臺灣博碩士論文加值系統

本研究係將疏水性高分子poly(2,6-dimethyl-p-phenylene oxide) (PPO)混合有機咪唑配體與二價鋅所合成的Zeolitic Imidazolate Framework-8 (ZIF-8) 刮於聚丙烯腈基材膜上製備成混合基質複合薄膜應用於醋酸水溶液的滲透蒸發脫水程序。通常在常溫操作下，醋酸跟水分子之間有很強的氫鍵作用力，在滲透蒸發程序中會產生Coupling的影響，使醋酸水溶液的脫水效能不佳，若要消除Coupling的影響必須將操作溫度提高，藉由提高分子動能降低分子之間的作用力，本研究利用疏水性PPO高分子進行分離醋酸水溶液，期望藉由PPO玻璃態的性質在高溫下依然具有分離能力，另添加ZIF-8期望分子篩的效應提升透過量與選擇性。研究中ZIF-8添加量改變及混合機質薄膜熱處理對滲透蒸發透過效能之影響被詳細探討，FESEM及SEM-EDX被用來觀察薄膜之結構型態及MOF在薄膜中的分布狀態，FTIR、DSC、TGA、接觸角量測則被用於鑑定ZIF-8/PPO複合薄膜之物、化特性。
研究結果發現添加ZIF-8會使透過量提高但透過水濃度下降，因此利用熱處理對混合基質複合薄膜進行後處理，實驗數據發現，熱處理溫度為100°C而熱處理時間為30分鐘時擁有最好的效能，其分離90wt%醋酸水溶液的透過量為112g/m2h而分離因子為1491。ZIF-8/PPO複合薄膜在高溫操作能同時提升透過量及透過水濃度，此結果證實高溫操作確實可降低醋酸跟水分子之Coupling效應。

In this study, ZIF-8 was added into a hydrophobic polymer, poly(2,6-dimethyl-p-phenylene oxide), and casted on PAN support membranes to form a mixed matrix composite membranes. The MMCMs was applied to separate 90wt% acetic acid aqueous solution. However, the pervaporation performance have limited by coupling effect between acetic acid and water at room temperature. This problem was solved by increasing operation temperature, because the kinetic energy of molecular was increased at high temperature that could decreased the interaction between water and acetic acid. On the other hand, the PPO polymer was a glassy polymer that the polymer chain cannot move easily at high temperature, so the pervaporation performance still good at high temperature.
The pervaporation separation performance was studied by changing the amount of ZIF-8 and heat treatment. The dispersion of ZIF-8 in the PPO active layer was evaluated by FESEM and EDX images to characterize the structure and dispersible. The membrane structure was correlated with the pervaporation performance. In other ways, the physicochemical properties of ZIF-8/PPO mixed matrix composite membranes was characterized by FTIR、TGA、DSC、water contact angle.
The pervaporation results show the performance is limited by coupling effect. In research, heat-treated ZIF-8/PPO mixed matrix composite membranes could improve the pervaporation performance. The flux is 112g/m2h and the separation factor is 1491 at best condition 100°C and 30minutes. The permeation rate and water concentration in permeat of ZIF-8/PPO mixed matrix composite membranes both increased with operation temperature increasing. It confirmed that coupling effect can be reduce by high temperature operation.

目錄
中文摘要 I
Abstract III
誌謝 V
目錄 VI
圖索引 VIII
表索引 XI
第一章 序論 1
1-1 前言 1
1-2薄膜分離技術 2
1-3 滲透蒸發分離系統 6
1-3-1滲透蒸發分離技術 6
1-3-2滲透蒸發原理 7
1-4 薄膜製備方式 8
1-4-1基材層之製備 8
1-4-2緻密層之製備 10
1-4-3有機/無機混成薄膜 10
1-5文獻回顧 12
1-5-1 高分子薄膜之滲透蒸發分離應用 12
1-5-2 無機薄膜之滲透蒸發分離應用 13
1-5-3 混合基質薄膜 (Mixed Matrix Membranes) 14
1-5-4含金屬有機骨架孔洞材料 (Metal Organic Frameworks, MOFs)之混合基質薄膜 16
1-5-5 滲透蒸發應用醋酸水溶液脫水程序 18
1-6實驗動機與目的 19
第二章 實驗 20
2-1 藥品 20
2-2 儀器與設備 21
2-3 薄膜製備 23
2-3-1聚丙烯腈基材膜之製備 23
2-3-2 Pristine PPO與ZIF-8/PPO混合基質複合薄膜的製備 23
2-4 ZIF-8顆粒與混合基質薄膜之鑑定與測試 24
2-4-1 掃描式電子顯微鏡 ( Scanning Electron Microscopy, SEM ) 24
2-4-2熱重分析儀(Thermogravimetry analyzer) 25
2-4-3 微差式掃描熱卡計分析 (Differential scanning calorimeter, DSC) 25
2-4-4 傅立葉轉換紅外線光譜儀 (Fourier transform infrared spectroscopy, FT-IR) 26
2-4-5 膨潤測試 ( Swelling test ) 27
2-4-6 薄膜表面親疏水性測試 27
2-4-7 滲透蒸發測試 (Pervaporation testing) 28
2-5 實驗流程圖 30
第三章 結果與討論 31
3-1 POLY(P-PHENYLENE OXIDE)濃度對薄膜滲透蒸發效能之影響 31
3-2 ZIF-8/PPO混合基質薄膜之ZIFS添加量變化對滲透蒸發效能的影響 37
3-3滲透蒸發條件變化對於分離效能的影響 47
3-3-1進料溫度對於滲透蒸發效能之影響 47
3-3-2進料濃度對於滲透蒸發效能之影響 49
3-4 熱處理對ZIF-8/PPO混合基質薄膜滲透蒸發效能的影響 51
3-4-1進料溫度對於熱處理ZIF-8/PPO混合基質薄膜滲透蒸發效能之影響 56
3-4-2進料濃度對於熱處理ZIF-8/PPO混合基質薄膜滲透蒸發效能之影響 57
3-5 滲透蒸發醋酸水溶液脫水程序之分離效能 59
第四章 結論 60
第五章 參考文獻 61









圖索引
Figure 1-1 Schematic representation of the nominal pore size and best theoretical model for the principal membrane separation processes [4]. 5
Figure 1-2 The principle of pervaporation [5]. 7
Figure 1-3 The schematic diagram of various nanoscale morphology of the mixed matrix structure [38]. 15
Figure 1-4 Construction of a designed MOF, from metal-containing node and bridging organic ligand to building unit and then to three-dimensional framework with pores. The last image highlights the geometrical assembly of the framework with the ligands and polyhedral cages acting as three- (yellow) and twenty-four- (red) connected nodes, respectively [41]. 17

Figure 2-1 The schematic diagram of pervaporation apparatus. 29

Figure 3-1 Effect of PPO concentration on the pervaporation performance of composite membranes . 33
Figure 3-2 The SEM cross-sectional images of pristine PPO membrane with different concentration(a) 2wt% PPO (b) 4wt%PPO (c) 8wt%PPO (d) 10wt%PPO (e) 16wt%PPO. 34
Figure 3-3 The SEM surface images of pristine PPO membrane with different concentration(a) 2wt% PPO (b) 4wt%PPO (c) 8wt%PPO (d) 10wt%PPO (e) 16wt%PPO. 35
Figure 3-4 The SEM cross-sectional images of pristine PPO membrane with different thickness(a) 16wt%PPO/25um wire bar (b) 16wt%PPO/9um wire bar . 36
Figure 3-5 ATR-FTIR spectra of the MMMs with different ZIF-8 content. 38
Figure 3-6 Lower wave number ATR-FTIR spectra of the MMMs with different ZIF-8 content . 39
Figure 3-7 TGA curve of MMMs with different ZIF-8 content. 40
Figure 3-8 Pervaporation performance of MMMs with different ZIF-8 content. 43
Figure 3-9 Water contact angle of ZIF-8/PPO mixed matrix composite membranes prepared with different ZIF-8 content. 43
Figure 3-10 The cross-sectionnal SEM-EDX images of MMMs with different ZIF-8 content. 44
Figure 3-11 The cross-sectional SEM images of pristine PPO composite membrane. 45
Figure 3-12 The cross-sectional SEM images of MMMs with different ZIF-8 content. 46
Figure 3-13 Effect of the operating temperature on pervaporation performance of 90 wt% aqueous acetic acid solution through pristine PPO membranes and 15wt%ZIF-8/PPO MMMs. 48
Figure 3-14 Effect of the acetic acid concentration in feed solution on pervaporation performance through pristine PPO membranes and 15wt% ZIF-8/PPO MMMs. 50
Figure 3-15 Effect of the acetic acid concentration in solution on swelling degree through pristine PPO membranes and 15wt% ZIF-8/PPO MMMs. 50
Figure 3-16 Effect of heat treatment time on pervaporation performance on 15wt%ZIF-8/PPO(heat temperature：100°C). 51
Figure 3-17 Effect of heat treatment temperature on pervaporation performance on 15wt%ZIF-8/PPO(heat time：30min.). 53
Figure 3-18 Effect of heat treatment temperature on PSI value on 15wt%ZIF-8/PPO. 53
Figure 3-19 The cross-sectional SEM images of 15wt%ZIF-8/PPO treated at different temperatures. 55
Figure 3-20 Effect of the operating temperature on pervaporation performance of 90 wt% aqueous acetic acid solution through 15wt%ZIF-8/PPO MMMs (Heat treatment condition：100°C, 30 minutes). 57
Figure 3-21 Effect of the acetic acid concentration in feed solution on pervaporation performance through 15wt% ZIF-8/PPO MMMs (Heat treatment condition：100°C, 30 minutes). 58





表索引
Table 1-1 Driving force and the two-phase systems separated by membranes for different membrane process [2]. 4

Table 3-1 Pervaporation performance of composite membranes with different thickness. 36
Table 3-2 Glass transition temperature of MMMs with different ZIF-8 content. 42
Table 3-3 TGA results of 15wt% ZIF-8/ PPO treated at different temperatures. 55
Table 3-4 The PV performance of membranes from this work and literatures. 59

1.L. Y. Jiang, Y. Wang, T. S. Chung, X. Y. Qiao, J. Y. Lai, Polyimides membranes for pervaporation and biofuels separation, Prog. Polym. Sci. 34 (2009) 1135–1160.
2.M. Mulder, Basic principles of membrane technology, Kluwer academic publishers, The Netherlands (1996)
3.R. W. Baker, Membrane Technology and Applications, McGraw-Hill, United States (2000).
4.T. Uragami, K. Okazaki, H. Matsugi, and T. Miyata, Structure and permeation characteristics of an aqueous ethanol solution of organic−inorganic hybrid membranes composed of poly(vinyl alcohol) and tetraethoxysilane, Macromolecules 35 (2002) 9156-9163.
5.H. Wang, X. Lin, K. Tanaka, H. Kita, K. I. Okamoto, Preparation of plasma-grafted polymer membranes and their morphology and pervaporation properties toward benzene/cyclohexane mixtures, J. Polym. Sci. Part A：Polym. Chem. 36 (1998) 2247-2259.
6.M. Y. Teng, K. R. Lee, D. J. Liaw, Y. S. Lin, J. Y. Lai, Plasma deposition of acrylamide onto novel aromatic polyamide membrane for pervaporation, Eur. Polym. J. 36 (2000) 663-672.
7.P. Vandeweerdt, H. Berghmans, Temperature-concentration behavior of solution polydisperse, atactic poly(methyl methacrylate) and its influence on the formation of amorphous microporous membranes, Macromolecules 24 (1991) 3547-3552.


8.F. J. Hua, T. G. Park, D. S. Lee, A facile preparation of highly interconnected macroporous poly(D, L-lactic acid-co-glycolic acid) (PLGA) scaffolds by liquid–liquid phase separation of a PLGA–dioxane–water ternary system, Polymer 44 (2003) 1911-1920.
9.L. Zeman, T. Fraser, Formation of air-cast cellulose acetate membranes Part II. Kinetics of demixing and macrovoid growth, J. Membr. Sci. 87 (1994) 267-279.
10.Y. C. Wang, C. L. Li, J. Huang, C. Lin, K. R. Lee, D. J. Liaw, J. Y. Lai, Pervaporation of benzene/cyclohexane mixtures through aromatic polyamide membranes, J. Membr. Sci. 185 (2001) 193-200.
11.J. H. Kim, S. B. Lee, S. Y. Kim, Incorporation effects of fluorinated side groups into polyimide membranes on their physical and gas permeation properties, J. Appl. Polym. Sci. 77 (2000) 2756-2767.
12.H. Strathmann, K. Kock, The formation mechanism of phase inversion membranes, Desalination 21 (1977) 241-255.
13.J. Y. Lai, M. J. Liu, K. R. Lee, Polycarbonate membrane prepared via a wet phase inversion method for oxygen enrichment from air, J. Membr. Sci. 86 (1994) 103-118.
14.F. C. Lin, D. M. Wang, J. Y. Lai, Asymmetric TPX membranes with high gas flux, J. Membr. Sci. 110 (1996) 25-36.
15.S. L. Huang, M. S. Chao, J. Y. Lai, Diffusion of ethanol and water through PU membrane, Eur. Polym. J. 34 (1998) 449-454.
16.S. Chemtech, Pervaporation Membranes for Organic Separation Instructions for Storage, Handling and Commissioning, Sulzer Chemtech GmbH.
17.C. K. Yeom, K. H. Lee, Pervaporation separation of water-acetic acid mixtures through poly(vinyl alcohol) membranes crosslinked with glutaraldehyde, J. Membr. Sci. 109 (1996) 257-265.
18.Y. Zhu, S. Xia, G. Liu, W. Jin, Preparation of ceramic-supported poly(vinyl alcohol)–chitosan composite membranes and their applications in pervaporation dehydration of organic/water mixtures, J. Membr. Sci. 349 (2010) 341–348.
19.J. Ge, Y. Cui, Y. Yan, W. Jiang, The effect of structure on pervaporation of chitosan membrane, J. Membr. Sci. 165 (2000) 75-81.
20.W. Zhang, G. W. Li, Y. J. Fang, X. P. Wang, Maleic anhydride surface-modification of crosslinked chitosan membrane and its pervaporation performance, J. Membr. Sci. 295 (2007) 130-138.
21.Y. J. Han, K. H. Wang, J. Y. Lai, Y. L. Liu, Hydrophilic chitosan-modified polybenzoimidazole membranes for pervaporation dehydration of isopropanol aqueous solutions, J. Membr. Sci. 463, (2014), 17–23.
22.C. K. Yeom, J. G. Jegal, K. H. Lee, Characterization of relaxation phenomena and permeation behaviors in sodium alginate membrane during pervaporation separation of ethanol–water mixture, J. Appl. Polym. Sci. 62 (1996) 1561-1576.
23.C. K. Yeom, K. H. Lee, Vapour permeation of ethanol-water mixtures using sodium alginate membranes with crosslinking gradient structure, J. Membr. Sci. 135 (1997) 225-235.
24.H. Badiger, S. Shukla, S. Kalyani, S. Sridhar, Thin film composite sodium alginate membranes for dehydration of acetic acid and isobutanol, J. Appl. Polym. Sci. 10.1002 (2014) 40018.
25.U. S. Toti, T. M. Aminabhavi, Different viscosity grade sodium alginate and modified sodium alginate membranes in pervaporation separation of water + acetic acid and water + isopropanol mixtures, J. Membr. Sci. 228 (2004) 199–208.
26.Y. J. Fu, C. L. Lai, J. T. Chen, C. T. Liu, S. H. Huang, W. S. Hung, C. C. Hu, K. R. Lee, Hydrophobic composite membranes for separating of water–alcohol mixture by pervaporation at high temperature, Chemical Engineering Science 111 (2014) 203–210.
27.K. Tanaka, R. Yoshikawa, C. Ying, H. Kita, K. Okamoto, Application of zeolite membranes to esterification reactions, Catalysis Today 67 (2001) 121–125.
28.M. H. Zhu, I. Kumakiri, K. Tanaka, H. Kita, Dehydration of acetic acid and esterification product by acid-stable ZSM-5 membrane, Microporous and Mesoporous Materials 181 (2013) 47–53.
29.H. Matsuda, H. Yanagishita, H. Negishi, D. Kitamoto, T. Ikegami, K. Haraya, T. Nakane, Y. Idemoto, N. Koura, T. Sano, Improvement of ethanol selectivity of silicalite membrane in pervaporation by silicone rubber coating, J. Membr. Sci. 210 (2002) 433–437.
30.S. Tanaka, T. Yasuda, Y. Katayama, Y. Miyake, Pervaporation dehydration performance of microporous carbon membranes prepared from resorcinol/formaldehyde polymer, J. Membr. Sci. 379 (2011) 52–59.
31.P. S. Tin, H. Y. Lin, R. C. Ong, T. S. Chung, Carbon molecular sieve membranes for biofuel separation, Carbon 49 (2011) 369 – 375.
32.I. Menendez, A. B. Fuertes, Aging of carbon membranes under different environments, Carbon 39 (2001) 733-740.
33.陳顯修, 氧氣化學吸附對碳分子篩薄膜氣體分離效能與化學老化行為之影響, 中原大學化學工程學系碩士學位論文 (2014).
34.H. M. Guan, T. S. Chung, Z. Huang, M. L. Chng, S. Kulprathipanja, Poly(vinyl alcohol) multilayer mixed matrix membranes for the dehydration of ethanol–water mixture, J. Membr. Sci. 268 (2006) 113–122.
35.Y. Shirazi, M. A. Tofighy, T. Mohammadi, Synthesis and characterization of carbon nanotubes/poly vinyl alcohol nanocomposite membranes for dehydration of isopropanol, J. Membr. Sci. 378 (2011) 551–561.
36.S. Y. Lu, C. P. Chiu, H. Y. Huang, Pervaporation of acetic acid/water mixtures through silicalite filled polydimethylsiloxane membranes, J. Membr. Sci. 176 (2000) 159–167.
37.S. J. Lue, I. M. Su, D. T. Lee, H. Y. Chen, C. M. Shih, C. C. Hu, Y. C. Jean, J. Y. Lai, Correlation between Free-Volume Properties and Pervaporative Flux of Polyurethane-Zeolite Composites on Organic Solvent Mixtures, J. Phys. Chem. B 2011, 115, 2947–2958.
38.T. S. Chung, L. Y. Jiang, Y. Li, S. Kulprathipanja, Mixed matrix membranes (MMMs) comprising organic polymers with dispersed inorganic fillers for gas separation, Prog. Polym. Sci. 32 (2007) 483–507.
39.S. Y. Hu, Y. Zhang, D. Lawless, X. Feng, Composite membranes comprising of polyvinylamine-poly(vinyl alcohol) incorporated with carbon nanotubes for dehydration of ethylene glycol by pervaporation, J. Membr. Sci. 417–418 (2012) 34–44.
40.I. F. J. Vankelecom,* S. Van den broeck, E. Merckx, H. Geerts, P. Grobet, and J. B. Uytterhoeven, Silylation to improve incorporation of zeolites in polyimide films, J. Phys. Chem., (1996)100(9), 3753-3758.
41.D. V. Baelen, B. Van der Bruggen, K. Van den Dungen, J. Degreve, C. Vandecasteele, Pervaporation of water–alcohol mixtures and acetic acid–water mixtures, Chem. Eng. Sci. 60 (2005) 1583-1590.
42.K. S. Park, Z. Ni, A. P. Coˆte, J. Y. Choi, R. Huang, Fernando J. U. Romo, H. K. Chae, M. O’Keeffe, O. M. Yaghi, Exceptional chemical and thermal stability of zeolitic imidazolate frameworks, PNAS July 5, 2006 vol. 103 no. 27 10186–10191.
43.G. M. Shi, T. Yang, T. S. Chung, Polybenzimidazole (PBI)/ zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of alcohols, J. Membr. Sci. 415–416 (2012) 577–586.
44.M. Amirilargani, B. Sadatnia, Poly(vinyl alcohol)/zeolitic imidazolate frameworks (ZIF-8) mixed matrix membranes for pervaporation dehydration of isopropanol, J. Membr. Sci. 469(2014)1–10.
45.T. M. Aminabhavi, U. S. Toti, Pervaporation separation of water–acetic acid mixtures using polymeric membranes, Des. Monomers Polym. 6 (2003) 211-236.
46.T. M. Aminabhavi, H. G. Naik, Synthesis of graft copolymeric membranes of poly(vinyl alcohol) and polyacrylamide for the pervaporation separation of water/acetic acid mixtures, J. Appl. Polym. Sci. 83 (2003) 244-258.
47.S. P. Kusumocahyo, K. Sano, M. Sudoh, M. Kensaka, Water permselectivity in the pervaporation of acetic acid–water mixture using crosslinked poly(vinyl alcohol ) membranes, Separation and Purification Technology 18 (2000) 141–150.
48.W. Sun, X. Wang, J. Yang, J. Lu, H. Han, Y. Zhang, J. Wang, Pervaporation separation of acetic acid–water mixtures through Sn-substituted ZSM-5 zeolite membranes, J. Membr. Sci. 335 (2009) 83–88.
49.M. Y. Kariduraganavar, S. S. Kulkarni, A. A. Kittur, Pervaporation separation of water–acetic acid mixtures through poly(vinyl alcohol)-silicone based hybrid membranes, J. Membr. Sci. 246 (2005) 83–93.
50.J. R. Li, Y. Ma, M. C. McCarthy, J. Sculley, J. Yu, H. K. Jeong, P. B. Balbuena and H. C. Zhou, Carbon dioxide capture-related gas adsorption and separation in metal-organic frameworks, Coord. Chem. Rev. 255 (2011) 1791-1823.
51.R. Mahajan, W. J. Koros, Mixed Matrix Membrane Materials With Glassy Polymers. Part 1, Polym. Eng. Sci. July 2002, Vol. 42, No. 7.
52.R. Mahajan, W. J. Koros, Mixed Matrix Membrane Materials With Glassy Polymers. Part 2, Polym. Eng. Sci.,July 2002, Vol. 42, No. 7.
53.N. D. Hilmioglu, A. E. Yildirim, A. S. Sakaoglu, S. Tulbentci, Acetic acid dehydration by pervaporation, Chem. Eng. Process. 40 (2001) 263-267.
54.J. Huang, M. L. Tu, Y. C. Wang, C. L. Li, K. R. Lee, J. Y. Lai, Dehydration of acetic acid by pervaporation through an asymmetric polycarbonate membrane, Eur. Polym. J. 37 (2001) 527-534.
55.Y.M. Lee, B. K. Oh, Pervaporation of water–acetic acid mixture through poly(4- vinylpyridine-co-acrylonitrile) membrane, J. Membr. Sci. 85 (1993) 13-20.
56.A. A. Kittur, S. M. Tambe, S. S. Kulkarni, M. Y. Kariduraganavar, Pervaporation separation of water–acetic acid mixtures through NaY zeolite-incorporated sodium alginate membranes, J. Appl. Polym. Sci. 94 (2004) 2101-2109.