本研究以聚偏二氟乙烯(poly(vinylidene fluoride), PVDF)膜材，並使用親水支撐層合成一平板親-疏水複合薄膜，來組裝模組進行直接接觸式薄膜蒸餾用於海水淡化之效能探討，進料分為模擬海水(3.5 wt%的NaCl水溶液)、淡水沙崙區域之海水。合成薄膜的組成為PVDF、磷酸三乙酯(Triethyl phosphate, TEP)及Tween20的混合溶液，其中共三種條件分別為20、40、60 wt%磷酸三乙酯水溶液之沉澱槽，藉由硬性沉澱槽換成軟性沉澱槽的方式來改善平板薄膜表面結構。從SEM解析得知隨著磷酸三乙酯(TEP)在沉澱槽比例的上升，其薄膜表面孔洞數量、孔徑也隨之提升，並探討其薄膜結構對蒸餾操作之影響。
    在海水前處理之部分，分為兩次過濾，ㄧ次過濾使用4 μm之親水性濾紙，二次過濾使用不同孔徑之親水性PVDF薄膜(0.1、0.2 μm)，並探討不同過濾方式對薄膜蒸餾之影響。
在實驗操作部分主要是探討不同的參數對薄膜蒸餾之滲透通量及鹽阻隔率之影響，DCMD中兩側流體流動是逆流方式，其它參數包括在進料溫度(50~70 oC)、進料速度(0.4~0.8 L/min)與不同進料(純水、模擬海水、海水)。
在DCMD中其結果顯示隨著沉澱槽TEP wt%的比例增加，所製成的薄膜之通量會高於沒改質的薄膜，是由於隨著TEP在沉澱槽的比例增加薄膜表面皮層結構不易形成，且大孔洞數變多。前處理方面，使用薄膜過濾後之滲透通量皆略高於濾紙過濾。提高進料溫度能明顯增加滲透通量，但極化現象也較嚴重，而增加進料流量則對於滲透通量之提升較不顯著，但對於高溫進料操作之溫度極化現象具有較明顯改善效果。

This research was divided into two parts. The first part was prepared the flat-sheet composite membranes of polyvinylidene fluoride (PVDF) supported on hydrophilic polyester. The effect of triethyl phosphate (TEP) concentration on the morphology of composite membrane was investigated in this study. The thin membranes were prepared by coating mixed PVDF and Tween20. In this work, TEP was selected as solvent and prepared with 20, 40 and 60 wt% in the coagulation bath. The results indicated that the pore size of membrane surface became larger as increase in TEP concentration.
The second part was studied the performance of direct contact membrane distillation (DCMD) for seawater desalination. The artificial seawater with 3.5 wt% NaCl was compared with seawater experimentally in this study. In the pretreatment of the DCMD, the seawater was carried out 4 μm hydrophilic filter paper for filtering the fine particle and biomass. The hydrophilic PVDF film with pore size of 0.1 and 0.2 μm was used for DCMD. The effect of operation parameters, such as feed temperature (50-70 oC), flow rate (0.4-0.8 L/min) and feed on permeate flux and salt rejection was investigated. The fluid on both sides of DCMD was presented with countercurrent mode.
The experimental results of DCMD showed that the membrane prepared from higher TEP concentration had a larger permeate flux because of its larger pore size on the surface. Increasing the feed temperature could significantly increase the flux, but the polarization phenomena became more serious. On the contrary, increasing feed flow rate was less significant for the increasing of the permeation flux, but the temperature polarization of the high temperature feed operation had more obvious improvement effect.

目錄
致謝	I
目錄	V
圖目錄	IX
表目錄	XII
第一章 緒論	1
1.1前言	1
1.2薄膜分離程序	3
1.3薄膜的應用	5
1.4薄膜蒸餾	8
1.5研究目標	10
第二章 文獻回顧	13
2.1薄膜蒸餾相關研究	13
2.2薄膜蒸餾之種類	17
2.2.1 直接接觸式薄膜蒸餾	17
2.2.3 空氣掃掠式薄膜蒸餾	18
2.2.4 真空式薄膜蒸餾	18
2.3薄膜之孔隙結構及性質	18
2.4影響滲透通量的因素	21
2.5薄膜製備	23
2.6高分子成膜理論	23
2.6.1成膜理論：熱力學	24
2.6.2 成膜理論：質傳動力學	26
第三章 實驗裝置與方法	30
3.1 實驗裝置	30
3.2薄膜製備	31
3.3 模組編號	31
3.4 薄膜性質分析	32
3.4.1 薄膜的形態和表面孔洞分析	32
3.4.2 薄膜膜厚及孔隙度測試	32
3.4.3 接觸角量測	33
3.4.4 機械強度測試	33
3.5 海水前處理	33
3.5.1 海水前處理	33
3.5.2 出水品質之分析方法	34
3.6 DCMD實驗步驟	35
3.7 DCMD操作條件	37
3.8分析方法	38
3.8.1 鹽類含量之分析方法與條件	38
3.8.2 鹽類阻隔率之計算	38
3.9 流量計校正	38
3.10 實驗設備及藥品	39
3.10.1 PVDF薄膜製備	39
3.10.2 DCMD薄膜蒸餾	39
3.10.3海水前處理	40
第四章 結果與討論	50
4.1 薄膜特性與結構分析	50
4.1.1 薄膜改質(鑄於支撐層)結構	50
4.1.2薄膜有無支撐層結構	57
4.1.3薄膜之孔洞與孔隙度	60
4.1.4 薄膜之接觸角	61
4.1.5機械強度測試	61
4.2海水出水品質分析	64
4.3 DCMD薄膜蒸餾	65
4.3.1 DCMD之鹽水滲透通量	65
4.3.2 鑄膜於支撐層與玻璃板上之比較	71
4.3.3鹽水之回復性探討	73
4.3.4 不同海水前處理的影響	76
4.3.5 DCMD之海水滲透通量	78
4.3.6 海水之回復性探討	84
4.4薄膜長時間操作測試	87
4.5 DCMD系統與文獻比較	89
第五章 結論	92
參考文獻	94









 
圖目錄
圖1.1 PVDF化學結構示意圖	11
圖1.2 薄膜分離程序之分類	12
圖1.3薄膜蒸餾物流流動示意圖	12
圖2.1 薄膜蒸餾膜組之型式	27
圖2.2 高分子(非結晶型)-溶劑-非溶劑成膜相圖	28
圖2.3 Schematic representation of mass transfer occurring at the membrane/coagulant surface.	28
圖2.4 未添加和添加界面活性劑的 PVDF 薄膜分別在製膜液、相轉移過程和初生薄膜的示意圖	29
圖3.1 DCMD 模組示意圖	41
圖3.2 DCMD 模組設計示意圖(進料側)	42
圖3.3 DCMD 模組設計示意圖(冷卻水側)	43
圖3.4 DCMD experiment set up	44
圖3.5親水支撐層之SEM結構圖	45
圖3.6 親水支撐層示意圖	45
圖3.7 NaCl檢量線	46
圖3.8 進料側流量計校正曲線	46
圖3.9 冷卻水側流量計校正曲線	47
圖4.1  5000倍SEM圖之薄膜上表面	53
圖4.2  30000倍SEM圖之薄膜上表面	54
圖4.3 500倍SEM圖之薄膜截面	55
圖4.4 10000倍SEM圖之薄膜截面	56
圖4.5 5000倍SEM圖之薄膜上表面	58
圖4.6 10000倍SEM圖之薄膜上表面	59
圖4.7 T60W20於DCMD之鹽水滲透通量	68
圖4.8 鹽水於50~70℃ &0.8 L/min進料流量下DCMD之滲透通量	68
圖4.9 鹽水於50℃不同進料流量下DCMD之滲透通量	69
圖4.10 鹽水於60℃不同進料流量下DCMD之滲透通量	69
圖4.11 鹽水於70℃不同進料流量下DCMD之滲透通量	70
圖4.12 鑄膜於支撐層與玻璃板DCMD之滲透通量比較	72
圖4.13 T20W20於70℃在不同進料速率下鹽水前後純水DCMD之滲透通量	74
圖4.14 T40W20於70℃在不同進料速率下鹽水前後純水DCMD之滲透通量	74
圖4.15 T60W20於70℃在不同進料速率下鹽水前後純水DCMD之滲透通量	75
圖4.16 不同前處理對DCMD滲透通量的影響	77
圖4.17 T60W20於DCMD之海水滲透通量	81
圖4.18 海水於50~70℃ &0.8 L/min進料流量下DCMD之滲透通量	81
圖4.19 海水於50℃不同進料流量下DCMD之滲透通量	82
圖4.20 海水於60℃不同進料流量下DCMD之滲透通量	82
圖4.21 海水於70℃不同進料流量下DCMD之滲透通量	83
圖4.22 三種不同模組於70℃不同進料&不同流量下DCMD之滲透通量	83
圖4.23 T20W20於70℃在不同進料速率下海水前後純水DCMD之滲透通量	85
圖4.24 T40W20於70℃在不同進料速率下海水前後純水DCMD之滲透通量	85
圖4.25 T60W20於70℃在不同進料速率下海水前後純水DCMD之滲透通量	86
圖4.26 T60W20薄膜於50℃進行兩天DCMD之滲透通量與導電度	88
圖4.27 DCMD滲透側經換算後之導電度與鹽阻隔率	88
圖4.28 T60W20於DCMD與其他論文之滲透通量比較	90

 
表目錄
表1.1 不同操作程序之驅動力分類 [Cheryan, 1998]	11
表3.1 製膜液組成與製備條件	48
表3.2 親水支撐層性質說明	48
表3.3 Characteristic of membrane module	49
表4.1 PVDF薄膜物性分析	63
表4.2 PVDF 薄膜拉伸強度分析	63
表4.3 DCMD results compared with references	91

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