臺灣博碩士論文加值系統

本研究以聚偏二氟乙烯(poly(vinylidene fluoride), PVDF)與分子篩混成富氧膜膜材，並使用親水支撐層合成一平板偏親-疏水複合薄膜，應用於富集氧氣之功用，探討添加不同比例的5A與13X分子篩對氣體分子之吸附作用，並分別選用磷酸三乙酯(TEP)與N-甲基吡咯烷酮(NMP)作為溶劑以製備薄膜，探討製膜條件對氣體分離的性能與其薄膜內部結構對氣體滲透性的影響，進而找出最適化製備薄膜的條件與最適化氣體滲透於薄膜之操作，以適用於富氧膜之應用。

富氧膜的製備條件為選用不同分子篩與溶劑製備複合薄膜，分析不同製膜條件對薄膜微結構、晶相成分、熱穩定性、孔徑大小、機械強度之影響。
在實驗操作部分，氣體分離的驅動力為壓力差，以透膜壓力作為操作變因，並以掃流方式操作平板式模組，比較薄膜對氧氣和氮氣的滲透通量、O2/N2的選擇率，再以人工合成空氣測試氣體分離之性能，以探討薄膜之富集氧氣功用，並比較薄膜之富氧濃度。

研究結果顯示，在透膜壓差為1kg/cm2時，以純氮、氧氣體進行滲透實驗，以TEP作為溶劑並添加50wt%的5A分子篩複合薄膜，可得最佳的O2/N2選擇率為5.079，而人工合成空氣測試氮氧分離的實驗，可知以TEP作為溶劑並添加50wt%的5A分子篩複合薄膜，能達到最佳富氧濃度為25.7%。

A study of manufacturing oxygen enrichment membrane using Polyvinylidene Fluoride hybrid with molecular sieve, and a hydrophilic support layer was used to synthesize a flat hydrophilic-hydrophobic composite film for oxygen enrichment. The gas molecules were adsorbed by different ratios of 5A and 13X molecular sieves, and triethyl orthophosphate (TEP) and NMP were used as solvents to prepare thin films. The influence of the internal structure of the film on the gas permeability, and the properties of gas separation were investigated. Further, the optimum conditions for the preparation of the membrane and the optimized gas permeation operation are found, and it is suitable for the application of the oxygen enrichment membrane.
The oxygen-enriched membrane were prepared by different molecular sieves and solvents, and the effects of different prepared conditions on the microstructure, crystalline phase composition, thermal stability, pore size, and mechanical strength of the membrane were also investigated.
In the gas permeation experiments, the transmembrane pressure was used as the operating factor to compare the permeation flux of oxygen and nitrogen and the O2/N2 selectivity. Using synthetic air as the feed gas, the membranes were used for air separation, and the oxygen enrich performance were tested.
The results showed that using pure nitrogen and oxygen gas as the feed gas, when the transmembrane pressure difference was 1 kg/cm2, using TEP as the solvent and adding 50wt% 5A molecular sieve composite film, the best O2/N2 selectivity is 5.079.
Using synthetic air as feed and the oxygen enrich experiments showed that, using TEP as a solvent and adding 50 wt% 5A molecular sieve composite film can achieve an optimal oxygen concentration of 25.7%.

目錄
中文摘要 I
英文摘要 II
目錄 IV
圖目錄 VIII
表目錄 XII
第一章 緒論 1
1.1 前言 1
1.2 薄膜分離程序 2
1.3 薄膜之氣體分離應用 5
1.4 研究動機與目的 7
第二章 文獻回顧 8
2.1 氧氮氣體分離機制 8
2.2 氣體分離膜之用途 10
2.3 富氧膜製備 11
2.3.1 分子篩之種類 11
2.3.2 製膜液之溶劑選用 12
2.3.3 薄膜製備之方法 12
2.4 薄膜之孔隙結構及性質 13
2.5 影響氣體滲透通量之因素 14
2.6 高分子成膜機制 14
第三章 實驗裝置與方法 15
3.1 實驗裝置設計 15
3.2 實驗藥品與設備 21
3.2.1 實驗藥品與材料 21
3.2.2 實驗設備 22
3.3 薄膜編號與製膜參數 25
3.4 薄膜製備方法 28
3.4.1 薄膜製膜液的配製 28
3.4.2 薄膜鑄膜方法 29
3.5 薄膜性質分析 31
3.5.1 薄膜性質分析儀器 31
3.5.2 薄膜的形態觀察和表面孔洞分析 32
3.5.3 薄膜材料晶體結構特性 32
3.5.4 薄膜表面孔徑與膜厚量測 33
3.5.5 接觸角量測 34
3.5.6 薄膜熱穩定性測試 34
3.5.7 薄膜機械強度測試 34
3.6 氣體分離操作條件 35
3.7 掃流式氣體分離實驗流程 35
3.7.1 合成空氣氣體分離實驗步驟 35
3.7.2 純氮、純氧氣體分離實驗步驟 36
3.8 實驗分析方法 38
3.8.1 富氧濃度分析 38
3.8.2 氣體滲透通量規一化之計算 38
3.8.3 氣體滲透性之計算 38
3.8.4 氣體選擇率 39
第四章 結果與討論 40
4.1 製備富氧膜之分子篩選用分析 40
4.2 薄膜微結構分析 42
4.2.1 薄膜表面型態分析 42
4.2.2 薄膜橫截面型態分析 51
4.3 薄膜特性分析 58
4.3.1 薄膜鑄膜於支撐層之表面改質分析 58
4.3.2 薄膜晶體結構分析 60
4.3.3 薄膜之熱穩定性分析 69
4.3.4 薄膜之膜厚與孔徑分析 78
4.3.5 薄膜之接觸角 80
4.3.6 薄膜機械強度測試 81
4.4 富氧膜應用於純氮氧氣體分離分析 83
4.4.1 透膜壓力對純氮氧氣體之滲透通量影響 83
4.4.2 溶劑與分子篩選用對氧氮氣體之選擇率分析 89
4.5 富氧膜應用於合成空氣氣體分離分析 93
4.5.1 測試合成空氣之氮氧分離 93
4.5.2 選用分子篩對滲透側之富氧性能影響 97
4.6 富氧膜與文獻比較 99
4.6.1 富氧膜製備文獻比較 99
4.6.2 Robeson upper bound文獻探討 101
第五章 結論 102
符號說明 104
參考文獻 105


 
圖目錄
圖1-1 薄膜分離程序之性質比較 4
圖1-2 分子篩複合富氧薄膜 6
圖3-1 平板式薄膜模組示意圖 15
圖3-2 模組設計示意圖(進料側) 16
圖3-3模組設計示意圖(滲透側) 17
圖3-4 薄膜氣體滲透與富氧濃度之實驗裝置 19
圖3-5薄膜純氮純氧氣體滲透之實驗裝置 20
圖3-5親水支撐層之SEM結構圖 30
圖3-6 親水支撐層示意圖 30
圖4-1 無添加分子篩之TEP薄膜上表面 44
圖4-2 無添加分子篩之NMP薄膜上表面 44
圖4-3 添加5A分子篩之TEP上表面圖 47
圖4-4 添加13X分子篩之TEP上表面圖 48
圖4-5 添加5A分子篩之NMP上表面圖 49
圖4-6 添加13X分子篩之NMP上表面圖 50
圖4-7 無添加分子篩之TEP薄膜橫截面 52
圖4-8 無添加分子篩之NMP薄膜橫截面圖 52
圖4-9 添加5A分子篩之TEP橫截面圖 54
圖4-10 添加13X分子篩之TEP橫截面圖 55
圖4-11 添加5A分子篩之NMP橫截面圖 56
圖4-12 添加13X分子篩之NMP橫截面圖 57
圖4-13 比較三種PVDF結晶相之XRD 61
圖4-14製備無添加分子篩之PVDF薄膜XRD 62
圖4-15 純5A分子篩之XRD 63
圖4-16 以TEP作為溶劑並添加不同比例5A分子篩之薄膜XRD 64
圖4-17 以NMP作為溶劑並添加不同比例5A分子篩之薄膜XRD 65
圖4-18 純13X分子篩之XRD 66
圖4-19 以TEP作為溶劑並添加不同比例13X分子篩之薄膜XRD 67
圖4-20 以NMP作為溶劑並添加不同比例13X分子篩之薄膜XRD 68
圖4-21 TEP之添加10wt%不同種類分子篩之熱重分析圖 72
圖4-22 TEP之添加10wt%不同種類分子篩之熱重一次微分圖 72
圖4-23 TEP之添加30wt%不同種類分子篩之熱重分析圖 73
圖4-24 TEP之添加30wt%不同種類分子篩之熱重一次微分圖 73
圖4-25 TEP之添加50wt%不同種類分子篩之熱重分析圖 74
圖4-26 TEP之添加50wt%不同種類分子篩之熱重一次微分圖 74
圖4-27 NMP之添加10wt%不同種類分子篩之熱重分析圖 75
圖4-28 NMP之添加10wt%不同種類分子篩之熱重一次微分圖 75
圖4-29 NMP之添加30wt%不同種類分子篩之熱重分析圖 76
圖4-30 NMP之添加30wt%不同種類分子篩之熱重一次微分圖 76
圖4-31 NMP之添加50wt%不同種類分子篩之熱重分析圖 77
圖4-32 NMP之添加50wt%不同種類分子篩之熱重一次微分圖 77
圖4-33 薄膜之孔徑分析圖 78
圖4-34薄膜之接觸角比較 80
圖4-35 透膜壓力對TEP之不同比例5A分子篩薄膜之O2滲透通量 85
圖4-36 透膜壓力對TEP之不同比例5A分子篩薄膜之N2滲透通量 85
圖4-37 透膜壓力對TEP之不同比例13X分子篩薄膜之O2滲透通量 86
圖4-38 透膜壓力對TEP之不同比例13X分子篩薄膜之N2滲透通量 86
圖4-39 透膜壓力對NMP之不同比例5A分子篩薄膜之O2滲透通量 87
圖4-40 透膜壓力對NMP之不同比例5A分子篩薄膜之N2滲透通量 87
圖4-41 透膜壓力對NMP之不同比例13X分子篩薄膜之O2滲透通量 88
圖4-42 透膜壓力對NMP之不同比例13X分子篩薄膜之N2滲透通量 88
圖4-43 透膜壓力對TEP之不同比例5A分子篩薄膜之O2/N2選擇率 90
圖4-44 透膜壓力對TEP之不同比例13X分子篩薄膜之O2/N2選擇率 90
圖4-45 透膜壓力對NMP之不同比例5A分子篩薄膜之O2/N2選擇率 92
圖4-46 透膜壓力對NMP之不同比例13X分子篩薄膜之O2/N2選擇率 92
圖4-47 TEP添加不同比例的5A分子篩薄膜之富氧濃度與時間關係 95
圖4-48 TEP添加不同比例的13X分子篩薄膜之富氧濃度與時間關係 95
圖4-49 NMP添加不同比例的5A分子篩薄膜之富氧濃度與時間關係 96
圖4-50 TEP添加不同比例的13X分子篩薄膜之富氧濃度與時間關係 96
圖4-51 不同比例分子篩複合薄膜在滲透側之富氧濃度 98
圖4-52 不同比例分子篩複合薄膜在純氮氧氣體滲透下之O2/N2選擇率 98
圖4-53 氧氣與氮氣分離之Robeson upper bound 文獻比較 101

表目錄
表1-1 不同操作程序之驅動力分類 3
表1-2 不同氣體對天然橡膠之溶解度 4
表2-1 不同氣體之物理性質與動力學直徑 9
表2-2 選用分子篩之種類 11
表2-3 一般製膜溶劑之毒性性質 12
表3-1 製膜液組成(一) 26
表3-2 製膜液組成(二) 26
表3-3 製膜液組成(三) 27
表3-4 製膜液組成(四) 27
表3-5 製膜液製備條件 28
表3-6 親水支撐層性質說明 29
表4-1 表面改質之滲透通量影響 59
表4-2 以TEP溶劑配製薄膜之裂解溫度 71
表4-3 以NMP溶劑配製薄膜之裂解溫度 71
表4-4 以TEP為溶劑之薄膜物性分析 79
表4-5 以NMP為溶劑之薄膜物性分析 79
表4-6 以TEP為溶劑之薄膜機械強度分析 81
表4-7 以NMP為溶劑之薄膜機械強度分析 82
表4-8 富氧膜之文獻比較 100

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