臺灣博碩士論文加值系統

現今我們的生活與石化燃料息息相關，面對未來全球石油供應短缺以及環境議題，替代能源的需求因此成為了一門重要課題。生質柴油為一普遍的生質能，其具有潔淨、再生性的特質，且燃燒性質近似於石化柴油，因此可以作為柴油燃料的替代品亦或與一般燃料混合。
為了克服一般因為油料中自由脂肪酸於鹼觸媒生產生質柴油時所遇到的皂化和水解問題，學者們提出預酯化-轉酯化之兩步驟式生產生質柴油之方法，本研究則在探討第一步驟的預酯化反應。有別於一般文獻上多採取小分子酸來進行預酯化反應而有失模擬真正生質柴油中的自由脂肪酸，我們設計了一合併式反應-滲透蒸發模組，透過己酸、丙醇預酯化反應以及有無結合滲透蒸發作為比較，根據勒沙特列原理，藉由不斷地將產物水移除，有利於反應向產物端進行，進而增加自由脂肪酸的轉化率。結果顯示Crosslinking PI薄膜的高度親水性。我們也針對不同的反應物初始醇/酸莫耳數比(M)、反應溫度、膜面積/反應溶液體積(S/V)比進行探討以尋求最佳條件。與未結合滲透蒸發相比，結果顯示在初始丙醇/己酸莫耳數比= 1.39、反應溫度70℃、5 wt % Amberlyst 15觸媒用量下，結合滲透蒸發可以在12小時內提升約3 %轉化率。而使用0.05 wt % 硫酸觸媒結合滲透蒸發則可以在9小時內提升約6 %轉化率。

Nowadays, our life is intimately linked with fossil fuels. With more and more concerns about oil shortage and environmental issues, seeking for alternative energy turns out to be crucial. Biodiesel is a kind of general biofuel, and it is clean, renewable and has combustion properties like petroleum-based diesel.
In order to overcome the saponification and hydrolysis problems of producing biodiesel by using alkaline catalysts which is usually caused by free fatty acid (FFA) contained in raw oil. A two-step method, pre-esterification followed by transesterification, is proposed. In our study, we focused on the first step: pre-esterification. In most literatures, small acid molecular compounds were used to perform the pre-esterification reactions, which is different from the main FFA component in the raw oil. We designed a reactor consisting of a pervaporation module. The esterifications of n-propanol and caproic acid were performed with/without pervaporation for comparison. By means of continuously removing the water from the solution via prevaporation, the overall reaction favors the product side, thus further to enhance the conversion of caproic acid based on Le Chatelier principle. The results showed the hydrophilic property of Crosslinking PI membrane. We also investigated various parameters including initial molar ratio of n-propanol to caproic acid (M), reaction temperature, ratio of effective membrane area to the reaction solution volume (S/V) to search the optimal condition. Compared with no pervaporation, the results showed that the conversion was enhanced 3 % at 70℃, using 5 wt % Amberlyst 15 catalyst and M= 1.39 by pervaporation in 12 hours. Instead of Amberlyst 15, the conversion was enhanced 6 % when 0.05 wt % sulfuric acid catalyst was used with pervaporation in 9 hours.

誌謝 i
中文摘要 iii
ABSTRACT iv
CONTENTS vi
LIST OF FIGURES ix
LIST OF TABLES xiii
Chapter 1 緒論 1
1.1 研究背景 1
1.2 研究目的 5
Chapter 2 文獻回顧 7
2.1 滲透蒸發原理 7
2.2 滲透蒸發質傳機制 8
2.2.1 Solution-Diffusion model 8
2.2.2 Pore-flow model 10
2.3 滲透蒸發的發展 12
2.4 Hansen 溶解度參數 13
2.5 滲透蒸發的應用 15
2.5.1 有機溶液脫水 15
2.5.2 混合溶液中移除有機物 17
2.5.3 有機-有機分離 18
2.6 酯化反應結合滲透蒸發 19
2.7 生質柴油之觸媒 23
Chapter 3 實驗方法 26
3.1 實驗藥品與器材 26
3.1.1 實驗藥品 26
3.1.2 氣體 26
3.1.3 器材 27
3.2 薄膜特性檢測及分析原理 28
3.2.1 接觸角量測儀(Contact Angle Meter) 28
3.2.2 場發射掃描式電子顯微鏡(Field Emission Scanning Electron Microscope, FE-SEM) 29
3.2.3 能量分散光譜儀(Energy dispersive spectrometer, EDS) 30
3.2.4 熱重示差同步掃描分析儀(Thermogravimetry/Differential Thermal Analysis Thermoanalyzer, TG-DTA) 32
3.2.5 氣相層析儀-火焰離子偵測器(Gas Chromatograph-Flame Ionization Detector, GC-FID) 33
3.3 滲透蒸發薄膜反應器 35
3.4 實驗步驟 37
3.4.1 滲透蒸發實驗步驟 37
3.4.2 預酯化結合滲透蒸發實驗步驟 38
3.4.3 預酯化產物分析 39
Chapter 4 薄膜特性分析結果與討論 46
4.1 接觸角(Contact angle)分析 46
4.2 場發射掃描式電子顯微鏡(FE-SEM)/能量分散光譜儀(EDS) 48
4.3 熱重分析(TGA) 51
Chapter 5 滲透蒸發分離實驗結果與討論 52
Chapter 6 預酯化反應結合滲透蒸發實驗結果與討論 56
6.1 不同反應溫度的影響 56
6.2 不同醇/酸莫耳數比(M)的影響 66
6.3 不同薄膜面積/反應溶液體積(S/V)的影響 75
6.4 不同酸觸媒的影響 81
Chapter 7 結論 87
REFERENCE 90
個人小傳 94

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