臺灣博碩士論文加值系統

本研究旨在開發一個能於常壓下將甲醇、一氧化碳及氧轉化為碳酸二甲酯的非均勻相觸媒，並探討最佳的反應條件及能達到的最大產率。
活性測試是在常壓下進行，使用一個連續流動的微型反應器。標準的反應條件為溫度190℃、空間速度1468 h-1、進料組成(莫耳比)CH3OH：CO：O2=50：36：14、進料流率24 cm3/min(STP)。反應時的主要產物為碳酸二甲酯，副產物為甲酸甲酯、二甲氧基甲烷以及二甲醚。
首先進行的是觸媒的篩選，在CuCl2/C、CuCl/C及PdCl2/C三個觸媒中進行反應活性的測試，結果發現僅CuCl2/C具有活性，觸媒中CuCl2的含量在13.5wt%時為最佳；另外發現添加PdCl2、KOH及CH3COOK等成分於CuCl2/C中，皆沒有促進CuCl2/C活性的效果，非但如此，它們的添加，反而造成CuCl2/C活性的下降。
其次進行的是最佳反應條件測試，測試時每次改變一個變數，測試範圍為甲醇分壓0.1~0.5 atm；CO分壓0.075~0.36 atm；氧氣分壓0.03~0.14atm；反應溫度150~210℃及空間速度733 ~2933 h-1。在測試甲醇分壓對反應時，為維持進料流率不變，減少的甲醇流率以氮氣流率平衡之。在測試CO及O2分壓對反應的影響時亦採用相同的方法。測試的結果得到的最佳反應條件為甲醇分壓0.2 atm；CO分壓0.36 atm；氧氣分壓0.14 atm；溫度180℃；空間速度1185 h-1。在最佳進料的反應條件下可達成的甲醇轉化率為45%，碳酸二甲酯選擇率為63% 。
CuCl2/C觸媒在反應時有嚴重的活性衰退現象，在反應11小時後甲醇轉化率下降約70%，但碳酸二甲酯的選擇率則由反應初時的30%上升一倍至60%，推測造成此一現象的原因應與反應時觸媒上析出多種二價銅的結晶並流失許多的氯有關。

The purpose of this research was to develop a heterogeneous catalyst that could convert methanol, carbon monoxide, and oxygen to dimethyl carbonate (DMC) under atmospheric pressure. Finding the optimal reaction conditions to achieve maximum DMC yield was another goal to be accomplished.
Activity of catalyst was tested under atmospheric pressure, using a continuous flow micro-reactor. The standard reaction conditions were temperature 190℃, space velocity 1468 h-1, feed composition (molar ratio) CH3OH/CO/O2 = 50/36/14, and feed rate 24 cm3/min (STP). The main product of the studied reaction was dimethyl carbonate, and the byproducts were methyl formate, dimethoxy methane and dimethyl ether.
The investigation started with a catalyst screening. After activity tests, only CuCl2/C, among CuCl2/C, CuCl/C and PdCl2/C, showed some activity. The optimal loading of CuCl2 in CuCl2/C was found to be 13.5wt%. Adding PdCl2, KOH and CH3COOK to CuCl2/C could only result in lowering the activity of CuCl2/C.
The second step took in this research was to find the optimal reaction conditions. The experimental variables were changed one at a time. The range of the variables studied were partial pressure of methanol 0.1~0.5 atm, partial pressure of CO 0.075~0.36 atm, partial pressure of oxygen 0.03~0.14 atm, reaction temperature 150~210℃, and space velocity 733~2933 h-1. In studying the influence of partial pressure of methanol on the rate of reaction, the feed rate of methanol was varied, and the change was balanced by a nitrogen flow to maintain a constant total flow rate. The same technique was also used in the studies of the influences of carbon monoxide and oxygen. The optimal reaction conditions found in this investigation were partial pressure of methanol 0.2 atm, partial pressure of CO 0.36 atm, partial pressure of oxygen 0.14 atm, reaction temperature 180℃, and space velocity 1185 h-1. Under the optimal conditions, 45% of methanol conversion and 63% of dimethyl carbonate selectivity could be achieved.
CuCl2/C catalyst deactivated seriously during the reaction. The conversion of methanol dropped about 70% in 11 hours. However, at the mean time, the selectivity of dimethyl carbonate increased was doubled, raising from 30% to 60%. The appearance of several crystalline structures containing Cu2+ and the loss of chlorine in the catalyst was thought to be the reasons for the deactivation.

第一章 緒 論………………………..…………………………………1
第二章文獻回顧………………………………………………………5
2.1碳酸二甲酯的合成………………………………………………..5
2.1.1 光氣法………………………………………………………..5
2.1.2 酯交換法……………………………………………………..7
2.1.3 羰基化法……………………………………………………..8
2.1.4 其它製程……………………………………………………18
2.2 碳酸二甲酯的應用……………………………………………..19
2.2.1 取代氯化甲烷和硫酸二甲酯當作甲基化劑………………19
2.2.2 取代光氣當作羰基化劑……………………………………21
第三章實 驗…………………………………………………………24
3.1 實驗試料及氣體………………………………………………...24
3.1.1 實驗氣體……………………………………………………24
3.1.2 實驗藥品……………………………………………………24
3.2 觸媒的製備……………………………………………………..25
3.3 甲醇加氧羰基化反應…………………………………………..25
3.4 觸媒的鑑定……………………………………………………..29
3.4.1 BET表面積與孔隙度……………………………………….29
3.4.2 程式升溫脫附(TPD) ………………………………………32
3.4.3 X光繞射分析(XRD) ……………………………………..34
3.4.4 化學分析電子能譜(ESCA) ………………………………..34
3.4.5 EDX分析………………………………………………….35
第四章結果與討論………………………………………………….39
4.1 碳酸二甲酯之氣相合成反應…………………………………..39
4.1.1 各種觸媒的比較……………………………………………39
4.1.2 氯化銅含量的探討…………………………………………40
4.1.3 反應物濃度(分壓)的影響………………………………….42
4.1.4 溫度的影響…………………………………………………42
4.1.5 空間速度的影響……………………………………………47
4.1.6 觸媒活性的衰退……………………………………………47
4.2觸媒的鑑定………………………………………………………51
4.2.1 觸媒的物理性質……………………………………………51
4.2.2 氨氣程式升溫脫附…………………………………………55
4.2.3 反應物程式升溫脫附………………………………………55
4.2.4 XRD分析………………………………………………….58
4.2.5 化學分析電子能譜(ESCA)分析………………………..…62
4.2.6 EDX分析………………………………………………….66
第五章結 論…………………………………………………………71
參考文獻………………………………………………………………..72
附 錄……………………………………………………………………78
作者簡介………………………………………………………………..83

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