臺灣博碩士論文加值系統

本研究旨在探討Au/C觸媒催化乙二醇液相選擇性氧化反應之動力學特性，主要討論影響反應的動力學條件包括有觸媒種類、Au/C觸媒使用量、氧化反應溫度、乙二醇添加量與氫氧化鈉鹼液添加量等效應。
首先比較討論Au/C(WGC)、Pt/C(E-tek)、Pd/C(home-made)與Au sol(京華堂)等四種不同的觸媒對於催化EG氧化反應的影響，結果顯示用Au/C觸媒催化的反應轉化率與GA產物選擇率均優於其他三種觸媒。由Au/C觸媒用量對反應活性之影響，金屬觸媒用量由0.0016g/L~0.016g/L，可見反應速率正比於Au/C觸媒用量。由反應溫度的結果，溫度為40~70℃，顯示在70℃時反應轉化率及GA選擇率最好，反應活化能(EAapp)為21 kJ/mol。由不同EG添加量的影響，顯示反應速率隨著EG添加量的增加而減少。從不同鹼液添加量對反應活性的影響，[OH]0添加量為81.63 mM、40.82 mM、20.4 mM、0 mM，顯示反應速率隨著鹼液添加量增加而提升。

The purpose of this study is focus on the kinetics of the selective oxidation reaction of ethylene glycol catalyzed by Au/C catalyst. Factor such as the type of catalyst, amount of catalysts added, temperature, ethylene glycol recruitment, and concentration of NaOH were investigated in this work.
Results showed that Au/C has the best activity and glycolic acid selectivity for ethylene glycol selective oxidation reaction amount catalysts of Au/C(WGC), Pt/C(E-tek), Pd/C(home-made) and Au sol. Further, the reactivity for is fond to be proportion to the amount of Au/C added in the range of 0.0016g/L~0.016g/L. The reactivity for is fond to be inverse proportion to the amount of ethylene glycol added in the range of 10mM??100mM. From the different concentration of NaOH, best the reactivity for is fond to be proportion to the concentration of NaOH added in the range of 0~81.63mM.

摘要 I
Abstract II
誌謝 III
目 錄 IV
圖目錄 VI
表目錄 VIII
第一章 緒 論 1
1.1 研究緣起 1
1.2 影響金觸媒催化的因素 2
1.3 研究動機 7
1.4 研究目的與方法 10
第二章 理論基礎與文獻回顧 11
2.1 金觸媒催化反應的應用 11
2.1.1 甲醇部分氧化之製氫反應 11
2.1.2 碳氫化合物選擇性氧化反應 11
2.1.3 一氧化碳氧化反應 11
2.1.3 一氧化碳氧化反應 12
2.1.4 水氣轉移反應 12
2.1.5 有機揮發物質之氧化反應 12
2.2 金觸媒催化液相醇類之選擇性氧化反應 13
2.3 影響金觸媒催化醇類液相選擇性氧化反應的因素 19
2.3.1 金前驅體: 20
2.3.2 保護劑(分散劑): 20
2.3.4 擔體種類: 24
2.3.5 觸媒合成方法: 24
2.3.6 反應液相pH值: 24
2.3.7 氧化反應之操作溫度: 25
2.4 金與鉑、鈀金屬觸媒催化各種醇類氧化反應之比較 28
2.5 金觸媒催化各種醇類液相氧化的動力學特性 29
第三章 實驗方法與步驟 36
3.1 實驗流程 36
3.2 實驗設計 37
3.2.1 化學藥品與氣體 37
3.2.2 實驗裝置與儀器 37
3.2.3 實驗方法 38
3.2.4實驗操作步驟 40
3.3 反應活性分析方法 42
3.3.1 取樣分析: 42
3.3.2再現性與空白反應測試 44
3.3.3 檢量線的建立 45
3.3.4 反應轉化率與選擇率定義 45
第四章 結果與討論 47
4.1 觸媒種類的影響 47
4.2 Au/C觸媒用量對EG氧化反應速率的影響 58
4.3 反應溫度的影響與活化能 62
4.4 EG添加量對Au/C觸媒催化EG氧化反應速率之影響 68
4.5 鹼液添加量對Au/C觸媒催化EG氧化反應速率之影響 72
4.6 反應速率方程式的推導 101
結論 102
參考文獻 103
附錄 109
附錄A GC再現性與穩定性之測試結果 109
附錄B 乙二醇氧化空白反應測試 115
附錄C 各標準品的檢量線 116
附錄D 乙二醇、乙醇酸、草酸的一般物性與熱力、輸送物性[84] 118
附錄E 用積分法、微分法分析動力學條件對反應活性的影響 119
附錄F 數值分析方法解方程式(4.16)式 123
附錄G 用積分法分析文獻Au/C觸媒催化各種醇類液相氧化反應特性 127

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