臺灣博碩士論文加值系統

本研究係利用紡製之Polyacrylonitrile (PAN)中空纖維膜(hollow fiber membrane)為前驅體(precursor)，以熱處理程序製備熱穩定化(stabilization)PAN中空纖維膜，並應用在滲透蒸發 (pervaporation) 分離操作程序。研究中針對不同熱處理條件所製備之熱穩定化PAN中空纖維膜進行具共沸組成之異丙醇(Isopropanol, IPA)水溶液之分離效能進行探討。研究結果發現，在熱處理溫度60~180℃之間，隨著熱處理溫度之增加透過量下降，透過水濃度增加。當溫度高於180℃時透過量又上升。以120℃熱處理12小時進行90wt%異丙醇水溶液之透過量與透過水濃度分別為186 g/m2h 與 99.2 wt﹪。由SEM觀察發現，經過熱處理後，中空纖維膜結構趨於緻密化且從FT-IR 圖譜分析發現，在熱處理溫度為210℃時， PAN中空纖維膜有除氫和環化反應發生。研究中亦探討進料溫度與進料濃度對異丙醇水溶液之滲透蒸發分離效能之影響。隨著進料溫度之上升透過量增加而透過水濃度下降；進料異丙醇濃度增加時，透過量下降而透過水濃度增加。研究中同時比較熱穩定化PAN中空纖維膜對乙醇水溶液、異丙醇水溶液以及四氟丙醇水溶液之滲透蒸發分離效能，其中以對四氟丙醇水溶液之滲透蒸發分離效能較佳。

In this study, Heat-treated polyacrylonitrile (PAN) hollow fiber membranes were prepared by heat-treating the PAN precursor hollow fiber membrane with different heat-treatment conditions. The influence of heat-treatment conditions on the pervaporation performances of aqueous isopropanol (IPA) solution through heat-treated PAN hollow fiber membranes were investigated. It shows that the permeation rate decreases and the water content in permeate increases with increasing heat-treatment temperature in the range of 60-180 OC. Nevertheless, the permeation rate increases again as the heat-treatment temperature increases. The permeation rate and water content in the permeate for a 90wt% aqueous isopropanol solution through the heat-treated PAN hollow fiber membranes at 120℃ for 12h were 186 g/m2h and 99.2 wt﹪, respectively. The SEMs observation depicts that the morphology of heat-treated PAN hollow fiber membranes were denser with increasing the heat-treatment temperature. As the heat treatment temperature higher than 210oC, dehydrogenation and cyclization reaction of the PAN molecular occurred during the heat-treatment process. Moreover, the inference of feed temperature and feed composition on the pervaporation performance through heat-treated PAN hollow fiber membranes were also investigated. It shows that an increase in the feed isopropanol concentration results in a decrease in the permeation rate and an increase in the separation factor. And the permeation rate increase and the separation factor decrease with increasing the feed solution temperature. The pervaporation performances for 90 wt% ethanol solution, isopropanol solution and tetrafluropropanol solution through heat-treated PAN hollow fiber membranes were also investigated. The tetrafluropropanol solution gave the best separation performance through heat-treated PAN hollow fiber membranes.

第一章 緒 論1
1-1 薄膜分離技術概論1
1-2 中空纖維膜之發展與文獻回顧3
1-3 中空纖維膜之優勢6
1-4 薄膜製備方式6
1-4-1 平板膜之製備6
1-4-1.1 熱誘導式相轉換法6
1-4-1.2 乾式相轉換法7
1-4-1.3 濕式相轉換法7
1-4-1.4 乾/濕式混合製程8
1-4-2 中空纖維膜之製備8
1-4-2.1 熔融紡絲法8
1-4-2.2 乾式紡絲法8
1-4-2.3 濕式紡絲法8
1-4-2.4 乾濕式紡絲法9
1-5 滲透蒸發9
1-6 薄膜之改質方法10
1-6-1 摻合11
1-6-2 接枝12
1-6-3 電漿改質13
1-6-4 熱穩定化改質14
1-7 研究目的16
第二章 實 驗 18
2-1 實驗藥品18
2-2 實驗儀器19
2-3 實驗方法20
2-3-1 鑄膜溶液配置20
2-3-2 PAN中空纖維膜之紡製20
2-3-3 熱穩定化PAN中空纖維膜製備程序21
2-3-4 熱性質分析24
2-3-5 模組之封裝與測試24
2-3-6 中空纖維膜之滲透蒸發測試25
2-3-7 中空纖維膜結構分析27
2-3-7-1 SEM27
2-3-7-2 AFM27
2-3-8 傅氏轉換紅外線光譜儀27
2-3-9 膨潤度測試28
第三章 結果與討論30
3-1 熱處理荷重對熱穩定化PAN中空纖維膜滲透蒸發之影響30
3-2 熱穩定化PAN中空纖維膜之結構型態31
3-3 熱處理溫度對熱穩定化PAN中空纖維膜滲透蒸發之影響31
3-4 熱處理時間對熱穩定化PAN中空纖維膜滲透蒸發之影響34
3-5 進料濃度的影響35
3-6 進料溫度的影響35
3-7 進料物種的影響36
3-8 中空纖維膜分離效能37
第四章 結 論38
第五章 參考文獻63
作者簡介72


































Figure captions
Fig 1-1. Schematic representation of a two-phase system separated by a membrane--------------------------------------------------------------- 2
Fig 1-2 The solution-diffusion model----------------------------------------- 10
Fig 1-3 Schematic of reactions during heat-treatment of PAN up to 400℃------------------------------------------------------------------------- 17
Fig 2-1 Hollow fiber spinning apparatus------------------------------------- 20
Fig 2-2 Different heat treatment temperature process----------------------- 22
Fig 2-3 Different heating rate and hold time--------------------------------- 23
Fig 2-4 The hollow fiber membrane module for pervaporation----------- 25
Fig 2-5 Schematic diagram of pervaporation apparatus-------------------- 26
Fig 2-6 DSC analysis for PAN polymer-------------------------------------- 29
Fig 3-1 Effect of heat-treatment temperature on the cross section morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 41
Fig 3-2 Effect of heat-treatment temperature on the outer edge morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 42
Fig 3-3 Effect of heat-treatment temperature on the inner edge morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 43
Fig 3-4 Effect of heat-treatment temperature on the middle morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 44
Fig 3-5 Effect of heat-treatment temperature on the outer surface morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 45
Fig 3-6 Effect of heat-treatment temperature on the inner surface morphology of PAN hollow fiber membrane. Heat-treatment temperature:(A) No heat-treatment, (B) 60℃, (C) 120℃, (D) 150℃, (E) 180℃, (F) 210℃------------------------------------------ 46
Fig 3-7 (A) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, no annealing-------------------------------------------- 47
Fig 3-7 (B) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 60℃----------------------- 48
Fig 3-7 (C) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 90℃----------------------- 49
Fig 3-7 (D) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 120℃--------------------- 50
Fig 3-7 (E) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 150℃--------------------- 51
Fig 3-7 (F) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 180℃--------------------- 52
Fig 3-7 (G) AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface, annealing temperature at 210℃--------------------- 53
Fig 3-8 Effect of heat treatment on the FTIR analysis of PAN(22wt﹪)/DMF /H2O hollow fiber membrane----------------------------- 54
Fig 3-9 The effect of heat treatment hold time on the pervaporation performance of stabilization PAN hollow fiber-------------------- 56
Fig 3-10 Effect of heat-treatment hold time on the outer surface morphology of PAN hollow fiber membrane(heat-treatment temperature = 120℃). Heat-treatment hold time:(A) No hold time,(B) 6hr,(C) 12hr,(D) 24hr--------------------------------------- 57
Fig 3-11 The effect of feed composition on pervaporation performance of stabilization PAN hollow fiber------------------------------------ 58
Fig 3-12 The effect of feed temperature on pervaporation performance of stabilization PAN hollow fiber------------------------------------ 59


























Table captions
Table 1-1 Membrane processes and the associated driving forces 3
Table 2-1 Process parameters and spinning conditions of wet spinning process…………………………………………………………. 21
Table 3-1 The effect of gravity on the pervaporation performance of stabilization PAN hollow fiber…………………………………. 39
Table 3-2 The effect of heat treatment temperature on the pervaporation performance of stabilization PAN hollow fiber………………... 40
Table 3-3 AFM analysis of PAN(22wt﹪)/DMF/H2O hollow fiber on the outer surface……………………………………………………. 55
Table 3-4 Effect of feed solution on the degree of swelling of stabilization PAN hollow fiber at 25℃………………………… 60
Table 3-5 The effect of feed solution on pervaporation performance of stabilization PAN hollow fiber…………………………………. 61
Table 3-6 Pervaporation performance of hollow fiber membranes………. 62

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