本研究以臭氧化處理方式，將木質素透過氧化反應生成-COOH基，取得水溶性木質素，將此產物稱為臭氧化木質素。利用臭氧化木質素作為改質劑，摻混入聚乙烯醇薄膜中，製備出聚乙烯醇/臭氧化木質素複合薄膜，應用於滲透蒸發分離程序中。
第一部分對木質素進行臭氧改質，取得水溶性臭氧化木質素，產物以X-光光電子能譜儀(XPS)和傅立葉轉換紅外光譜儀(FTIR)進行分析，確認木質素被氧化而生成羧基，與原來木質素具有的磺酸基共同作用，使此木質素具有水溶性。
第二部分將製備完成的聚乙烯醇/臭氧化木質素複合薄膜應用於3.5 %氯化鈉水溶液的滲透蒸發脫鹽程序中。首先探討不同臭氧化木質素摻混比例對滲透蒸發脫鹽的影響，得到當臭氧化木質素的摻混比例為50 wt%時(CR-PVA/OZEL(50/50))，複合薄膜具有最佳的滲透蒸發效率。在0.4-0.5 torr、25 ℃的操作條件下，當選擇層厚度為0.53奈米時，記錄到的通透量為14.5 kg/m^2 h，去鹽率達到99.92 %。以此複合薄膜進行不同操作溫度(25-80 ℃)、不同進料濃度(3.5 wt%-15 wt%之氯化鈉溶液)及人工海水脫鹽測試。除了在80 ℃下水通量可達到74.1 kg/m2 h、去鹽率仍維持99.99 %以上之外，此薄膜對高濃度的水溶液進料，也有相當的穩定性以及良好的脫鹽分離效率。
第三部分改變CR-PVA/OZEL(50/50)複合薄膜的交聯劑，以4-sulfophthalic acid (SPTA)取代馬來酸酐做為交聯劑，發現在高溫進料的操作下，可使薄膜的水通量大幅提升1.4-1.5倍，證明含有磺酸根之交聯劑能有效提升水在薄膜間的擴散速率，進而提高薄膜在滲透蒸發脫鹽程序中的水通量。

This study adopted an ozone oxidation treatment method to convert lignin into water-soluble lignin by generating -COOH groups through oxidation reactions. The resulting product is referred to as ozone-oxidized lignin. By using ozone-oxidized lignin as a modifier, it is blended into polyvinyl alcohol (PVA) films to prepare PVA/ozone-oxidized lignin composite films for application in pervaporation desalination processes.

In the first part, lignin is subjected to ozone modification. Water-soluble ozone-oxidized lignin is obtained, and the product is analyzed using X-ray photoelectron spectroscopy (XPS) and Fourier transform infrared spectroscopy (FTIR) to confirm the oxidation of lignin and the formation of carboxyl groups. These carboxyl groups interact with the sulfonic acid groups present in the original lignin, imparting water solubility to the modified lignin.

In the second part, the prepared PVA/ozone-oxidized lignin composite films are applied in the pervaporation desalination process using a 3.5% sodium chloride aqueous solution. The influence of different ratios of ozone-oxidized lignin blending on the pervaporation desalination is investigated. It is found that the composite film with a 50 wt% blending ratio of ozone-oxidized lignin (CR-PVA/OZEL(50/50)) exhibits the optimal pervaporation efficiency. Under the operating conditions of 0.4-0.5 torr and 25 ℃, with a selected film thickness of 0.53 nanometers, a permeate flux of 14.5 kg/m2h is recorded, and the salt rejection rate reaches 99.92%. The composite film is tested for desalination using different operating temperatures (25-80 ℃), feed concentrations (3.5 wt%-15 wt% sodium chloride solution), and artificial seawater. Besides achieving a water flux of 74.1 kg/h-m2 and a salt rejection rate exceeding 99.99% at 80 ℃, the film also demonstrates good stability and desalination separation efficiency for high-concentration feed solutions.

In the third part, the crosslinking agent of the CR-PVA/OZEL(50/50) composite film is changed. 4-sulfophthalic acid (SPTA) is used as a replacement for maleic anhydride as the crosslinking agent. It is found that under high-temperature feed operation, the water flux of the film can be significantly increased by 1.4-1.5 times. This demonstrates that crosslinking agents containing sulfonic acid groups can effectively enhance water diffusion rates within the film

摘要 I
Abstract III
總目錄 V
圖目錄 VIII
表目錄 XII
第一章、 緒論 1
1-1前言 1
1-2現今的海水淡化技術 2
1-3滲透蒸發分離程序(Pervaporation) 8
1-3-1原理 8
1-3-2滲透蒸發分離程序之薄膜與分離機制 10
1-3-3滲透蒸發分離程序中常見的高分子材料 14
1-4以PVA高分子製備薄膜 17
1-4-1PVA性質 17
1-4-2改良PVA高分子薄膜 18
1-5研究動機 21
第二章、文獻回顧 22
2-1前言 22
2-2滲透蒸發分離程序 23
2-3以高分子製備薄膜應用於滲透蒸發分離程序 24
2-3-1前言 24
2-3-2滲透蒸發脫鹽程序 25
2-4 PAN基材改質 30
2-5木質素 33
2-5-1木質素的改質 36
2-5-2木質素於薄膜分離之應用 38
2-6研究方法 40
第三章、實驗 42
3-1實驗藥品 42
3-2實驗儀器 44
3-3滲透蒸發脫鹽程序實驗步驟 47
3-4以臭氧氧化的方式來改質木質素 49
3-5以改質木質素為主體與聚乙烯醇高分子之複合薄膜製備 51
第四章、結果與分析 52
4-1水溶性木質素製備 52
4-2改質木質素結構及性質分析 54
4-3複合薄膜之性質研究 60
4-3-1不同改質木質素摻混比例的塊材之交聯度測試 60
4-3-2不同改質木質素摻混比例的塊材之吸水測試 61
4-3-3不同複合薄膜表面之接觸角測試 62
4-3-4分析不同改質木質素摻混比例的塊材之分子間結構 64
4-3-5分析不同改質木質素摻混比例的塊材對水之擴散速率 67
4-4複合薄膜應用於滲透蒸發程序 68
4-4-1不同改良木質素摻混比例之複合薄膜滲透蒸發脫鹽程序測試 68
4-4-2不同進料操作溫度之複合薄膜滲透蒸發脫鹽程序測試 71
4-4-3不同進料濃度之複合薄膜滲透蒸發脫鹽程序測試 75
4-4-4人工海水之複合薄膜滲透蒸發脫鹽程序測試 77
4-4-5比較不同複合薄膜的滲透蒸發脫鹽程序測試 78
4-4-6本實驗與其他研究之薄膜於滲透蒸發脫鹽程序表現之比較 80
第五章、結論 82
第六章、參考文獻 84

1. The United Nations World Water Development Report 2019: leaving no one behind. 2019; Available from: https://en.unesco.org/themes/water-security/wwap/wwdr/2019
2. IDA Water Security Handbook, 2019 – 2020 and GWI DesalData. 2020; Available from: https://idadesal.org/
3. Betsy Otto and Leah Schleifer, Domestic Water Use Grew 600% Over the Past 50 Years. 2020; Available from: https://www.wri.org/blog/2020/02/growth-domestic-water-use
4. Khawaji, A. D.; Kutubkhanah, I. K.; Wie, J.-M. Advances in seawater desalination technologies. Desalination 2008, 221, 47-69.
5. Castro-Muñoz, R. Breakthroughs on tailoring pervaporation membranes for water desalination: A review. Water Research 2020, 187, 116428.
6. Raluy, G.; Serra, L.; Uche, J. Life cycle assessment of MSF, MED and RO desalination technologies. Energy 2006, 31, 2361-2372.
7. 薄膜分離技術於廢水處理之應用概述; Available from: https://www.ftis.org.tw/cpe/download/she/issue23/subject23-2.htm
8. Cadotte, J. E.; Petersen, R. J.; Larson, R. E.; Erickson, E. E. A new thin-film composite seawater reverse osmosis membrane. Desalination 1980, 32, 25-31.
9. Subramani, A.; Jacangelo, J. G. Emerging desalination technologies for water treatment: a critical review. Water Research 2015, 75, 164-87.
10. Skuse, C.; Gallego-Schmid, A.; Azapagic, A.; Gorgojo, P. Can emerging membrane-based desalination technologies replace reverse osmosis? Desalination 2021, 500, 114844.
11. McCutcheon, J. R.; Elimelech, M. Influence of concentrative and dilutive internal concentration polarization on flux behavior in forward osmosis. Journal of Membrane Science 2006, 284, 237-247.
12. Rezaei, M.; Alsaati, A.; Warsinger, D. M.; Hell, F. Samhaber, W. M. Long-Running Comparison of Feed-Water Scaling in Membrane Distillation. Membranes (Basel) 2020, 10(8), 173.
13. Biesheuvel, P.M.; van der Wal, A. Membrane capacitive deionization. Journal of Membrane Science 2010, 346, 256-262.
14. Xia, L. L.; Li, C. L.; Wang, Y. In-situ crosslinked PVA/organosilica hybrid membranes for pervaporation separations. Journal of Membrane Science 2016, 498, 263–275.
15. Chang, P.-Y.; Wang, J.; Li, S.-Y.; Suen, S.-Y. Biodegradable Polymeric Membranes for Organic Solvent/Water Pervaporation Applications. Membranes (Basel) 2021, 11(12), 970.
16. Kober, P. A. PERVAPORRATION, PERSTILLATION AND PERCRYSTALLIZATION. Journal of the American Chemical Society 1917, 39(5), 944-948.
17. Shao, P.; Huang, R.Y. M. Polymeric membrane pervaporation. Journal of Membrane Science 2007, 287 (2), 162-179.
18. Chapmana, P. D.; Oliveira, T.; Livingstona, A. G.; Li, K. Membranes for the dehydration of solvents by pervaporation. Journal of Membrane Science 2008, 318 (1), 5-37.
19. Prihatiningtyas, I.; Bruggen, B. V. d. Nanocomposite pervaporation membrane for desalination. Chemical Engineering Research and Design 2020, 164, 147-161.
20. Pinnau, I.; Freeman, B. D. (2000) Membrane Formation and Modification, American: American Chemical Society
21. Baker, R.W. (2004) Membrane Technology and Applications. 2nd Edition, Hoboken: John Wiley & Sons.
22. Zhang, S.; Drioli, E. Pervaporation membranes. Separation Science and Technology 1995, 30(1), 1-31.
23. Castro-Muñoz, R. Breakthroughs on tailoring pervaporation membranes for water desalination: A review. Water Research 2020, 187, 116428.
24. Liu, G.; Jin, W. Pervaporation membrane materials: Recent trends and perspectives. Journal of Membrane Science 2021, 636, 119557.
25. Rezakazemi, M.; Marjani, A.; Shirazian, S. Organic solvent removal by pervaporation membrane technology: experimental and simulation. Environmental Science and Pollution Research 2018, 25, 19818–19825.
26. Karimi, H.; Bajestani, M. B.; Mousavi, S. A.; Garakani, R. M. Polyamide membrane surface and bulk modification using humid environment as a new heat curing medium. Journal of Membrane Science 2017, 523, 129-137.
27. Hirai, S.; Phanthong, P.; Wakabayashi, T.; Yao, S. Fabrication of Porous Polyimide Membrane with Through-Hole via Multiple Solvent Displacement Method. ChemistryOpen 2021, 10(3), 352-359.
28. Sapalidis, A.A. Porous Polyvinyl Alcohol Membranes: Preparation Methods and Applications. Symmetry 2020, 12(6), 960.
29. Chiellini, E.; Corti, A.; D'Antone, S.; Solaro, R. Biodegradation of poly (vinyl alcohol) based materials. Progress in Polymer Science 2003, 28, 963-1014,
30. Rynkowska, E.; Fatyeyeva, K.; Marais, S.; Kujawa, J.; Kujawski, W. Chemically and Thermally Crosslinked PVA-Based Membranes: Effect on Swelling and Transport Behavior. Polymers (Basel) 2019, 11(11), 1799.
31. Sau S.; Pandit S.; Kundu S. Crosslinked poly (vinyl alcohol): Structural, optical and mechanical properties. Surfaces and Interfaces 2021, 25, 101198.
32. Dmitrenko, M.; Penkova, A.; Kuzminova, A.; Missyul, A.; Ermakov, S.; Roizard, D. Development and Characterization of New Pervaporation PVA Membranes for the Dehydration Using Bulk and Surface Modifications. Polymers 2018, 10(6), 571.
33. Saqib, J.; Aljundi, I. H. Membrane fouling and modification using surface treatment and layer-by-layer assembly of polyelectrolytes: state-of-the-art review. Journal of Water Process Engineering 2016, 11, 68–87.
34. Amnuaypanich, S.; Patthana, J.; Phinyocheep, P. Mixed matrix membranes prepared from natural rubber/poly(vinyl alcohol) semi-interpenetrating polymer network (NR/PVA semi-IPN) incorporating with zeolite 4A for the pervaporation dehydration of water-ethanol mixtures. Chemical Engineering Science 2009, 64, 4908–4918.
35. Toti, U. S.; Aminabhavi, T. M. Different viscosity grade sodium alginate and modified sodium alginate membranes in pervaporation separation of water + acetic acid and water + isopropanol mixtures. Journal of Membrane Science 2004, 228, 199-208.
36. Wang, X.-P. Modified alginate composite membranes for the dehydration of acetic acid. Journal of Membrane Science 2000, 170, 71.
37. Zhang, W.; Ying, Y.; Ma, J.; Guo, X.; Huang, H,.; Liu, D.; Zhong, C. Mixed matrix membranes incorporated with polydopamine-coated metal-organic framework for dehydration of ethylene glycol by pervaporation. Journal of Membrane Science 2017, 527, 8-17.
38. Tseng, C.; Liu, Y.-L. Creation of water-permeation pathways with matrix-polymer functionalized carbon nanotubes in polymeric membranes for pervaporation desalination. Journal of Membrane Science 2022, 2, 2.
39. Castro-Mu ̃noz, R.; Buera-Gonz ́alez, J.; Iglesia, ́O. d. l.; Galiano, F.; Fíla, V.; Malankowska, M.; Rubio, C.; Figoli, A.; T ́ellez, C.; Coronas, J. Towards the dehydration of ethanol using pervaporation cross-linked poly(vinyl alcohol)/graphene oxide membranes. Journal of Membrane Science 2019, 582, 423-434.
40. Bai, L.; Qu, P.; Li, S.; Gao, Y.; Zhang, L. Poly(vinyl Alcohol)/ Cellulose Nanocomposite Pervaporation Membranes for Ethanol Dehydration. Materials Science Forum 2011, 675-677, 383-386.
41. Li, B.-B.; Xu, Z.-L.; Qusay, F. A.; Li, R. Chitosan-poly (vinyl alcohol)/poly (acrylonitrile) (CS–PVA/PAN) composite pervaporation membranes for the separation of ethanol–water solutions. Desalination 2006, 193 (1-3), 171-181.
42. Wijaya, S.; Duke, M. C.; Johan, C. Carbonised template silica membranes for desalination. Desalination 2009, 236(1), 291-298.
43. Liang, B.; Pan, K.; Li, L.; Giannelis, E.P.; Cao, B. High performance hydrophilic pervaporation composite membranes for water desalination. Desalination 2014, 347, 199-206.
44. Chaudhri, S. G.; Rajai, B. H.; Singh, P. S. Preparation of ultra-thin poly(vinyl alcohol) membranes supported on polysulfone hollow fiber and their application for production of pure water from seawater. Desalination 2015, 367, 272-284.
45. Zhang, R.; Liang, B.; Qu, T.; Cao, B.; Li, P. High-performance sulfosuccinic acid cross-linked PVA composite pervaporation membrane for desalination. Environmental Technology 2019, 40, 312-320.
46. Liang, B.; Li, Q.; Cao, B.; Li, P. Water permeance, permeability and desalination properties of the sulfonic acid functionalized composite pervaporation membranes. Desalination 2018, 433, 132-140.
47. Cheng, C.; Shen, L.; Yu, X. F.; Yang, Y.; Li, X.; Wang, X. Robust construction of a graphene oxide barrier layer on a nanofibrous substrate assisted by the flexible poly(vinylalcohol) for efficient pervaporation desalination. Journal of Materials Chemistry A 2017, 5, 3558-3568.
48. Sun, J.; Qian, X.; Wang, Z.; Zeng, F.; Bai, H.; Li, N. Tailoring the microstructure of poly(vinyl alcohol)-intercalated graphene oxide membranes for enhanced desalination performance of high-salinity water by pervaporation. Journal of Membrane Science 2020, 599, 117838.
49. Toutianoush, A.; Tieke, B. Pervaporation separation of alcohol/water mixtures using self-assembled polyelectrolyte multilayer membranes of high charge density. Materials Science and Engineering: C 2002, 22, 459-463.
50. Zhao, Z.-P.; Li, J.; Wang, D.; Chen, C.-X. Nanofiltration membrane prepared from polyacrylonitrile ultrafiltration membrane by low-temperature plasma: 4. Grafting of N-vinylpyrrolidone in aqueous solution. Desalination 2005, 184, 37-44.
51. Zhao, Z.-P.; Li, J.; Zhang, D.; Chen, C.-X. Nanofiltration membrane prepared from polyacrylonitrile ultrafiltration membrane by low-temperature, plasma I. Graf of acrylic acid in gas. Journal of Membrane Science 2004, 232, 1-8.
52. Ulbricht, M.; Oechel, A.; Lehmann, C.; Tomaschewski, G.; Hicke, H.-G. Gas-phase photoinduced graft polymerization of acrylic acid onto polyacrylonitrile ultrafiltration membranes. Journal of Applied Polymer Science 1995, 55, 1707-1723.
53. Zhang, G.; Yan, H.; Ji, S.; Liu, Z. Self-assembly of polyelectrolyte multilayer pervaporation membranes by a dynamic layer-by-layer technique on a hydrolyzed polyacrylonitrile ultrafiltration membrane. Journal of Membrane Science 2007, 292, 1-8.
54. Zhang, G.; Gao, X.; Ji, S.; Liu, Z. Electric field enhanced assembly of polyelectrolyte composite membranes. Journal of Membrane Science 2008, 307, 151-155.
55. Wang, X.-P.; Li, N.; Wang, W.-Z. Pervaporation properties of novel alginate composite membranes for dehydration of organic solvents. Journal of Membrane Science 2001, 193, 85-95.
56. Zhang, G.; Meng, H.; Ji, S. Hydrolysis differences of polyacrylonitrile support membrane and its influences on polyacrylonitrile-based membrane performance. Desalination 2009, 242 (1-3), 313-324.
57. Austria, H. F. M.; Lecaros, R. L. G.; Hung W.-S.; Tayo, L. L.; Hu, C.-C.; Tsai, H.-A.; Lee, K.-R.; Lai, J.-Y. Investigation of salt penetration mechanism in hydrolyzed polyacrylonitrile asymmetric membranes for pervaporation desalination. Desalination 2019, 463, 32-39.
58. Glasser, W. G.; Northey, R. A.; Schultz T. P. (1999) Lignin: Historical, Biological, and Materials Perspectives, American: American Chemical Society
59. Wang, J.; John Manley, R. St.; Feldman, D. Synthetic polymer-lignin copolymers and blends. Progress in Polymer Science 1992, 17, 611-646.
60. Calvo-Flores, F. G.; Dobado, J. A.; Isac-García, J.; Martín- Martínez, F. J. (2015) Lignin and lignans as renewable raw materials: chemistry, technology, and applications. Hoboken: John Wiley & Sons.
61. Haq, I.; Mazumder, P.; Kalamdhad, A. S. Recent advances in removal of lignin from paper industry wastewater and its industrial applications – A review. Bioresource Technology 2020, 312, 123636.
62. Laurichesse, S.; Avérous, L. Chemical modification of lignins: Towards biobased polymers. Progress in Polymer Science 2014, 39, 1266-1290.
63. Niaounakis, M. (2015) Biopolymers: Applications and Trends. American: William Andrew
64. Aïtcin, P.-C.; Flatt, R. J (2016) Science and Technology of Concrete Admixtures. England: Woodhead Publishing.
65. Figueiredo, P.; Lintinen, K.; Hirvonen, J. T.; Kostiainen, M.; Santos, H. A. Properties and chemical modifications of lignin: Towards lignin-based nanomaterials for biomedical applications. Progress in Materials Science 2018, 93, 233-269.
66. Mvula, E.; Naumov, S.; Sonntag, C. v. Ozonolysis of Lignin Models in Aqueous Solution: Anisole, 1,2-Dimethoxybenzene, 1,4-Dimethoxybenzene, and 1,3,5-Trimethoxybenzene. Environmental Science & Technology 2009, 43, 16, 6275-6282.
67. Shi, C.; Zhang, S.; Wang, W.; Linhardt, R. J.; Ragauskas, A. J. Preparation of Highly Reactive Lignin by Ozone Oxidation: Application as Surfactants with Antioxidant and Anti-UV Properties. ACS Sustainable Chemistry & Engineering 2020, 8, 22-28.
68. Chen, Y.-T. Liao, Y.-L.; Sun, Y.-M.; Hu, C.-C.; Lai, J.-Y.; Liu, Y.-L. Lignin as an effective agent for increasing the separation performance of crosslinked polybenzenoxazine based membranes in pervaporation dehydration application. Journal of Membrane Science 2019, 578, 156-162.
69. Chen, Y.-T.; Sun, Y.-M.; Hu, C.-C.; Lai, J.-Y.; Liu, Y.-L. Employing lignin in the formation of the selective layer of thin-film composite membranes for pervaporation desalination. Materials Advances 2021, 2, 3099-3106.
70. Ralph, J.; Lapierre, C.; Boerjan, W. Lignin structure and its engineering. Current Opinion in Biotechnology 2019, 56, 240-249
71. Li, H.; Pang, Z.; Gao, P.; Wang, L. Fe(III)-catalyzed grafting copolymerization of lignin with styrene and methyl methacrylate through AGET ATRP using triphenyl phosphine as ligand. RSC Advances 2015, 5, 54387-54394.
72. 郭明智(2018)。全組成分離木質素產品應用開發。行政院原子能委員會委託研究計畫研究報告(編號: NL1070400)，未出版。
73. Colthup, N. B. Spectra-Structure Correlations in the Infra-Red Region. Journal of the Optical Society of America 1950, 40, 397-400.
74. Yang, G.; Xie, Z.; Cran, M.; Ng, D.; Gray, S. Enhanced desalination performance of poly (vinyl alcohol)/carbon nanotube composite pervaporation membranes via interfacial engineering. Journal of Membrane Science 2019, 579, 40-51.
75. Tseng, C.; Liu, Y.-L. Poly(vinyl alcohol)/carbon nanotube (CNT) membranes for pervaporation dehydration: The effect of functionalization agents for CNT on pervaporation performance. Journal of Membrane Science 2023, 668, 121185.
76. Chen, H. L.; Wu, L.G.; Tan, J.; Zhu, C. L. PVA membrane filled β-cyclodextrin for separation of isomeric xylenes by pervaporation. Chemical Engineering Journal 2000, 78, 159-164.
77. Zhang, R.; Xu, X.; Cao, B.; Li, P. Fabrication of high-performance PVA/PAN composite pervaporation membranes crosslinked by PMDA for wastewater desalination. Petroleum Science 2018, 15, 146-156.
78. Xue, Y. L.; Huang, J.; Lau, C. H.; Cao, B.; Li, P. Tailoring the molecular structure of crosslinked polymers for pervaporation desalination. Nature Communications 2020, 11, 1461.
79. Cheng, C.; L. Shen, D.; Yu, X.; Yang, Y.; Wang, X. Robust construction of a graphene oxide barrier layer on a nanofibrous substrate assisted by the flexible poly(vinylalcohol) for efficient pervaporation desalination. Journal of Materials Chemistry A 2017, 5, 3558-3568.
80. Xing, Y.; Xue, Y.; Qin, D.; Zhao, P.; Li, P. Microwave-induced ultrafast crosslinking of Poly (vinyl alcohol) blended with nanoparticles as wave absorber for pervaporation desalination. Journal of Membrane Science Letters 2022, 2, 100021.