臺灣博碩士論文加值系統

隨著科技日新月異的發展，各國對於能源的需求日益升高，目前仍舊高度依賴使用非再生能源，造成嚴重環境汙染、溫室效應等問題，因此人們開始尋找可再生的替代能源，其中生質柴油備受矚目，然而隨著生質柴油的大量生瓹，甘油(生質柴油製程中副瓹物)瓹量也大幅上升，造成甘油價格於市場中大幅降低，因此將甘油轉變為更有價值之瓹品引起人們興趣，其中單甘油酯可用於食品、製藥、清潔品及塑膠等領域中受到關注。
單甘油酯工業上主要由轉酯化反應及酯化反應藉由催化劑催化合成，異質催化劑因其可重複使用性與易分離性受到大量研究可望取代傳統均質催化劑，然而異質催化劑有催化劑溶出問題，失去使用異質催化劑之優點，過往都以巨觀方式觀察催化劑，因此本研究將以微觀方式觀察催化劑溶出現象，找出催化劑表面結晶取向與催化劑溶出之關係。
本研究使用於酯化反應製備單甘油酯有高轉化率及高選擇性之氧化鋅當作催化劑，以固態燒結法製備氧化鋅錠，使用XRD 分析氧化鋅催化劑晶體結構，SEM 分析催化劑反應前後表面形貌變化，EBSD 分析結晶取向分布與溶出現象之關係，AFM分析反應前後試片表面高度差變化，使用油酸當作反應物模擬酯化反應製備單甘油酯。
結果指出油酸反應中，靠近{1010}及{2110}結晶取向面於反應中變化速率最慢，並且於反應前期幾乎未有明顯，因此擁有較良好抗溶出能力；然而於反應後期所有結晶取向面皆與油酸反應，於反應前期靠近{1010}及{2110}結晶取向面擁有56 kJ/mol 的活化能，而反應後期所有結晶面擁有約為31 kJ/mol的活化能。

With the increasing production of biodiesel, glycerol is oversupply which causing economic and environmental considerations. People are interesting in converting glycerol into value added product. Monoglyceride as a good surfactant has a variety of applications, such as food, cosmetic industries, pharmaceuticals, detergents and plastic products.
Monoglyceride can be synthesized by esterification of fatty acid with glycerol through a catalyst. Various heterogeneous catalysts have developed to facilitate reaction. However, heterogeneous catalysts have the problem of leaching active sites. In order to better understand this issue, we analyze the catalyst in micro-scale compared to the macro-scale analysis using in past. In this study, SEM and AFM were used to observe the surface morphology, and EBSD was used to find the relationship between surface facts of zinc oxide catalyst and leaching. Oleic acid was used to simulate the esterification environment.
The results showed that planes near *101̅ 0+ and *112̅ 0+ directions have better resistivity because of later happening of leaching with activation energy about 58 kJ/mol. By the analysis method we used, it can analyze great number of grains with different orientations at the same time.

摘要 I
誌謝 XVI
目錄 XVII
表目錄 XX
圖目錄 XXI
第一章 前言 1
第二章 文獻回顧 4
2.1 乳化劑 4
2.2 單甘油酯 5
2.2.1 單甘油酯結構與性質 5
2.2.2 單甘油酯應用 7
2.2.3 單甘油酯製備方法 10
2.3 用於單酸甘油酯製備之催化劑 12
2.3.1 均質鹼性催化劑 12
2.3.2 異質鹼性催化劑 13
2.3.3 均質酸性興催化劑 14
2.3.4 異質酸性催化劑 15
2.3.5 異質酸性催化劑反應機制 18
2.4 催化劑溶出現象 20
第三章 實驗流程 23
3.1 實驗藥品 24
3.2 實驗儀器 25
3.3 試片製備與分析 26
3.3.1 氧化鋅試片製備與分析 26
3.3.2 氧化鋅試片前處理 26
3.3.3 EBSD取樣面積 27
3.3.4 氧化鋅催化劑溶出反應 28
3.3.5 實驗分析儀器 28
第四章 結果與討論 30
4.1 氧化鋅粉末與錠之分析 30
4.1.1 晶體結構分析 30
4.1.2 氧化鋅錠微結構觀察 31
4.2 氧化鋅溶出反應 32
4.2.1 EBSD取樣面積收斂測試 32
4.2.2 試片差異性測試 34
4.2.3 油酸溶出反應 36
4.2.3.1 表面粗糙度變化 36
4.2.3.2 油酸150 ℃溶出反應 43
4.2.3.3 油酸125 ℃溶出反應 50
4.2.3.4 油酸100 ℃溶出反應 56
4.2.3.5 油酸75 ℃溶出反應 62
4.2.3.6 油酸50 ℃溶出反應 67
4.2.4 表面反應 74
第五章 結論與未來展望 83
5.1 結論 83
5.2 未來展望 84
參考文獻 85

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