隨著世界工業、科技業爆炸性發展，人類大量開採造成能源危機，將引發能源缺乏、環境汙染與溫室效應等問題，因此具有永續、低汙染、乾淨之替代性能源逐漸成為眾所矚目的焦點，而生質柴油更為替代性能源中重要之發展項目之一。但隨生質柴油相關研究日與漸增，轉酯化後不可避免之副產物甘油大量產出，至使其市場趨於飽和，因此尋找甘油之高值化應用為鞏固甘油價格及提升原料經濟價值之最佳解決方式。
本研究使用Dean-Stark反應系統進行高溫之甘油醚化反應生成目標產物二聚甘油與三聚甘油等寡聚甘油，藉由GC、GC-MS、NMR確定產物組成與定量分析。首先以硫酸及氫氧化鈉進行均相反應測試，藉以確立反應效果、酸鹼催化特性及產物組成，隨後使用ZSM5沸石進行反應並以硝酸鈣改質，實驗參數包括動力學分析、觸媒使用量、改質量與濃度、矽鋁比與擔載活性物等。同時使用XRD、IR、SEM、EDS、TPD、BET、TGA鑑定觸媒特性，探討反應結果與觸媒特性關係，最後利用天然礦物高嶺土合成較低矽鋁比之沸石進行醚化反應性測試與回收再利用效果討論。
從實驗結果得知，經醚化反應後之產物成分為甘油、二聚甘油、三聚甘油、環狀二聚甘油、環狀三聚甘油及少量副產物如丙烯醛等醛類結構。以改質後Ca/ZSM5進行醚化反應在溫度250~260 ℃、持續反應8小時、觸媒使用量 2wt%可以得到超過85%之甘油轉化率，22%二聚甘油、58%三聚甘油之產物，未改質之低矽沸石LTA可達約65%甘油轉化率、32%二聚甘油、31%三聚甘油。
本實驗成功鑑定醚化反應之產物成分，並有效的以Ca改質沸石觸媒ZSM5進行催化，並尋找出觸媒最適化條件且輔以儀器分析，最後以性質較鹼之沸石進行比較，探討均相、非均相催化效果之特性及可行性。

In this study, the zeolite ZSM5 were chosen to catalyze the etherification reaction of glycerol to polyglycerol (mainly, diglycerol + triglycerol) in a Dean-Stark apparatus as a batch reactor. Zeolite ZSM5 was modified by the incipient wetness impregnation method with calcium nitrate to enhance the yield and selectivity. After the modification, the solids were rinsed thoroughly with deionized water and calcined at 500 oC. Zeolitic properties were characterized with XRD, FT-IR, SEM, BET, TGA and TPD. Etherification reaction was tested with different kinds of catalysts: acid homogeneous (sulfuric acid), base homogeneous (NaOH), heterogeneous (e.g. zeolite H-ZSM5, Ca-impregnated zeolite ZSM5 (Ca/ZSM5), as-synthesized zeolite of Linde Type A (zeolite LTA)), and other supported alkaline earth metals (Mg, Sr) were also examined for comparison. The products were analyzed by GC-BID, GC-MS, and 13C-NMR to gather the information of the product mixture (linear and cyclic di-, tri-glycerol). Variables of the catalyzed etherification process, such as catalyst-to-glycerol ratio, catalyst Si/Al ratio, operation temperature, modification concentration and kinetics, were studied in order to optimize the reaction condition. The combined yield and selectivity of polyglycerol (diglycerol + triglycerol) under optimal conditions exceeded 85% and 80% after 6 h of reaction proceeding at 260 ℃ with Ca/ZSM5 catalyst. According to Arrhenius equation, the activation energy of the pseudo-first order reaction was estimated as of 107.71 kJ/mol, confirming the high energy barrier in such catalyzed etherification of glycerol.

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