本研究以實驗室合成之聚偏二氟乙烯(poly(vinylidene fluoride), PVDF)中空纖維膜組裝之模組進行直接接觸式薄膜蒸餾(direct contact membrane distillation)及真空式薄膜蒸餾(vacuum membrane distillation)實驗，進料溶液為3.5 wt%之鹽水溶液，操作參數為進料溫度(50~70 oC)及進料速率(0.2~0.5 L/min)，真空式薄膜蒸餾其真空度為持在8 kPa，直接接觸式薄膜蒸餾之冷水側溫度為13 oC及進料速率0.4 L/min。
製備中空纖維膜的條件為改變芯液之組成，其中共4種條件分別為20、30、40、60 wt%磷酸三乙酯(TEP)水溶液，藉由硬性換成軟性的方式來改善中空纖維膜內表面結構。從SEM解析得知隨著磷酸三乙酯(TEP)在芯液的比例增加薄膜內表面皮層結構不易形成，且大孔洞數變多。
真空式及直接接觸式薄膜蒸餾操作中，提高進料溫度能明顯增加滲透通量，但極化現象也較嚴重，此外薄膜於真空式薄膜蒸餾會有fouling現象，造成氯化鈉顆粒析出於殼測薄膜表面，此種現象會造成薄膜之有效面積減少，降低純水通量。增加進料流率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。
其結果顯示隨著芯液中TEP wt%的比例增加，所製成的薄膜在直接接觸式薄膜蒸餾有較高的通量，在真空式薄膜蒸餾中更加明顯。孔洞較大的薄膜對於進料溫度及速率的增加在通量的提升效果高於小孔洞之薄膜。此外短模組在真空及直接接觸式薄膜蒸餾操作中的滲透通量都明顯高於長模組。

In this study, laboratory made poly(vinylidene fluoride), PVDF, hollow fiber membranes were used in vacuum and direct contact membrane distillation of saline solution. The feed solution was 3.5 wt% NaCl solution, the operating parameters included feed temperature (50 ~ 60 oC), feed rate (0.2 ~ 0.5 L / min), the vacuum pressure in the permeate side was controlled at 8 kPa for vacuum membrane distillation, and cooling water controlled at 13 oC with rate 0.4 L / min for direct contact membrane distillation. 
The hollow fiber membranes were prepared by varying the composition of the bore liquid. There were four conditions, which 20、30、40、60 wt% triethylphosphate (TEP) solution. The inner skin of the hollow fiber membrane was improved by changed the bore liquid from hard coagulation (water bath) to soft coagulation. Analysis the structure by SEM morphology, which membrane have large pore size in the inner surface by increasing the weight percent of TEP in bore liquid.
In the vacuum and direct contact membrane distillation experiment, raising the temperature of the feed can significantly increase the flux, but the polarization phenomena become more serious. In addition, the membrane surface will have fouling phenomenon that NaCl was separated out to the shell side membrane surface in vacuum membrane distillation. This situation will cause decrease the effective area of the membrane and reduce the flux. Increasing feed flow rate has a finite effect on increasing the flux, but the temperature polarization phenomenon can be reduced by the feed flow rate as higher feed temperature. 
The experimental results showed the higher flux performance on direct contact membrane distillation which prepared by higher weigh percent of TEP bore liquid solution obviously in the vacuum membrane distillation. The large pore size membrane flux which increased by higher inlet temperature more obvious then the small one. Furthermore, the short module have higher flux then long module in the same inlet condition.

目錄
第一章	1
1.1前言	1
1.2薄膜的應用	2
1.3薄膜分離	5
1.4薄膜蒸餾	7
1.5研究之目的	9
第二章	13
2.1薄膜蒸餾法	13
2.1.1直接接觸式薄膜蒸餾	13
2.1.2空氣間隙式薄膜蒸餾	14
2.1.3真空式薄膜蒸餾	14
2.2殼管式模組	16
2.3薄膜之孔隙結構及性質	17
2.4影響滲透通量的因素	19
2.5薄膜製備(相轉換法)	21
2.6高分子成膜理論	21
2.6.1成膜理論(熱力學)	22
2.6.2成膜理論(質傳動力學)	24
2.7PVDF中空纖維膜	25
第三章	28
3.1實驗裝置與流程	28
3.1.1PVDF薄膜製備及解析	28
3.1.2中空纖維模組製作及模組編號	30
3.2薄膜性質分析	33
3.2.1薄膜形態和表面孔洞分析	33
3.2.2薄膜膜厚及孔隙度測試	33
3.2.3Bubble point method	34
3.3DCMD 薄膜蒸餾	35
3.4VMD 薄膜蒸餾	38
3.5分析方法	41
3.5.1鹽類含量之分析方法與條件	41
3.5.2鹽類阻隔率之計算	41
3.6流量計校正	41
3.7實驗設備及藥品	43
第四章 結果與討論	45
4.1SEM解析探討	45
4.2DCMD薄膜蒸餾	53
4.2.1薄膜改質後在DCMD之探討	53
4.2.2膜組長度對於DCMD之影響	54
4.2.3鹽水濃度之影響	55
4.3VMD薄膜蒸餾	56
4.3.1薄膜改質後在VMD實驗之探討	56
4.4VMD和DCMD兩系統比較	56
4.5VMD和DCMD兩系統與文獻比較	57
4.6薄膜阻隔率	57
第五章 結論	68
參考文獻	70


 
圖目錄
圖1.1薄膜分離程序之分類[Cheryan, 1998]……………………………………….10
圖1.2 PVDF………………………………………………………………………….10
圖1.3薄膜蒸餾物流流動示意圖…………………………………………………...11
圖2.1蒸餾膜組之型式……………………………………………………………………...15
圖2.2 Schematic representation of mass transfer occurring at the membrane coagulant surface ……………………………………………………………………………….24
圖2.3高分子(非結晶型)-溶劑-非溶劑成膜相圖…………………………………..25
圖3.1噴紡法製備毛細管薄膜之裝置示意圖[陳勝昌, 2013]…………………...29
圖3.2中空壓克力模組……………………………………………………………...32
圖3.3DCMD與VMD模組設計示意圖……………………………………………32
圖3.4Bubble point experiment set up………………………………………………..34
圖3.5DCMD experiment set up……………………………………………………..37
圖3.6VMD experiment set up……………………………………………………….40
圖3.7進料側流量計校正曲線……………………………………………………...42
圖3.8冷卻水側流量計校正曲線…………………………………………………...42
圖4.1添加不同比例的TEP於芯液70倍之薄膜截面……………………………49
圖4.2添加不同比例TEP於芯液400倍之薄膜截面……………………………..50
圖4.3添加不同比例TEP於芯液10000倍之薄膜內表面………………………..51
圖4.4添加不同比例TEP於芯液10000倍之薄膜外表面………………………..52
圖4.5鹽水於70 ℃ & 0.5L/min 進料速率下DCMD之滲透通量……………...58
圖4.6鹽水於50 ℃ 在不同進料速率下DCMD之滲透通量……………………58
圖4.7鹽水於60℃在不同進料速率下DCMD之滲透通量………………………59
圖4.8鹽水於70℃在不同進料速率下DCMD之滲透通量………………………59
圖4.9 DCMD M-14-10-T0-T30、M-7-10-T0-T30膜組長度之影響……………...60
圖4.10 70℃&0.5L/min操作條件下鹽水濃度對DCMD的影響…………………60
圖4.11鹽水於50~70℃%0.5L/min進料速率下VMD之滲透通量……………...61
圖4.12鹽水於50℃在不同流率下VMD之滲透通量……………………………61
圖4.13鹽水於60℃在不同流率下VMD之滲透通量……………………………62
圖4.14鹽水於70℃在不同流率下VMD之滲透通量……………………………62
圖4.15模組於鹽水50℃ & 0.2~0.5 L/min對VMD & DCMD之影響………….63
圖4.16模組於鹽水60℃ & 0.2~0.5 L/min對VMD & DCMD之影響………….63
圖4.17模組於鹽水70℃ & 0.2~0.5 L/min對VMD & DCMD之影響………….64
圖4.18 M-14-10-T0-T30於50℃進行一天DCMD之通量及導電度…………….65
圖4.19 M-14-10-T0-T20於50℃進行一天DCMD之通量及導電度…………….65

表目錄
表1.1不同操作程序之驅動力分類[Cheryan, 1998] …………………12
表3.1 Process parameters/spinning condition………………………….29
表3.2中空纖維管之膜組規格………………………………………...31
表3.3Characteristic of hollow fiber module……………………………31
表4.1	Characteristic of membrane in different bore liquid…………...66
表4.2	DCMD result compare with references………………………..66
表4.3	VMD result compare with references………………………….67
 

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