体排除法测定多孔陶瓷膜孔径分布．[J]．南京化工大学学报 1998，20(3)
[45] K. Venkataraman, W. T. Choate, E. R. Tore, et al. Characterization studies of ceramic membranes.A novel technique using a coulter porometer. [J]. Membrane Sci, 1998, 39:259～271
[46] K. Venkataraman, W. T. Choate, E. R. Torre et al. Characterization studies of ceramic membranes. A novel technique using a coulter porometer.[J]. Mem Sci, 1988, 39:259～271
[47] 黄培，刑卫红，徐南平等．气体泡压法测定无机微滤膜孔径分布研究． [J]．水处理技术．1996，22(2)：80～84
[48] 时钧、袁权等．膜技术手册．[M]．北京 化学工业出版社 2001，1
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