臺灣博碩士論文加值系統

本論文之目的為進行丙烯環氧化反應，利用第三丁基過氧化氫(TBHP)作為氧化劑氧化丙烯成環氧丙烷，並改變操作條件以觀察對反應之影響，期能達到足以商業化之結果。

催化丙烯之環氧化反應的觸媒分別有均相與異相兩種，異相中之鈦觸媒或均相中之鉬觸媒，皆可以得到極佳的反應結果。本論文著重於均相之鉬觸媒，採用Mo(CO)6作為催化劑。以第三丁基過氧化氫(TBHP)作為氧化劑，第三丁基醇(TBA)作為溶劑，於高壓反應器進行環氧化反應。分別探討溶劑種類、反應濃度、反應溫度、反應時間、觸媒添加量等因素，並進行動力學與活化能之探討。溫度、丙烯濃度、觸媒量對此反應有顯著影響，發現較適當的其中溫度範圍為110至120°C，觸媒量範圍為200至500ppm，丙烯/氧化劑莫耳比大於15。在最佳操作條件下，可得環氧丙烷之產率為91.6%，TBHP轉化率為99.09%，PO選擇率為92.43%，反應動力學符合TBHP吸附之Eley-Rideal mechanism，活化能為133kJ/mole，吸附熱為-33kJ/mole。

This thesis is to study the epoxidation kinetics of propylene to propylene oxide using tert-butyl hydroperoxide (TBHP) as the oxidant.

There are two different catalyst for in the epoxidation of propylene; homogeneous molybdenum and heterogeneous titanium. Both are able to obtain excellent reaction results. This study focus on the homogeneous molybdenum catalyst, Mo(CO)6. Tert-butyl hydroperoxide (TBHP) as the oxidant, tert-butyl alcohol (TBA) as the solvent, and the epoxidation reaction is carried out in a high pressure reactor. By changing solvent species, reactant concentration, reaction temperature, reaction time, catalyst amount, we obtain the kinetics and activation energy. Temperature, propylene concentration of propylene, and the quantity of the catalyst have significant effects on this reaction, and is the appropriate temperature range is about 110 and 120°C, catalyst concentration range is between 200 and 500 ppm, the ratio of propylene to oxidant is greater than 15. Under the optimum reaction condition, we obtained a propylene oxide yield of 91.6% at TBHP conversion of 99.09% (PO selectivity is 92.43%), Based on the Rley-Rideal mechanism, a formal kinetic model is used to fit the experience data. The activation energy is 133kJ/mole and the heat of adsorption is -33kJ/mole.

目錄
摘要
英文摘要
目錄 I
表目錄 IV
圖目錄 V
第一章 緒論 1
1.1 環氧化物 1
1.2 環氧丙烷之歷史沿革 4
1.3 環氧丙烷簡介 6
1.4 環氧丙烷的製備法 8
1.6 環氧化反應之反應機構與觸媒選擇 12
1.7 研究動機 16
第二章 實驗 17
2.1 實驗裝置 17
2.2 丙烯環氧化 21
2.2.1 環氧化反應實驗步驟 21
2.3 產物分析 22
2.3.1 碘滴定分析 22
2.3.2 氣相層析儀分析 23
2.3.3 火焰離子偵測器 (FID) 25
2.3.4 定性分析 26
2.4 定量分析(內部標準品法) 28
2.5 實驗藥品及儀器 31
第三章 結果與討論 33
3.1 氧化劑濃度計算法 33
3.1.1 定義產率、轉化率及選擇率 34
3.2 丙烯之環氧化反應 35
3.2.1 不同溶劑對環氧化反應之影響 35
3.2.2 改變反應溫度對於環氧化反應之影響 37
3.2.3 改變觸媒濃度對環氧化反應之影響 41
3.2.4 改變丙烯量對環氧化反應之影響 44
3.2.5 進行動力學分析 48
3.3 以70wt%TBHP in water為氧化劑進行丙烯環氧化反應 56
3.3.1 改變反應溫度進行環氧化反應 56
3.3.2 改變反應時間進行環氧化反應 59
第四章 結論 60
參考文獻 62

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