本研究以濕式相轉換法製備薄膜，應用於薄膜蒸餾中，並以聚偏二氟乙烯(PVDF)和聚甲基丙烯酸甲酯(PMMA)作為膜材，二甲基亞碸(DMSO)為溶劑，探討添加不同PMMA含量(3.6 wt%、7.2 wt%、10.8 wt%、14.4 wt%)對於薄膜結構、平均孔徑、接觸角等影響。
在薄膜蒸餾中，探討不同參數對薄膜蒸餾之滲透通量以及鹽阻隔率之影響，將以AGMD與WGMD在不同進料溫度(50、60、70℃)、流速(0.4、0.6、0.8 L/min)與間隙高度(0、1、3 mm)進行性能探討，以及對薄膜進行回復性和耐久性測試，最後將WGMD和DCMD進行滲透通量以及產出比率(GOR)比較，探討不同薄膜蒸餾之優缺點。
結果顯示，當鑄膜溶液中的PMMA含量增加時，所製備的薄膜表面孔徑、孔洞數、孔隙度與接觸角皆有增加的趨勢，因此有利於薄膜蒸餾之滲透通量的提升。
在薄膜蒸餾中，WGMD的通量隨著間隙高度的降低、進料溫度與流速的增加，皆使滲透通量上升，在進料溫度70℃、流速0.8 L/min、間隙高度為0 mm且PMMA含量為14.4 wt%時，可得到最高滲透通量26.04 L/m2.h。薄膜回復性測試中顯示出三種薄膜於3.5 wt%的NaCl進料中皆有良好的回復性，且在連續24小時的WGMD操作中，F2A8薄膜保持著穩定的滲透通量與99.99%以上的阻隔率，代表此薄膜在長時間操作下有良好的穩定性。最後在WGMD與DCMD的性能比較中，雖然DCMD的滲透通量皆比WGMD高，但在WGMD的GOR皆高於DCMD，代表WGMD在熱能的使用效率較DCMD好，因此WGMD仍具有一定的優勢。

This work studied the preparation of the flat-sheet polyvinylidene fluoride (PVDF)/poly(methyl methacrylate) (PMMA) composite membrane by immersion-precipitation for applying in membrane distillation. The casting dope comprise PVDF, PMMA, and dimethyl sulfoxide .In this work, DMSO was selected as solvent, and the effect of PMMA content (3.6 wt%、7.2 wt%、10.8 wt% and 14.4 wt%, respectively) in the casting dope on the morphology of membrane was investigated.
    In membrane distillation, the performance of air gap membrane distillation (AGMD) and water gap membrane distillation (WGMD) at different feed temperature (50-70 ℃), flow rate (0.4-0.8 L/min), gap width (0, 1, 3 mm) was investigated. Finally, the advantages and the disadvantages between DCMD and WGMD was investigated by permeate flux and gained output ratio (GOR).
    The experimental results indicated that the pore size, porosity and contact angle of membrane became larger and the thickness of skin layer smaller as increase in PMMA content. The water has higher thermal conductivity than air, thereby the flux of WGMD is higher than AGMD. The flux of membrane distillation increased as the decrease in the gap width and increase the feed temperature and flow rate. The highest flux of WGMD is 26.04 L/m2hr, when the feed temperature is 70 ℃, flow rate is 0.8 L/min and the gap width is 0 mm.
    The results of long-term operation show that the flux of the F2A8 membrane have good stability, and the salt rejection maintain 99.99%. In the performance comparison between WGMD and DCMD, although the flux of DCMD is higher than WGMD, the GOR of WGMD is higher than DCMD, which means that WGMD is better than DCMD in energy efficiency.

中文摘要	I
英文摘要	II
目錄	IV
圖目錄	VII
表目錄	IX
第一章 緒論	1
1.1 前言	1
1.2 海水淡化技術	2
1.3 薄膜的種類與應用	4
1.4 薄膜蒸餾技術	6
1.5 綠色溶劑	8
1.6 研究動機與目的	10
第二章 文獻回顧	11
2.1 薄膜蒸餾歷史與發展	11
2.2 影響薄膜蒸餾滲透通量的因素	17
2.2.1薄膜材料性質	17
2.2.2 進料溶液	19
2.2.3 蒸氣壓差	20
2.2.4 進料流速	20
2.2.5 間隙高度	21
2.3 高分子薄膜製備方法	22
2.4 成膜理論-熱力學	24
2.5成膜理論-質傳動力學	27
2.6 PVDF/PMMA複合膜	28
第三章 實驗裝置與方法	29
3.1 實驗藥品	29
3.2 實驗設備	31
3.3 PVDF∕PMMA複合薄膜製備	33
3.3.1 PVDF∕PMMA製膜液配置	33
3.3.2 PVDF∕PMMA鑄膜方式	33
3.3.3 薄膜編號	34
3.4 薄膜性質分析	40
3.4.1 薄膜性質分析儀器	40
3.4.2 薄膜結構分析	41
3.4.3 薄膜膜厚與孔隙度量測	42
3.4.4 薄膜接觸角量測	43
3.4.5 薄膜機械強度測試	43
3.4.6 薄膜晶體結構特性測試	43
3.4.7 鑄膜液黏度測試	44
3.5 薄膜蒸餾裝置	45
3.5.1 直接接觸式薄膜蒸餾實驗模組	45
3.5.2 間隙式薄膜蒸餾實驗模組	45
3.6 薄膜蒸餾實驗	51
3.6.1 薄膜蒸餾操作條件	51
3.6.2 流量計校正	52
3.6.3 薄膜蒸餾實驗步驟	53
3.7 薄膜蒸餾結果分析	55
3.7.1 滲透通量分析與計算	55
3.7.2 薄膜蒸餾產出比率分析	56
3.7.3 鹽類含量之分析方法與阻隔率計算	56
第四章 結果與討論	58
4.1 鑄膜液黏度分析	58
4.2 薄膜結構與性質分析	60
4.2.1 薄膜SEM圖結構分析	60
4.2.2 薄膜孔徑與孔隙度分析	66
4.2.3 薄膜接觸角分析	67
4.2.4 薄膜機械強度分析	67
4.2.5 薄膜晶體結構分析	68
4.3 間隙式薄膜蒸餾	74
4.3.1 不同PMMA含量薄膜之滲透通量比較	74
4.3.2 AGMD與WGMD之滲透通量比較	75
4.3.3 薄膜於WGMD中不同操作條件之探討	78
4.3.4 各薄膜於不同進料濃度之回復性探討	84
4.3.5 薄膜於長時間操作中之結果	86
4.4 DCMD與WGMD性能比較	88
4.5 薄膜蒸餾通量與產水成本之文獻比較	91
第五章 結論	96
參考文獻	99
 
圖目錄
圖1-1 MSF與MED運作原理示意圖[4]	3
圖1-2 薄膜相關程序與分離成分示意圖[7]	5
圖1-3 常用溶劑選擇指標表[12]	9
圖2-1 (A) DCMD, (B) AGMD, (C) SGMD, (D) VMD示意圖[18]	16
圖2-2 AGMD、DCMD、PGMD與VMD的蒸氣傳輸機制圖[31]	16
圖2-3 高分子-溶劑-非溶劑之三相圖[59]	26
圖2-4 製膜液與沉澱槽擴散示意圖[52]	27
圖3-1 中空水槽示意圖 (鑄膜)	35
圖3-2 中空水槽示意圖 (沉澱槽)	36
圖3-3 親水支撐層之SEM圖	37
圖3-4 親水支撐層示意圖[ASAHI KASEI公司]	37
圖3-5 PVDF/PMMA複合膜製作流程示意圖	38
圖3-6 DCMD模組示意圖	46
圖3-7 DCMD 壓克力模組示意圖(進料與滲透側)	47
圖3-8 AGMD與WGMD模組示意圖	48
圖3-9 AGMD與WGMD進料側壓克力模組示意圖	49
圖3-10 AGMD與WGMD冷卻側壓克力模組示意圖	50
圖3-11進料側流量計校正曲線	52
圖3-12 冷卻水側流量計校正曲線	52
圖3-13 直接接觸式薄膜蒸餾裝置示意圖	54
圖3-14 間隙式薄膜蒸餾裝置示意圖	55
圖3-15 氯化鈉水溶液檢量線	57
圖4-1 20000倍薄膜表面SEM圖	62
圖4-2 50000倍薄膜表面SEM圖	63
圖4-3 500倍薄膜截面SEM圖	64
圖4-4 20000倍薄膜截面SEM圖	65
圖4-5 三種PVDF結晶相之XRD[66]	69
圖4-6 PVDF粉末之XRD分析圖	70
圖4-7 PMMA粉末之XRD分析圖	70
圖4-8 支撐層之XRD分析圖	71
圖4-9製備不同PMMA含量之薄膜XRD圖(1)	72
圖4-10製備不同PMMA含量之薄膜XRD圖(2)	73
圖4-11 不同PMMA含量薄膜於WGMD之滲透通量比較圖	75
圖4-12 F2A8薄膜於AGMD與WGMD之滲透通量比較圖	77
圖4-13 薄膜於間隙高度0mm以及50 ℃下不同進料流速之通量圖	80
圖4-14 薄膜於間隙高度0mm以及60 ℃下不同進料流速之通量圖	80
圖4-15 薄膜於間隙高度0mm以及70 ℃下不同進料流速之通量圖	81
圖4-16 F2A8薄膜於間隙高度0mm中不同進料溫度與流速之通量圖	81
圖4-17 薄膜於60 ℃下間隙高度3mm以及不同進料流速之通量圖	82
圖4-18 薄膜於60 ℃下間隙高度1mm以及不同進料流速之通量圖	82
圖4-19 薄膜於60 ℃下間隙高度0mm以及不同進料流速之通量圖	83
圖4-20 F2A8薄膜於60 ℃下不同間隙高度與進料流速之通量圖	83
圖4-21薄膜於WGMD中進料3.5 wt%鹽水前後之純水通量圖	85
圖4-22 薄膜於WGMD中進料15 wt%鹽水前後之純水通量圖	85
圖4-23 F2A8薄膜於WGMD中操作24小時之滲透通量與導電度圖	87
圖4-24 不同薄膜於DCMD與WGMD下之滲透通量圖	90
圖4-25 不同薄膜於DCMD與WGMD下之GOR圖	90
圖4-26 不同太陽能集熱方式示意圖[81]	94
圖4-27 不同海水淡化方式之成本圖(左為大型系統；右為小型系統)[82]	95

 
表目錄
表3-1 親水支撐層性質表	39
表3-2 薄膜製備條件表	39
表3-3 薄膜編號表	40
表3-4 薄膜蒸餾操作條件表	51
表4-1 鑄膜液黏度表	59
表4-2 薄膜性質分析表	69
表4-3 DCMD實驗結果之文獻比較表	93
表4-4 一般DCMD與熱回收系統DCMD之成本與性能評估表[81]	94
表4-5 DCMD搭配三種太陽能集熱方式之成本與性能評估表[82]	95

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