臺灣博碩士論文加值系統

本研究成功地製備出可應用於滲透蒸發(Pervaporation)分離程序分離乙二醇(Ethylene Glycol, EG)水溶液之聚二甲基矽氧烷/聚丙烯腈(Polydimethylsiloxane/ Polyacrylonitrile, PDMS/PAN)複合薄膜。研究中探討電漿處理聚丙烯腈薄膜對聚二甲基矽氧烷/聚丙烯腈複合薄膜分離乙二醇水溶液之效能影響。為符合汽車抗凍劑回收之需求，進料濃度範圍為小於70wt.%之乙二醇水溶液。文中以透過量(Permeation rate )及滲透蒸發選擇指數(Permeation Separation Index, PSI)進行效能探討； 探討進料溫度範圍為30~70℃，並計算出透過物種之活化能(Ea)。探討變數包含改變電漿功率、處理時間、鑄膜液濃度及塗佈厚度等。以原子力顯微鏡(AFM)、掃描式電子顯微鏡(SEM)探討薄膜特性。
研究結果顯示，氧氣電漿50瓦、60秒時為最佳的處理條件。聚丙烯腈基材膜膜表面的孔洞隨著電漿功率增加而增加，較薄的選擇層有較高透過量。
結果顯示，0550PDMS複合薄膜可成功地對乙二醇水溶液進行脫水；在進料為10wt.%乙二醇水溶液，操作溫度在30℃時，有較高之透過量、透過水濃度和PSI分別為1,135g/m2h、99.0wt.%與250,766。 0550PDMS複合薄膜，在進料溫度為30℃下，分離70wt.% 乙二醇水溶液時其透過量、透過水濃度及PSI分別為546 g/m2h、88.5wt.%及9,795。

Polydimethylsiloxane/ polyacrylonitrile (PDMS/p-PAN) composite membranes were successfully prepared in the present work for pervaporation separation of aqueous ethylene glycol solutions. In this study, we study on the effect of plasma treatment conditions on the pervaporation performance of aqueous ethylene glycol (EG) solution through PDMS/p-PAN composite membranes. The concentration range investigated (CEG < 70 wt.%) was selected according to existing motor vehicle antifreeze recycle requirements. The permeation rate and Pervaporation Separation Index (PSI) were monitored as the dehydration proceeded. The effect of temperature on the pervaporation performance was investigated in the range of 30–70°C. In addition, the activation energy of permeation (Ea) was calculated. The effects of preparation conditions including plasma treatment power, plasma treatment time, concentration of casting solution and casting thickness of the composite membrane active layer on the permeation rate and water concentration in permeate are discussed. In addition, the thickness of the dense selective layer was also adjusted by changing the coating thickness and the casting solution concentration. Atomic force microscopy (AFM) and scanning electron microscopy (SEM) studies were used to characterize the membranes. Best results were obtained using oxygen plasma pretreatment followed by 50w, 60sec. The pore size on PAN substrate membrane surface increased with increasing plasma power.
The results obtained demonstrated the successful performance of 0550PDMS composite membrane for the dehydration of aqueous ethylene glycol solution. It was observed that at 30°C and with 10wt.% EG concentration, higher permeation rate, water concentration in permeate and PSI could be obtained was 1,135g/m2h, 99.0 wt.% and 250,766, respectively. Moreover, the results were obtained with 0550PDMS composite membrane, giving a permeation rate of 546g/m2h, water concentration in permeate of 88.5wt.% and PSI of 9,795 for a 70wt.% ethylene glycol aqueous solution at 30°C.

目錄

中文摘要 ----------------------------------------------------------------------- I
英文摘要 ----------------------------------------------------------------------- II
目錄 ----------------------------------------------------------------------------- IV
圖索引 -------------------------------------------------------------------------- VIII
表索引 -------------------------------------------------------------------------- XIII
符號說明 ----------------------------------------------------------------------- XIV

第一章 前言 -------------------------------------------------------------- 1

1-1 研究背景------------------------------------------------------------- 1
1-2 研究動機與目的 ----------------------------------------- 3

第二章 文獻回顧 --------------------------------------------- 6

2-1 薄膜的定義 -------------------------------------------------------- 6
2-2 薄膜製備方法 ----------------------------------------------------- 8
2-2-1 燒結法------------------------------------------------------- 8
2-2-2 拉伸法------------------------------------------------------- 8
2-2-3 軌跡蝕刻法------------------------------------------------- 8
2-2-4 溶出法------------------------------------------------------- 9
2-2-5 相轉換法---------------------------------------------------- 9
2-3 薄膜改質 ----------------------------------------------------------- 12
2-3-1 交聨 --------------------------------------------------------- 12
2-3-2 摻合 --------------------------------------------------------- 12
2-3-3 接枝 --------------------------------------------------------- 12
2-3-4 滲透交聯聚合法 ------------------------------------------ 13
2-3-5 電漿改質----------------------------------------------------- 13
2-3-6 蒸氣沉積合成法-------------------------------------------- 16
2-4 薄膜分離技術概述 ----------------------------------------------- 17
2-5 滲透蒸發原理 ----------------------------------------------------- 20
2-6 聚二甲基矽氧烷高分子------------------------------------------- 22
2-7 乙二醇特性 ---------------------------------------------- 23
2-8 有機物分離文獻回顧 ------------------------------------ 24

第三章 實驗 ------------------------------------------------------------- 36

3-1 複合薄膜製備 ----------------------------------------------------- 36
3-1-1 基材膜之製備 ---------------------------------------------- 36
3-1-2 緻密層之製備 ---------------------------------------------- 37
3-2 實驗藥品 ------------------------------------------------ 39
3-3 實驗儀器 ------------------------------------------------ 40
3-4 薄膜製備 ------------------------------------------------- 42
3-4-1 聚丙烯腈基材膜之製備 --------------------------------- 42
3-4-1.1 鑄膜溶液配置 ------------------------------ 42
3-4-1.2 基材膜之製備 ------------------------------ 42
3-4-2 電漿表面改質聚丙烯腈薄膜 ---------------------- 42
3-4-3 聚二甲基矽氧烷/聚丙烯腈複合膜之製備 --------- 43
3-4-3.1 鑄膜溶液配置 ------------------------------ 43
3-4-3.2 複合薄膜之製備 ---------------------------- 43
3-5 薄膜檢測 ------------------------------------------------- 44
3-5-1 掃描式電子顯微鏡 --------------------------------- 44
3-5-2 掃描式電子顯微鏡之X 射線能量散佈分析儀 ---- 44
3-5-3 原子力顯微鏡 --------------------------------------------- 44
3-5-4 滲透蒸發測試 ----------------------------------- 45
3-6 實驗架構 ------------------------------------------------ 47

第四章 結果與討論 ---------------------------------------------- 54

4-1 純基材與複合膜材滲透蒸發分離效能比較 ----------------- 54
4-2 氧氣電漿處理條件對滲透蒸發分離效之影響 -------------- 56
4-2-1 電漿處理時間探討 ----------------------------------- 56
4-2-2 電漿功率------------------------------------------------ 56
4-3 電漿功率對基材膜面之影響 ------------------------------ 58
4-4 製膜條件對PDMS/p-PAN複合膜滲透蒸發分離效能影響 60
4-4.1 刮膜厚度對滲透蒸發分離效能之影響 --------------- 60
4-4.2 成膜條件滲透蒸發效能之比較 ------------------------ 61
4-5 進料濃度對滲透蒸發分離效能之影響 ---------------------- 63
4-6 進料溫度對滲透蒸發分離效能之影響 ----------------------- 64

第五章 結論 ------------------------------------------------------------ 88

第六章 參考文獻 ------------------------------------------------------- 90

作者自述 ---------------------------------------------------------------- 99

圖索引
第一章
Fig. 1-1
Operating ranges and expected glycol concentrations for the individual process steps.
5
第二章
Fig. 2-1
Schematic representation of membrane cross-sections.
26
Fig. 2-2
Schematic representation of the nominal pore size and best theoretical model for the principal membrane separation processes.
27
Fig. 2-3
Milestones in the development of pervaporation.
28
Fig. 2-4
The principle of pervaporation.
29
Fig. 2-5
Liquid zone and vapor zone in series by Binning et al.
30
Fig. 2-6
Schematic representation of a two-phase system separated by a membrane.
31
Fig. 2-7
Solute concentration profile across the membrane and some previous studies using the
32
resistance-in-series model.
Fig. 2-8
PDMS chemical structure.
33
Fig. 2-9
Morphology of the substrate surfaces prepared by using different PAN concentration.
34
第三章
Fig. 3-1
Schematic diagram of composite membranes fabricated in the present work.
48
Fig. 3-2
Schematic diagram of continuous wet-inversion membrane formation unit.
49
Fig. 3-3
Plasma reactor.
50
Fig. 3-4
Pervaporation testing apparatus.
52
Fig. 3-5
The schematic diagram of pervaporation apparatus.
53
第四章
Fig. 4-1
Effect of O2 plasma treatment timeon pervaporation performance of 70wt.% aqueous EG solution through the
67
0550PDMS composite membrane at 30℃. (plasma power: 50w)
Fig. 4-2
Effect of O2 plasma treatment time on PSI value of0550PDMS composite membrane for 70wt.% aqueous EG solution at 30℃. (plasma power: 50w)
68
Fig. 4-3
Effect of O2 plasma power on pervaporation performanceof 70wt.% aqueous EG solution through the 0550PDMS composite membrane at 30℃
69
Fig. 4-4
Surface morphology of the O2 plasma treated PAN membranes with different plasma power. (a) pristine, (b)10w, (c) 30w, (d) 50w, (e) 70w. (30K magnification).
70
Fig. 4-5
AFM (2-D) images of PAN membrane surface treated by O2plasma with various power for 60sec: (a) pristine PAN, (b) 10w, (c) 30w, (d) 50w, (e) 70w.
71
Fig. 4-6
AFM (3-D) images of PAN membrane surface treated by O2plasma with various power for 60sec: (a) pristine PAN, (b) 10w, (c) 30w, (d) 50w, (e) 70w.
72
Fig. 4-7
Effect of O2 plasma power on permeate concentration of 70wt.% aqueous EG solution through the 0550PDMS composite membrane at 30℃.
73
Fig. 4-8
Effect of O2 plasma power on PSI value for a 70wt.% aqueous EG solution at 30℃ through 0550PDMS
75
composite membrane.
Fig. 4-9
Effect of plasma treatment time on the permeation flux of PDMS/p-PAN composite membranes. (Feed condition: 70wt.% aqueous EG solution at 30℃)； Membrane: (■)0505PDMS, (●) 2005PDMS, (▲) 0550PDMS, (▼)2050PDMS.
76
Fig. 4-10
Effect of plasma treatment time on the water concentration in permeate of PDMS/p-PAN composite membranes. (Feed condition: 70wt.% aqueous EG solution at 30℃)；Membrane: (■) 0505PDMS, (●) 2005PDMS, (▲)0550PDMS, (▼) 2050PDMS.
77
Fig. 4-11
SEM surface images of the O2 plasma treated PAN membranes by different plasma treated time. Plasma treatedtime with 60sec: (A) 1k, (B) 10k, (C) 20k, (D) 30k; Plasma treated time with 120sec : (a) 1k, (b) 10k, (c) 20k, (d) 30k. (30K magnification) (power: 50w)
78
Fig. 4-12
SEM surface morphology of PDMS/p-PAN membranes. PDMS casting condition : (a) 5wt.%-5μm, (b) 20wt.%-5μm, (c) 5wt.%-50μm, (d) 20wt.%-50μm. (10K magnification)
79
Fig. 4-13
SEM cross-section images of the PDMS/p-PAN composite membranes. (a) pristine PAN, (b) 0505PDMS, (c) 0550PDMS, (d) 2005PDMS, (e) 2050PDMS. (10K magnification).
81
Fig. 4-14
Effect of casting condition on the pervaporation performance of 70wt.% aqueous EG solution through the
82
PDMS/p-PAN composite membrane at 30℃
Fig. 4-15
Effect of feed concentration on the pervaporation performance of 0550PDMS composite membrane at 30℃.
83
Fig. 4-16
Effect of feed concentration on PSI value of 0550PDMS composite membrane at 30℃.
84
Fig. 4-17
Effect of feed temperatures on the pervaporation performance of 70wt.% aqueous EG solution through the 0550PDMS composite membrane.
85
Fig. 4-18
Arrhenius plots of EG and water for separating 70wt.% aqueous EG solution through the0550PDMS composite membrane.
86

表索引
第二章
Table 2-1
Driving forces and the two-phase systems separated by membranes for different membrane processes.
35
第三章
Table 3-1
Designation of PDMS/p-PAN composite membranes.
51
第四章
Table 4-1
Pervaporation performance for PAN membranes and PDMS/p-PAN composite membranes. (Feed: 70wt.% aqueous EG solution at 30℃)
66
Table 4-2
Physical properties of water、ethylene glycol and PDMS.
74
Table 4-3
Activation energy for pervaporation.
87

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