臺灣博碩士論文加值系統

本研究論文，主要是使用聚丙烯腈 (polyacrylonitrile, PAN)作為複合薄膜的支撐層，幾丁聚醣 (chitosan)作為複合薄膜的緻密皮層，並使用矽氧烷作為交聯劑，其中交聯劑包括四乙氧基矽烷 (tetraethoxysilane, TEOS)、胺基丙基三乙基矽烷 (3-aminopropyltriethoxysilane, APTES)、3-縮水甘油丙基三甲氧矽烷 (3-glycidoxypropyl-trimethoxysilane, GPTMS)，以單一純silane和共混雙silane的方式對幾丁聚醣進行改質，以製備新型的PAN/chitosan/silanes奈米過濾複合薄膜。本實驗所使用的儀器包含了掃描式電子顯微鏡 (scanning electron microscope, SEM)、高壓過濾裝置、感應耦合電漿光學放射光譜儀 (inducitively coupled plasma optical emission spectrometer, ICP-OES)。本實驗的研究重點包括： (1)由SEM淬斷面和平面圖，探討silane和幾丁聚醣之間的相容性； (2)由網狀交聯結構的產生、無機材料本身的不透水性以及薄膜厚度所造成的質傳阻力的影響，探討影響通量的最主要原因； (3)探討鹽類的濃度對於鹽類通量的影響； (4)分析立體障礙性和交聯點數量，以確定阻鹽率較佳的複合薄膜製程。

In this research paper, primarily using polyacrylonitrile (PAN) as the composite film support layer, chitosan composite films as dense layer, and using silanes as a cresslinking agent, where the crosslinking agent includes tetraethoxysilane (TEOS), 3-aminopropyltriethoxysilane (APTES), and 3-glycidoxypropyl-trimethoxysilane (GPTMS) ,the chitosan were modified by using single pure silane and silanes mixture to prepare novel PAN/chitosan/silanes nanofiltration composite films. The instruments used in this experiment include scanning electron microscope (SEM), high pressure filtration device, and inducitively coupled plasma optical emission spectrometer (ICP-OES). The emphasis of research work is put on : (1) analyzing the compatibility of silane and chitosan by surface and cross-section of SEM； (2) analyzing the impact on flux of crosslinked network structure, inorganic material impermeability, and film thickness； (3) analyzing the effect on salt flux of the concentration of salts； (4) determining the process for higher salt-retardation composite membrane by analyzing steric hindrance and extent of crosslinking.

目錄
摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VI
表目錄 IX
第一章 緒論 1
1.1 前言 1
1-1-1 海水淡化 1
1.2 過濾方法 3
1.2.1 薄膜分離技術介紹 4
1-3 有機-無機複合薄膜 5
1-4 複合薄膜製備方法 6
1-5 幾丁質與幾丁聚醣 7
1-5-1 幾丁聚醣的特性與應用 7
1-5-2 幾丁聚醣的交聯反應 7
1-6 研究動機與目標 8
第二章 實驗 9
2-1 實驗藥品與材料 9
2-2 實驗儀器 10
2-3 實驗流程圖 12
2-4 實驗步驟 13
2-4-1 PAN支撐層製備 13
2-4-2 chitosan/ silane 溶液製備 13
2-4-3 PAN/ chitosan/ silane複合薄膜製備 13
2-4-4 實驗樣品命名 13
2-5 複合薄膜分析與測試 14
2-5-1 掃描式電子顯微鏡 (SEM) 14
2-5-2 純水過濾實驗 14
2-5-3 單一鹽類過濾實驗 14
2-5-4 感應耦合電漿光學放射光譜儀 (ICP-OES) 14
2-5-5幾丁聚醣與矽氧烷相容性之探討 14
2-5-5-1水接觸角測試 (water contact angle test) 14
2-5-5-2 未洗過之純silane複合薄膜SEM淬斷圖 15
第三章 結果與討論 17
3-1 複合薄膜結構型態分析 17
3-1-1 掃描式電子顯微鏡 (SEM) 17
3-2 單一鹽類與純水之通量實驗 18
3-3 單一鹽類過濾實驗 19
3-4幾丁聚醣與矽氧烷相容性之探討 21
第四章 結論 71
參考文獻 72

圖目錄
圖1-1 全世界生產乾淨水的比例 1
圖1-2 1980到2016間，薄膜法與蒸發法所生產的純淨水比較 3
圖1-3 薄膜系統依照原溶液進入薄膜中，分為終端系統與橫流系統 4
圖1-4 幾丁質與幾丁聚醣化學結構的比較 7
圖2-1 高壓過濾設備設計圖(集廣公司提供) 16
圖2-2 高壓過濾實體圖 16
圖3-1 幾丁聚醣的羥基與矽氧烷的反應式 22
圖3-2 幾丁聚醣的氨基與矽氧烷的反應式 22
圖3-3 矽氧烷的自身聚合反應 22
圖3-4 PAN的SEM淬斷面 (A)0.5kx (B)5kx 23
圖3-5 PC-150的SEM淬斷面 (A)0.5kx (B)5kx 24
圖3-6 PCT-20-150的SEM淬斷面 (A)0.5kx (B)5kx 25
圖3-7 PCG-20-150的SEM淬斷面 (A)0.5kx (B)5kx 26
圖3-8 PCA-20-150的SEM淬斷面 (A)0.5kx (B)5kx 27
圖3-9 PCTA-20-150的SEM淬斷面 (A)0.5kx (B)5kx 28
圖3-10 PCTG-20-150的SEM淬斷面 (A)0.5kx (B)5kx 29
圖3-11 PCGA-20-150的SEM淬斷面 (A)0.5kx (B)5kx 30
圖3-12 PC- 200的SEM淬斷面 (A)0.5kx (B)5kx 31
圖3-13 PCT-20-200的SEM淬斷面 (A)0.5kx (B)5kx 32
圖3-14 PCG-20-200的SEM淬斷面 (A)0.5kx (B)5kx 33
圖3-15 PCA-20-200的SEM淬斷面 (A)0.5kx (B)5kx 34
圖3-16 PCTA-20-200的SEM淬斷面 (A)0.5kx (B)5kx 35
圖3-17 PCTG-20-200的SEM淬斷面 (A)0.5kx (B)5kx 36
圖3-18 PCGA-20-200的SEM淬斷面 (A)0.5kx (B)5kx 37
圖3-19 PCT-60-150的SEM淬斷面 (A)0.5kx (B)5kx 38
圖3-20 PCG-60-150的SEM淬斷面 (A)0.5kx (B)5kx 39
圖3-21 PCA-60-150的SEM淬斷面 (A)0.5kx (B)5kx 40
圖3-22 PAN的SEM平面圖 (A)0.5kx (B)50kx 41
圖3-23 PC-150的SEM平面圖 (A)0.5kx (B)50kx 42
圖3-24 PC-200的SEM平面圖 (A)0.5kx (B)50kx 43
圖3-25 PCT-20-150的SEM平面圖 (A)0.5kx (B)50kx 44
圖3-26 PCG-20-150的SEM平面圖 (A)0.5kx (B)50kx 45
圖3-27 PCA-20-150的SEM平面圖 (A)0.5kx (B)50kx 46
圖3-28 PCTA-20-150的SEM平面圖 (A)0.5kx (B)50kx 47
圖3-29 PCTG-20-150的SEM平面圖 (A)0.5kx (B)50kx 48
圖3-30 PCGA-20-150的SEM平面圖 (A)0.5kx (B)50kx 49
圖3-31 PCT-20-200的SEM平面圖 (A)0.5kx (B)50kx 50
圖3-32 PCG-20-200的SEM平面圖 (A)0.5kx (B)50kx 51
圖3-33 PCA-20-200的SEM平面圖 (A)0.5kx (B)50kx 52
圖3-34 PCTA-20-200的SEM平面圖 (A)0.5kx (B)50kx 53
圖3-35 PCTG-20-200的SEM平面圖 (A)0.5kx (B)50kx 54
圖3-36 PCGA-20-200的SEM平面圖 (A)0.5kx (B)50kx 55
圖3-37 PCT-60-150的SEM平面圖 (A)0.5kx (B)50kx 56
圖3-38 PCG-60-150的SEM平面圖 (A)0.5kx (B)50kx 57
圖3-39 PCA-60-150的SEM平面圖 (A)0.5kx (B)50kx 58
圖3-40 PAN、PC-150、PCT-20-150、PCG-20-150、PCA-20-150與商業膜NF270在壓力為4 bar下的純水通量 59
圖3-41 PAN、PC-150、PCTA-20-150、PCTG-20-150、PCGA-20-150與商業膜NF270在壓力為4 bar下的純水通量 59
圖3-42 PAN、PC-200、PCT-20-200、PCG-20-200、PCA-20-200與商業膜NF270在壓力為4 bar下的純水通量 60
圖3-43 PAN、PC-200、PCTA-20-200、PCTG-20-200、PCGA-20-200與商業膜NF270在壓力為4 bar下的純水通量 60
圖3-44 PAN、PC-150、PCT-60-150、PCG-60-150、PCA-60-150與商業膜NF270在壓力為4 bar下的純水通量 61
圖3-45 PAN、PC-150、PCT-60-150、PCG-60-150、PCA-60-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之通量 61
圖3-46 PAN、PC-150、PCT-20-150、PCG-20-150、PCA-20-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之通量 62
圖3-47 PAN、PC-150、PCTA-20-150、PCTG-20-150、PCGA-20-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之通量 62
圖3-48 PAN、PC-200、PCT-20-200、PCG-20-200、PCA-20-200與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之通量 63
圖3-49 PAN、PC-200、PCTA-20-200、PCTG-20-200、PCGA-20-200與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之通量 63
圖3-50 PAN、PC-150、PCT-20-150、PCG-20-150、PCA-20-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之阻鹽率 64
圖3-51 PAN、PC-150、PCTA-20-150、PCTG-20-150、PCGA-20-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之阻鹽率 64
圖3-52 PAN、PC-200、PCT-20-200、PCG-20-200、PCA-20-200與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之阻鹽率 65
圖3-53 PAN、PC-200、PCTA-20-200、PCTG-20-200、PCGA-20-200與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之阻鹽率 65
圖3-54 PAN、PC-150、PCT-60-150、PCG-60-150、PCA-60-150與商業膜NF270在壓力為4 bar下的100 ppm硫酸鎂水溶液之阻鹽率 66
圖 3-55 PCT-20-150未洗過的SEM淬斷圖 (A)0.5kx (B)5kx 68
圖 3-56 PCG-20-150未洗過的SEM淬斷圖 (A)0.5kx (B)5kx 69
圖 3-57 PCA-20-150未洗過的SEM淬斷圖 (A)0.5kx (B)5kx 70

表目錄
表1-1 比較不同膜過濾系統 5
表2-1 實驗樣品命名表 13
表3-1 膜表面的水接觸角測試 67

參考文獻
1.Chow, C.W.K., WATER ANALYSIS | Potable Water A2 - Worsfold, Paul, in Encyclopedia of Analytical Science (Second Edition), A. Townshend and C. Poole, Editors. 2005, Elsevier: Oxford. p. 253-262.
2.Misdan, N., W.J. Lau, and A.F. Ismail, Seawater Reverse Osmosis (SWRO) desalination by thin-film composite membrane—Current development, challenges and future prospects. Desalination, 2012. 287: p. 228-237.
3.Subramanian, S. and R. Seeram, New directions in nanofiltration applications — Are nanofibers the right materials as membranes in desalination? Desalination, 2013. 308: p. 198-208.
4.Xu, G.-R., J.-N. Wang, and C.-J. Li, Polyamide nanofilm composite membranes (NCMs) supported by chitosan coated electrospun nanofibrous membranes: Preparation and separation performance research. Desalination, 2013. 328: p. 31-41.
5.Gray, N.F., Chapter Thirty-Five - Filtration Methods, in Microbiology of Waterborne Diseases (Second Edition). 2014, Academic Press: London. p. 631-650.
6.Nagy, E., 10 - Nanofiltration, in Basic Equations of the Mass Transport through a Membrane Layer. 2012, Elsevier: Oxford. p. 249-266.
7.Tsai, H.-A., et al., Study on the pervaporation performance and long-term stability of aqueous iso-propanol solution through chitosan/polyacrylonitrile hollow fiber membrane. Journal of Membrane Science, 2008. 309(1–2): p. 146-155.
8.Fathizadeh, M., A. Aroujalian, and A. Raisi, Effect of added NaX nano-zeolite into polyamide as a top thin layer of membrane on water flux and salt rejection in a reverse osmosis process. Journal of Membrane Science, 2011. 375(1–2): p. 88-95.
9.Guo, R., et al., PVA–GPTMS/TEOS hybrid pervaporation membrane for dehydration of ethylene glycol aqueous solution. Journal of Membrane Science, 2006. 281(1–2): p. 454-462.
10.Guo, R., et al., Novel PVA–silica nanocomposite membrane for pervaporative dehydration of ethylene glycol aqueous solution. Polymer, 2007. 48(10): p. 2939-2945.
11.Lalia, B.S., et al., A review on membrane fabrication: Structure, properties and performance relationship. Desalination, 2013. 326: p. 77-95.
12.鄭領英, 膜的高科技應用. 五南圖書出版有限公司, 2003.
13.Nguyen, Q.T., et al., Dry-cast process for synthetic microporous membranes: Physico-chemical analyses through morphological studies. Journal of Membrane Science, 2010. 358(1–2): p. 13-25.
14.Apel, P., Track etching technique in membrane technology. Radiation Measurements, 2001. 34(1–6): p. 559-566.
15.Barma, S. and B. Mandal, Effects of sintering temperature and initial compaction load on alpha-alumina membrane support quality. Ceramics International, 2014. 40(7, Part B): p. 11299-11309.
16.Tabatabaei, S.H., P.J. Carreau, and A. Ajji, Microporous membranes obtained from polypropylene blend films by stretching. Journal of Membrane Science, 2008. 325(2): p. 772-782.
17.Wang, Q., et al., Preparation and properties of polyamide/titania composite nanofiltration membrane by interfacial polymerization. Desalination, 2014. 352: p. 38-44.
18.林志銘, 幾丁聚醣/奈米二氧化矽複合薄膜之製備：改質劑效應. 國立宜蘭大學化學工程與材料工程學系碩士論文, 2012.
19.Roualdes, S., V. Rouessac, and J. Durand, 1.09 - Plasma Membranes, in Comprehensive Membrane Science and Engineering. 2010, Elsevier: Oxford. p. 159-197.
20.Cai, B., H. Ye, and L. Yu, Preparation and separation performance of a dynamically formed MnO2 membrane. Desalination, 2000. 128(3): p. 247-256.
21.Guo, J., et al., Dynamically formed inner skin hollow fiber polydimethylsiloxane/polysulfone composite membrane for alcohol permselective pervaporation. Chemical Engineering Journal, 2010. 158(3): p. 558-565.
22.黃智銘, 幾丁聚醣吸附啤酒中嘌呤之研究. 國立成功大學化學研究所碩士論文, 2002.
23.Wan Ngah, W.S., et al., Comparative study on adsorption and desorption of Cu(II) ions by three types of chitosan–zeolite composites. Chemical Engineering Journal, 2013. 223: p. 231-238.
24.Abou El-Reash, Y.G., A.M. Abdelghany, and A.A. Elrazak, Removal and separation of Cu(II) from aqueous solutions using nano-silver chitosan/polyacrylamide membranes. International Journal of Biological Macromolecules, 2016. 86: p. 789-798.
25.Vieira, R.S., et al., Adsorption and desorption of binary mixtures of copper and mercury ions on natural and crosslinked chitosan membranes. Adsorption, 2007. 13(5-6): p. 603-611.
26.Chen, J., et al., Synthesis and characterization of water-soluble chitosan grafted with hydrophilic aliphatic polyester. International Journal of Biological Macromolecules, 2015. 74: p. 433-438.
27.Desai, K., et al., Nanofibrous chitosan non-wovens for filtration applications. Polymer, 2009. 50(15): p. 3661-3669.
28.Zhang, Y., et al., Fabrication of porous zeolite/chitosan monoliths and their applications for drug release and metal ions adsorption. Carbohydrate Polymers, 2015. 117: p. 657-665.
29.Liu, Y.-L., et al., Chitosan−Silica Complex Membranes from Sulfonic Acid Functionalized Silica Nanoparticles for Pervaporation Dehydration of Ethanol−Water Solutions. Biomacromolecules, 2005. 6(1): p. 368-373.
30.Sun, H., et al., Surface-modified zeolite-filled chitosan membranes for pervaporation dehydration of ethanol. Applied Surface Science, 2008. 254(17): p. 5367-5374.
31.Premakshi, H.G., K. Ramesh, and M.Y. Kariduraganavar, Modification of crosslinked chitosan membrane using NaY zeolite for pervaporation separation of water–isopropanol mixtures. Chemical Engineering Research and Design, 2015. 94: p. 32-43.
32.Shao, L., et al., Graphene oxide cross-linked chitosan nanocomposite membrane. Applied Surface Science, 2013. 280: p. 989-992.
33.Tojima, T., et al., Chitosan beads with pendant α-cyclodextrin: preparation and inclusion property to nitrophenolates. Carbohydrate Polymers, 1999. 40(1): p. 17-22.
34.Spirk, S., et al., Chitosan–silane sol–gel hybrid thin films with controllable layer thickness and morphology. Carbohydrate Polymers, 2013. 93(1): p. 285-290.
35.林怡婷, PAN/chitosan/silica奈米複合膜的製備與應用於奈米過濾程序之探討. 國立宜蘭大學化學工程與材料工程學系碩士論文, 2016.
36.Rasool, N. and T. Yasin, Synthesis of carboxymethyl-chitosan/acrylic acid hydrogel using silane crosslinker. e-Polymers, 2008.
37.陳信吉, 交聯幾丁聚醣薄膜在奈米過濾的應用. 中原大學化學工程學系(所)碩士論文, 2005.
38.Musale, D.A., A. Kumar, and G. Pleizier, Formation and characterization of poly(acrylonitrile)/Chitosan composite ultrafiltration membranes. Journal of Membrane Science, 1999. 154(2): p. 163-173.
39.Klaysom, C., et al., Polyamide/Polyacrylonitrile (PA/PAN) thin film composite osmosis membranes: Film optimization, characterization and performance evaluation. Journal of Membrane Science, 2013. 445: p. 25-33.
40.Marbelia, L., et al., Polyacrylonitrile membranes for microalgae filtration: Influence of porosity, surface charge and microalgae species on membrane fouling. Algal Research, 2016. 19: p. 128-137.
41.蔡依庭, 矽氧烷交聯幾丁聚醣複合薄膜用於水過濾. 國立宜蘭大學化學工程與材料工程學系碩士論文, 2015.
42.張育誠, 吳國光, 焦鴻文, 疏水性材料. 經濟部能源局能源報導－環保新知, 2011: p. 35-37.