臺灣博碩士論文加值系統

本研究主要是製備聚氨基甲酸酯薄膜（簡稱 PU）添加不同的沸石重量比例（10wt%、20wt%、30wt%）所形成的複合膜去探討在滲透蒸發裝置中的分離效果。但是文中還是主要以添加30wt%的PU複合膜為主。因為PU本身對於有機物的吸附效果已經不錯，再加上沸石獨特的多孔洞、高吸附特性，所以吾人希望藉由取其優點能提高分離鄰/對二甲苯異構物。文中並利用DSC、XRD、SEM…等等分析方法去探討添加沸石對其物性的影響。實驗結果方面，對單成份氣體吸附而言，添加了沸石可以使得鄰二甲苯的擴散係數由純PU薄膜的2.17×10-13 m2/s上升5.67×10-13 m2/s；對二甲苯的擴散係數由純PU的2.75×10-13 m2/s下降為1.92×10-13 m2/s。吾人亦探討不同活性下對PU+沸石複合膜個別成份的影響，但影響不大。對於單成份液體吸附而言，純PU的個別吸附量與添加沸石後的吸附量其兩者的差異並不多，故吾人在液體吸附量方面，僅可慮有添加沸石的PU薄膜。在滲透蒸發實驗結果方面，利用此複合膜使得進料50/50的分離效果（o-/p- xylene）可由PU薄膜的1.37提高到1.89。由此知道此複合膜在搭配此滲透蒸發裝置的確有助於提高分離鄰/對二甲苯異構物。吾人亦探討溫度與沸石重量比例的變因，結果發現添加沸石比例會有助於提高分離的效果；但是提高溫度反而會使得分離效果變差。吾人亦有利用Flory-Huggins與UNIQUAC equation等方程式去模擬實驗值，結果發現與實驗值較為接近，但是以UNIQUAC equation較為準確。

This study is to prepare polyurethane membranes ( so-called PU ) by adding different zeolite weight fraction(10wt%,20wt%,30wt% ) to form composite membranes to investigate separation factor in the pervaporation equipment.But in this study is mainly using 30wt% PU. Becauase it’s high sorption ability on organic solvent and zeolite’s unique porosity , high sorption ability.Therefore, our study hope these advantages can increase separation factor for o-/p-Xylene isomers.This study also use DSC, XRD, SEM methods to investigate adding zeolite effect on its physical properties.In singal compoenet vapor sorption, adding zeolite can make o-Xylene’s diffusion coefficient increase from pure PU’s 2.17×10-13m2/s to 5.67×10-13m2/s;But it make p-Xylene’s diffusion coefficient decrease from pure PU’s2.75×10-13m2/s to 1.92×10-13m2/s. This study also investigate the effect with different activity for individual compoennt’s diffusion coefficient.From experiment’s result, its effect is very small.For singal component liquid sorption, because pure PU’s sorption ability is not different between pure PU and zeolite’s PU.Hence, in this study is only to consider zeolite’s PU.In the pervaporation ‘s results, using composite PU membrane can make separation factor(o-/p-Xylene) from pure PU’s 1.37 to 1.89.As a result, we know this composite membrane really contribute to increase separation factor for o-/p-Xylene isomers in pervaporation . We also disscus different conditions such as temperature and zeolite weight fraction.From our results, adding zeolite weight fraction can increase separation factor but increasing temperature will decrease its separation factor. We also use Flory-Huggins and UNIQUAC equations to simulate experiment’s result.From this result, we can find simulation’s vales is well agreement to experiment’s vales but UNIQUAC equation is better than Flory-Huggins equation.

目錄
論文指導教推薦論文口試委員審定書 i
論文口試委員審定書 ii
論文口試委員審定書 iii
致謝 iv
中文摘要 v
英文摘要 vii
目錄 viii
圖目錄 xii
表目錄 xv
第一章、緒論 1
第二章、文獻回顧 2
2-1 二甲苯製程發展之介紹 2
2-1-1對二甲苯之簡介 2
2-1-2間二甲苯之簡介 3
2-1-3 鄰二甲苯之簡介 4
2-2 薄膜的介紹 6
2-2-1 薄膜的定義 6
2-2-2 薄膜技術的發展 6
2-2-3 薄膜技術的優點 7
2-3滲透蒸發 8
2-3-1 滲透蒸發於分離二甲苯異構物之相關研究 11
2-4 沸石（Zeolite）之介紹, 13
2-5 PU彈性體的介紹 15
第三章、實驗方法與材料 17
3-1 藥品 18
3-2材料與實驗設備 18
3-3實驗流程圖 20
3-4物性分析 21
3-4-1 DSC分析 21
3-4-2 Ｘ-ray 繞射分析 21
3-4-3 SEM分析 22
3-5 PU薄膜的製備 22
3-6 氣體吸附實驗 23
3-6-1 單成份氣體吸附實驗 23
3-6-2 擴散係數的計算 24
3-7 單成份吸附模擬 24
3-7-1吸附模擬 24
3-7-2 Flory-Huggins Theory 25
3-7-3 △GE 與的計算, 27
3-7-4 iM的計算 27
3-7-5 UNIQUAC model 28
3-8膨潤度單成份與雙成份液體吸附實驗 28
3-8-1 膨潤度實驗 28
3-8-2 雙成份液體進料吸附實驗 29
3-8-3 UNIQUAC三成份系統 30
3-9滲透蒸發實驗 30
3-9-1儀器裝置 31
3-9-2氣相層析儀（GC）分析條件 32
3-9-3質傳模擬 32
3-9-4 Fick’s First Law 33
3-9-5 Maxwell-Stefan equation29 35
第四章、結果與討論 38
4-1 物性分析與測試 38
4-1-1 DSC分析結果 38
4-1-2 XRD測試分析 38
4-1-3 SEM 形態分析 39
4-2 氣體吸附實驗 44
4-2-1單成份氣體吸附實驗 44
4-2-2利用UNIQUAC、Flory-Huggins Eq.模擬活性與體積分率 44
4-3 液體吸附實驗 53
4-3-1 單成份液體吸附實驗 53
4-3-2 雙成份液體吸附實驗 53
4-4 滲透蒸發實驗 60
4-4-1 PU、PU+Zeolite型之滲透蒸發實驗25°C 60
4-4-2 溫度變因 62
4-4-3沸石濃度變因 63
4-5 滲透蒸發程序中因兩成份極性所造成diffusion coupling現象 63
第五章、結論 74
符號表 76
參考文獻 79

1.呂永方，蒸餾固化法製程在二甲苯工業應用，長庚大學化工與材料工程研究所碩士論文，台灣 (2001)
2. 江敏川，間二甲苯的利用與展望，石油季刊，（1974）17-23.
3. 中國大陸鄰二甲苯市場概況，化工資訊與商情，（2003）109-111.
4. M. Mulder, Basic principles of membrane technology, Kluwer Academic Publishers（1996）
5. Y. Wang, C. Li, J. Huang, C. Lin, K.R. Lee, D.J. Lia, J.Y. Lai, Pervaporation of benzene/cyclohexane mixtures throuugh aromatic polyamide membranes, J. Memb. Sci. 185 (2001) 193-200.
6. T. K. Poddar, and K. K. Sirkar, A hybrid vapor permation and membrane based absorption stripping for voc removal and recovery from gaseous emissions, J. Membr. Sci. 132（1997）229-236.
7. 侯翔殷，以支持性液態薄膜分離二甲苯異構物之研究，長庚大學化工與材料工程研究所碩士論文，台灣（2002）
8. S.X. Chen, R.T. Lostritto, Diffusion of benzocaine in poly(ethylene-vinyl acetate) membranes-effects of vehicle ethanol concentration and membrane vinyl-acetate content, J. Control. Release.38（1996）185-191.
9. J.P.G. Villaluenga, A.T. Mohammadi, A reviews of separation bezene/cyclohexane mixtures by pervaporation processes, J. Membr. Sci. 169（2000）159-174.
10. P. A. Kober, Pervaporation, Perstillation and Percrystallization, J. Am. Chem. Soc.. 39 (1971) 944
11. M.H.V. Mulder, F. Kruitz, C.A. Smolders, Separation of isomeric xylenes by pervaporation through cellulose ester membrane, J. Membri. Sci.11（1982）349-363.
12. K. Wegner, J. Dong, Y.S. Lin, Polycrystalline MFI zeolite membranes:xylene pervaporation and its implication on membrane microstructure, J. Membri. Sci.158（1999）17-27.
13. T. Matsufuji, N. Nishiyama, M. Mastukata, K. Ueyama, Separation of butane and xylene isomers with MFI-type zeolitic membrane synthesized by a vapor-phase transport method, J. Membr. Sci.178（2000）25-34.
14. H.L. Chen, L.G. Wu, J. Tan, C.L. Zhu, PVA membrane filled β-cyclodextrin for separation of isomeric xylenes by pervaporation, J. Chem. Eng.78（2000）159-164.
15. S. Marcus, S.B. Claudia, Crosslinkable copolyimides for the membrane-based separation of p-/o-xylene mixtures, Reactive & Functional Polymers. 49（2001）205-213.
16. 莊惠鈞，以輔助輸送之液態薄膜分離二甲苯異構物之研究，長庚大學化工與材料研究所碩士論文，台灣（2000）
17. 嚴毅 ，製備PDMS/沸石複合膜及其滲透蒸發輸送機制研究，台灣大學化工研究所碩士論文，台灣（2000）
18. 蔡穆昀，二甲苯混合液之分離程序，清華大學化學工程研究所碩士論文，台灣（1991）
19. J. Muszynski, G.A. Wolinska, P. Penczek, Synthesis, characterization, and pervaporation properties of segmented
poly(urethane—urea)s, J.Appl. Polym. Sci. 71（1999）1615—1625.
20.彭欣泓，以製備摻合環糊精之聚氨基甲酸酯薄膜的性質探討與研究，長庚大學化工材料所碩士論文，台灣（2002）
21. L. Enneking, A. Heintz, R.N. Lichtenthaler, Sorption equilibria of the ternary mixture bezene/cyclehexene/cyclohexane in polyurethane and PEBA membrane polymers, J. Membr. Sci. 115（1996）161-170.
22. D. Roizard, A. Nilly, P. Lochon, Preparation and study of crosslinked polyurethane films to fractionate toluene-n-heptane mixtures by pervaporation, Sep. Purif.Technol. 22-23（2001）45-52.
23. J. Anne, C. Robert, L. Pierre, Permeability of block copolymers to vapors and liquids, Prog. Polym. Sci., 27 （2002）1803-1877
24. C.M. Balik, On the extraction of diffusion coefficients from gravimetric data for sorption of small molecules by polymer thin films, Macromolecules 29 (1996)3025-3029.
25. P.J. Flory, Principles of Poylmer Chemistry, Cornell University Press, Ithaca ,New York, (1953)pp 511-514.
26. O.Redlich, Thermodynamics: Fundamentals, Applications（1976）
27. J. Gmehling, U. Onken, W. Arlt, Vapor-Liquid Equilibrium Data Collection, Frankfurt, 1997
28. E.W. Funk, J.M. Prausnitz, Thermodynamic properties of liquid mixtures:aromatic-saturated hydrocarbon systems, Ind. Eng. Chem.62 (1970) 8-15.
29. A. Hentz, W. Stephan, A generalized solution-diffusion model of the pervaporation process thrpugh composite membranes PartI. Prediction of mixture of solubility in the dense activity layer using the UNIQUAC model, J.Membr. Sci. 89 (1994) 143-151.
30. H. D. Kamaruddin, W. J. Koros, Some observations about application of Fick’s first law for membrane separation of multicomponent mixtures, J. Membr. Sci. 135, (1977) 147-159.
31. 黃湘瑗，Silicalite/ PDMS奈米複合膜在醋酸水溶液滲透蒸發分離之應用，清華大學化學工程研究所碩士論文，台灣（2000）
32. F.R. Chen, H.F. Chen, A diffusion model of the pervaporation separation of ethylene glycol-watwer mixtures through crosslinked poly（vinyl alcohol）membrane, J. Membr. Sci. 139（1998）