臺灣博碩士論文加值系統

本研究製做了支撐性的銅及銀觸媒，並用於催化甲醇部份氧化(partial oxidation of methanol, POM)反應(CH3OH + 1/2O2 → 2H2 + CO2)，希望發展出低溫且低CO污染的氫氣製程，並探討金屬種類、支撐物和溫度對反應活性及產物選擇率的影響。
銅觸媒(Cu/ZnO-Al2O3)是以共沉澱法和連續沉澱法來製備，觸媒的分散度(DCu)會受到製備方法的影響。使用共沉澱法製備出的DCu會比使用連續沉澱法要來的好；在製備觸媒時，調整溶液的pH值在7會比在9要來的好。在活性測試實驗中，甲醇轉化率會隨著觸媒中DCu和反應溫度的增加而提升，產物包含H2、H2O、CO2和CO。然而，當反應溫度低於175 ℃時，銅觸媒便會失去了活性。
銀觸媒是以共沉澱法(Ag/ZnO) 和初濕含浸法(Ag/Al2O3、Ag/ZnO-Al2O3)來製備。在催化POM反應方面，使用Ag/ZnO觸媒，可以得到較高的甲醇轉化率及氫氣選擇率。若是觸媒是以Al2O3做為支撐物(Ag/Al2O3、Ag/ZnO-Al2O3)，反應則會產生較多的H2O、HCHO和HCOOCH3。然而，不論是用ZnO或Al2O3做為觸媒的支撐物，即使反應溫度低於175 ℃，仍然可以得到不錯的催化活性。此外，我們由反應產物隨支撐物、溫度和金屬的變化推測了POM的反應機制。

Supported catalysts of copper and silver were prepared in this research for the partial oxidation of methanol (POM) reaction. We hope to develop a low temperature and low CO contamination POM process of hydrogen production, and to study effects of metal, support and temperature on reaction activity and product selectivity.
Copper catalysts (Cu/ZnO-Al2O3) were prepared by coprecipitation and sequential precipitation methods. The copper dispersion (DCu) was significantly affected by the preparation method and the pH of copper solution. The coprecipitation method and a solution with pH ~ 7 was preferred for preparation of high DCu catalysts. In activity measurements, the methanol conversion increased with DCu and reaction temperature, and produced H2、H2O、CO2 and CO. The light-off temperature of copper catalysts was found at 175 ℃.
Silver catalysts were prepared by coprecipitation (Ag/ZnO) and incipient wetness (Ag/Al2O3、Ag/ZnO-Al2O3) methods. Silver catalysts were generally active at T < 175 ℃, but their activity and selectivity varied with kind of support. Ag/ZnO catalyst exhibited high methanol conversion and hydrogen selectivity. Al2O3-supported silver catalysts (Ag/Al2O3、Ag/ZnO-Al2O3) displayed high yields of H2O、HCHO and HCOOCH3. Besides, a POM reaction mechanism had been proposed to account the effects of support、temperature and metal on the reaction activity and the product distribution.

第一章 緒論
1-1 前言
1-2 燃料電池(Fuel Cell)
1-3 甲醇製氫
1-4 銅和銀金屬觸媒
1-5 研究目的和方向
第二章 實驗
2-1 藥品
2-2 氧化銅樣品的製備
2-3 銅觸媒的製備
2-3.1 以共沉澱法(CP)製備銅觸媒
2-3.2 以連續沉澱法(SP)製備銅觸媒
2-4 銀觸媒的製備
2-4.1 以初濕含浸法(IW)製備銀觸媒
2-4.2 以共沉澱法(CP)製備銀觸媒
2-5 樣品的命名
2-6 觸媒的特性鑑定
2-6.1 熱分析儀(TG/DTA)
2-6.2 程溫還原反應(TPR)
2-6.3 BET表面積測定
2-6.4 元素分析(ICP-AES)
2-6.5 穿透式電子顯微鏡(TEM)
2-6.6 銅觸媒之分散度量測
2-7 觸媒的活性測試
第三章 結果與討論
3-1 氧化銅的特性鑑定
3-1.1 熱分析(TG/DTA)
3-1.2 程溫還原分析(TPR)
3-2 銅觸媒的特性鑑定
3-2.1 程溫還原分析(TPR)
3-2.2 分散度的量測
3-2.3 BET表面積測量
3-3 銀觸媒的特性鑑定
3-3.1 銀顆粒的大小分佈
3-4 銅觸媒的甲醇部份氧化(POM)反應之催化活性
3-4.1 溫度對催化活性的影響
3-5 銀觸媒的催化活性
3-5.1 支撐物對催化活性的影響
3-5.2 支撐物與反應溫度對選擇性的影響
3-5.3 POM反應機制
3-5.4 支撐物與反應溫度對反應機制的影響
3-5.5 氧醇比(nO2/nMeOH)對催化活性的影響
3-6 銅和銀觸媒催化特性的比較
3-7 未來的研究方向
第四章 結論
第五章 參考文獻

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