臺灣博碩士論文加值系統

自從世界對生質柴油產業之可再生能源需求不斷增加，副產物甘油的過量生產正式成為值得關注的問題。甘油和醇經過醚化反應合成甘油烷基醚在學術研究與工業議題上是項活躍的研究領域，尋找潛在的催化劑與最佳工業參數條件的可能性。在本研究中，使用二種催化劑硫酸鋁和三氟甲基磺酸鉍進行甘油醚化反應在批次式反應器下探討，透過使用正丁醇生產含氧添加劑。詳細反應條件研究包括：醚化反應之參數，如催化劑使用量（反應物總量0.01-20wt%），甘油/正丁醇的莫爾比(1：2-1：6)，反應溫度(230-270℃)和反應時間(2-7h)。結果顯示甘油的轉化率(>92%)可以在溫度(230-270℃)的溫度範圍內觀察到。反應在溫和的操作壓力(7-26 kg/cm2)下進行。甘油生產主要產品為單丁基甘油醚(ME)，二丁基甘油醚(DE)，三丁基甘油醚(TE)。在反應後之產物混合物在室溫下透過冷卻過程使其自動分離成油相與水相溶液。並將產物油相透過簡單的熱重分析儀分析汽油與柴油的組成並定為辛烷值添加劑。透過氣相層析儀(GC)與熱重分析法(TG)來分析油相產物的組成。本研究也將討論觸媒的再循環性。

Since the world’s growing demand for renewable energy in biodiesel industry, overproduction of glycerol is becoming an issue of concern. Etherification of glycerol with alcohol to synthesize the alkyl ethers of glycerol is an active research area of academic and industrial issues to explore the possibility to identify the potential catalysts and optimize the process parameter. In this work, the catalytic etherification of glycerol has been investigated with two kinds of catalyst, Aluminum Sulfate and bismuth(III) trifluoromethanesulfonate, in a batch reactor by using n-butanol to produce oxygenated additives. A detailed study of the reaction conditions includes catalyst loading (0.01-20 wt % total amount of reactants), molar ratio of glycerol/n-butanol (1: 2 to 1: 6), reaction temperature (230-270℃), and reaction time (2-7 h). The results indicate that the high conversion (>92%) of glycerol can be observed at the temperature ranges (230-270℃) and operating pressure (7-25atm). The glycerol products towards mono-butyl-glycerol ether (ME), di-butyl-glycerol ether (DE), and tri-butyl-glycerol ether (TE). After the reaction, the product mixture was automatically separated into an organic phase and an aqueous phase through the cooling process at room temperature overnight. Furthermore, the components in the organic phase can be tailored to an octane booster for gasoline and a diesel-like fuel by a simple distillation. The composition of oil phase products are analyzed by gas chromatography (GC) and thermogravimetric (TG) methods. The recyclability of catalyst are also discussed in this work.

中文摘要 I
英文摘要 II
致謝 III
目錄 IV
圖目錄 VII
表目錄 X
第一章 緒論 1
1.1 前言 1
1.2 生質燃料 2
1.3 甘油的應用 3
1.4 含氧添加劑 4
1.5 酸性觸媒 5
1.5.1 硫酸鋁觸媒介紹 5
1.5.2 三氟甲基磺酸鉍觸媒介紹 6
1.6 甘油轉化的文獻回顧 6
1.7 研究動機 12
第二章 實驗方法 13
2.1 實驗藥品與條件 13
2.2 反應系統 14
2.3 實驗步驟 15
2.4 產物分析 16
2.4.1 SEM-EDS分析 16
2.4.2 氣相層析質譜儀 (GC-Mass) 分析 17
2.4.3 氣相層析儀 (GC) 分析 18
2.4.4 酸價滴定分析 18
2.4.5 熱重分析 19
第三章 以硫酸鋁觸媒催化甘油與正丁醇之醚化反應 22
3.1 使用硫酸鋁觸媒之不同反應條件 22
3.1.1 時間與催化劑用量對反應之響 22
3.1.2 溫度對反應之影響 23
3.1.3 反應物比例對反應之影響 24
3.2 以硫酸鋁觸媒反應之 SEM-EDS 分析 24
3.3 以硫酸鋁觸媒反應之 GC-MASS 分析 26
3.4 以硫酸鋁觸媒反應之 GC 分析 31
3.5 以硫酸鋁觸媒反應之 TG 分析 35
3.6 以硫酸鋁觸媒萃取回收之重複反應分析 38
3.7 以硫酸鋁觸媒反應之酸價分析 39
3.8 以硫酸鋁觸媒催化甘油與正丁醇之醚化結果探討 42
第四章 以三氟甲基磺酸鉍觸媒催化甘油與正丁醇之醚化反應 43
4.1 不同觸媒用量與反應時間分析 43
4.2 以三氟甲基磺酸鉍觸媒反應之 SEM-EDS 分析 45
4.3 三氟甲基磺酸鉍之三種不同觸媒萃取回收流程圖 46
4.4 比較Process II與Process III反應後油層酸價與純水萃取次數關係 47
4.5 Process I、Process II與 Process III反應後油層酸價分析 50
4.6 Process I、Process II與 Process III反應後油產率分析 52
4.7 以三氟甲基磺酸鉍觸媒反應產物之 GC-MASS 分析 54
4.8 Process I、Process II與 Process III反應後油產物之GC分析 55
4.9 以三氟甲基磺酸鉍觸媒催化甘油與正丁醇之醚化結果探討 57
第五章 結論 58
參考文獻 60

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