臺灣博碩士論文加值系統

本研究選擇商用CuO/ZnO/MgO/Al2O3觸媒作為具銅鋅界面效應觸媒以及自製高分散性銅鈰觸媒作為具銅鈰界面效應觸媒，比較二者在甲醇蒸氣重組反應動力學上的差異，以了解不同界面效應對反應特性的影響。藉由XPS、AES、EXAFS、TPR及N2O吸附分析二種觸媒特徵與活性面積。自製銅鈰觸媒經XPS與銅分散度確認具大量Cu-Ce界面。反應測試結果顯示商用銅鋅觸媒的TOF略高於銅鈰觸媒。為了解此二觸媒於甲醇蒸汽重組反應特性差別，選取10Cu/CeO2觸媒與商用CuO/ZnO/MgO/Al2O3觸媒，在甲醇分壓(18.8~37.6 kPa)以及水分壓(25.0~50.0 kPa)範圍，分析銅鋅觸媒以及銅鈰觸媒的動力學特性；銅鋅觸媒以及銅鈰觸媒對甲醇蒸氣重組反應的甲醇反應級數分別為0.83以及0.75，對水的反應級數則分別為-0.4以及-0.01。篩選文獻中報導不同的反應機制模型對應的反應速率式，以研究數據代入分析以確認是否符合，結果顯示商用CuO/ZnO/MgO/Al2O3觸媒與10Cu/CeO2觸媒皆符合以甲氧基裂解脫氫為反應速率決定步驟的反應機制模型，但因Cu-Zn界面與Cu-Ce界面的作用不同，以致此二觸媒活性位置吸附特性有所差異導致反應動力學參數的差異。

In order to compare cu-zn interface with cu-ce interface on kinetic analysis of methanol steam reforming, Cu/ZnO/MgO/Al2O3 and Cu/CeO2 with highly cu dispersion is selected as cu-zn interface catalyst and cu-ce interface catalyst. With analysis of XPS, AES, EXAFS, TPR and N2O, the features and activation area of this two kind of catalysts are realized. The results of methanol steam reforming show TOF of CuO/ZnO/MgO/Al2O3 catalyst is a little higher than Cu/CeO2.
Further to compare CuO/ZnO/MgO/Al2O3 with Cu/CeO2 on features of methanol steam reforming reaction, 10Cu/CeO2 is selected to compare with CuO/ZnO/MgO/Al2O3. Features on kinetic analysis of cu-zn catalyst and cu-ce catalyst are analyzed at different Pmethanol and Pwater. Methanol reaction order of cu-zn catalyst and cu-ce catalyst is 0.83 and 0.75, and water reaction order is -0.4 and -0.01. Selecting rate equations, reported on literatures, then equations are fitted with data of this study. The rate determine step of two catalysts both are methoxy decomposition reaction. Because effect of cu-zn interface and cu-ce interface are different, the cu-zn catalyst fits the mechanism with one kind of active site, and cu-ce catalyst fits the mechanism with two kinds of active site.

目錄
摘要 I
Abstract II
誌謝 III
目錄 IV
圖目錄 VI
表目錄 XI
第一章 緒論 13
1.1 前言 13
1.2 文獻回顧 15
1.2.1 銅觸媒與擔體影響 15
1.2.2 甲醇蒸氣重組反應 17
第二章 研究設備與方法 21
2.1 研究目的 21
2.2 研究架構與方法 21
2.3 藥品與儀器設備 22
2.3.1 藥品部分 22
2.3.2 氣體部分 22
2.3.3 儀器部分 22
2.4 觸媒製備 23
2.4.1 SBA-15中孔洞氧化矽基材製備 23
2.4.2 Cu/CeO2觸媒製備 23
2.4.3 KATALCOJM51-8商用觸媒製備 24
2.5 觸媒特性分析 24
2.5.1 感應耦合電漿原子放射光譜儀 24
2.5.2 表面積及孔隙測定儀 25
2.5.3 穿透式電子顯微鏡分析 25
2.5.4 X-ray powder diffraction 25
2.5.5 NSRRC X-ray powder diffraction 25
2.5.6 X-ray光電子能譜儀&歐傑電子能譜儀 25
2.5.7 NSRRC EXAFS 26
2.5.8 程溫還原反應、分散度及活性面積鑑定 26
2.6 甲醇蒸氣重組反應 27
2.6.1 甲醇蒸氣重組反應測試 27
2.6.2 Power law’s 反應速率式分析 27
2.6.3 反應機制分析 27
第三章 結果與討論 28
3.1 觸媒特性鑑定 28
3.2 甲醇蒸氣重組反應 51
3.3 Power law’s動力學分析 57
3.4 反應機制分析 65
第四章 結論 75
Reference 76
附錄A A
附錄B E

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