對氯苯胺(p-Chloroaniline；p-CA)是有機合成、精細化工中間體的重要化工原料，廣泛應用於醫藥、有機合成、農藥、溶劑、染料、顏料、橡膠助劑等各領域中，主要應用於生產苯酚、硝基苯、苯胺、二苯醚以及殺蟲劑DDT等。
p-CA可由對氯硝基苯(p-Chloronitrobenzene；p-CNB)的直接氫化得到。在鹵素硝基芳香族的選擇性氫化製程中，沒有脫氯反應的產生是我們最希望得到的結果，而這個選擇性的結果則取決於觸媒的種類與反應的條件。在鹵素硝基芳香族之氫化中，常因為Hydro- Dehalogenation的發生造成一些副產物的生成，為避免不必要的反應發生，反應製程與觸媒的選擇是最重要的。本研究以p-CNB之觸媒氫化為反應系統，並於實驗中選用自行製備之奈米Ni-B觸媒，此觸媒是依中央大學陳郁文教授實驗室所提供的觸媒製備方法，以化學還原法所製得的Ni-B奈米合金觸媒。此觸媒對於主要產物p-CA的選擇率能達到99 %以上，可避免過度氫化的現象。
在氫化反應過程中，由於氫氣在有機溶劑中之溶解度不高，氣液間會存在著相當大之界面質傳阻力，此外在液體內部的擴散阻力也會對反應速率造成限制。本研究中在半批次操作下進行存在高壓二氧化碳之氫化反應，分別以不同反應物濃度、操作壓力、溫度及二氧化碳分壓比例為變數，用以觀察高壓二氧化碳的存在對氫化反應之影響。由實驗結果可知對於此p-CNB氫化反應，二氧化碳的存在是可以提升p-CNB轉化率的。在溫度為343、353或363 K下進行氫化反應，結果顯示不論在低溫或高溫下含有二氧化碳時的p-CNB轉化率皆大幅的提升，提升比例高達60 %以上。而在不同溫度操作時，反應系統中存在二氧化碳之最佳分壓比例亦有所不同，其分壓比例值由363 K時的20 %變成353及343 K時的10 %。而溫度353 K下存在二氧化碳之氫化反應時的p-CNB轉化率可高於363 K純氫氣實驗時的轉化率，意即在較低溫與較低的氫氣壓力下就可得到相同的轉化率，如此便能達到降低操作成本的成效。
從膨脹度實驗以及平衡溶解度實驗數據來看，二氧化碳的引進確實造成了甲醇體積的膨脹與氫氣溶解度的增加。CO2的存在使甲醇形成CO2-Expanded Methanol，除了可增加氫氣溶解度外，亦因溶劑體積膨脹導致液體密度與黏度的降低，而減少質傳阻力，例如液相中之擴散阻力，進而使p-CNB轉化率增加。

摘要 I
目錄 III
表目錄 IV
圖目錄 V
壹、緒論 1
貳、文獻回顧 6
2.1 硝基芳香族之觸媒選擇性氫化反應 7
2.2 Ni-B奈米觸媒之研究 10
2.3 存在高壓二氧化碳之應用與化學反應研究 13
2.4 CO2-Expanded Solvent之研究 17
參、實驗方法 25
3.1. 實驗儀器與藥品 26
3-1-1實驗儀器 26
3-1-2 實驗藥品 27
3.2. Ni-B奈米觸媒製備步驟 28
3.3. 對氯硝基苯之氫化反應 29
3.4. 甲醇之體積膨脹度反應 30
3.5. CO2 + H2 +MeOH三元系統之平衡溶解度 30
肆、實驗結果與討論 38
4.1 p-CNB氫化反應 38
4.1.1 轉速的影響 38
4.1.2 p-CNB初濃度的影響 39
4.1.3 壓力與溫度的影響 40
4.2 甲醇體積膨脹度實驗 43
4.3 H2+CO2+MeOH三元系統中之氫氣溶解度 44
伍、結論 77
陸、參考文獻 79

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