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Student Number 92324019
Author Hsin-Yin Yu(余心印)
Author's Email Address 92324019@cc.ncu.edu.tw
Statistics This thesis had been viewed 1561 times. Download 860 times.
Department Chemical and Materials Engineering
Year 2004
Semester 2
Degree Master
Type of Document Master's Thesis
Language zh-TW.Big5 Chinese
Title Production of hydrogen via partial oxidation of methanol over Au/TiO2 catalysts
Date of Defense 2005-06-28
Page Count 112
Keyword
  • deposition-precipitation
  • gold catalyst
  • hydrogen
  • partial oxidation of methanol
  • titania support
  • Abstract Selective production of hydrogen by partial oxidation of methanol (CH3OH + 1/2O2 → 2H2 + CO2) over Au/TiO2 catalysts, prepared by deposition-precipitation method was studied. The catalysts were characterized by ICP-AES, TGA, XRD, TEM, and XPS analyses. TEM observations show that the Au/TiO2 catalysts exhibit hemispherical gold particles, which are strongly attached to metal oxide support at their flat planes. The size of the gold particles decreases from 3.9 nm to 1.8 nm with the rise in pH during preparation of the catalysts 6 to 9 and increases from 3.0 nm to 4.7 nm with the rise in calcination temperature up to 673 K. XPS analyses demonstrate that in uncalcined catalysts gold existed in three different states i.e. metallic gold (Au0), non-metallic gold (Auδ+) and Au2O3 and in catalysts calcined at 573 K only in metallic state. The catalytic activity is strongly dependant on the gold particle size, with smaller particles produces higher hydrogen selectivity. The catalyst precipitated at pH 8 and uncalcined catalysts show highest activity for hydrogen generation. The partial pressure of oxygen plays an important role in determining the product distribution. There is no carbon monoxide detected, when the O2/CH3OH molar ratio in the feed is 0.3. Both hydrogen selectivity and methanol conversion increase with increasing the reaction temperature. The reaction pathway is suggested to consist of consecutive methanol partial oxidation, methanol decomposition, and methanol steam reforming.
    Table of Content 內容?????????????????頁數
    中文摘要………………………………………………………………Ⅰ
    英文摘要………………………………………………………………Ⅲ
    目錄……………………………………………………………………Ⅴ
    圖索引…………………………………………………………………Ⅸ
    表索引………………………………………………………………ⅩⅢ
    第一章 緒論…………………………………………………1
    1.1 前言……………………………………………………………1
    1.2 燃料電池原理…………………………………………………...1
    1.3 燃料電池的種類………………………………………………...4
    1.4 甲醇製氫………………………………………………………..6
    1.5 金觸媒…………………………………………………………..7
    1.6 研究內容與論文架構…………………………………………...8
    第二章 文獻回顧…………………………………………….9
    2.1 金的物性與化性 ……………………………………………...9
    2.2 金觸媒的製備方法…………………………………………….10
    2.3 煅燒程序……………………………………………………….15
    2.4 擔體效應……………………………………………………….16
    2.5 金的活性位置………………………………………………….17
    2.6 金觸媒的應用………………………………………………….21
    2.6-1 低溫一氧化碳氧化反應……………………………………21
    2.6-2 有機揮發物質氧化反應……………………………………26
    2.6-3 水氣轉移反應………………………………………………27
    2.6-4 碳氫化合物選擇性氧化反應………………………………28
    2.6-5 甲醇部分氧化反應…………………………………………28
    第三章?篘蝷隤k與裝置…………………………..……….31
     3.1 奈米金觸媒的製備…………………………………………….31
    3.2 觸媒代號說明………………………………………………….33
    3.3 奈米金觸媒的鑑定分析……………………………………….33
    3.3-1 感應耦合電漿原子放射光譜儀(ICP-AES)分析……….34
    3.3-2 觸媒總表面積、孔隙體積及孔徑大小分析……………….35
    3.3-3 熱重分析(TGA)………………………………………….37
    3.3-4 X射線繞射分析(XRD)………………………………….37
    3.3-5 穿透式電子顯微鏡(TEM)……………………………….39
    3.3-6 掃瞄式電子顯微鏡分析(SEM)…………………………41
    3.3-7 X射線光電子分析(XPS)………………………………..43
    3.4 觸媒活性測試—甲醇部分氧化反應………………………….44
    3.5 實驗流程與操作變數………………………………………….49
    3.6 數據的計算與實例…………………………………………….52
    3.6-1 奈米金觸媒理論載量的定義與計算………………………52
    3.6-2 轉化率的定義與計算………………………………………52
    3.6-3 選擇率的定義與計算………………………………………57
    3.7 藥品、氣體及儀器設備……………………………………….59
    3.7-1 藥品…………………………………………………………59
    3.7-2 氣體…………………………………………………………59
    3.7-3 儀器設備……………………………………………………60
    第四章?痕G與討論……………………………………...…62
    4.1 物性分析……………………………………………………….62
    4.1-1 操作變數對金屬載量的影響………………………………..62
    4.1-2 煅燒條件的選擇……………………………………………63
    4.1-3 觸媒表面積測定……………………………………………66
    4.1-4 X射線繞射分析(XRD)…………………………………68
    4.1-5 穿透式電子顯微鏡分析(TEM)…………………………70
    4.1-6 掃瞄式電子顯微鏡(SEM)……………………………….76
    4.1-7 X射線光電子分析(XPS)……………………………….80
    4.2 化性分析……………………………………………………….82
    4.2-1 金載量對觸媒活性的影響…………………………………82
    4.2-2 煅燒溫度對觸媒活性的影響………………………………85
    4.2-3 pH值對觸媒活性的影響…………………………………..89
    4.2-4 進料比例對觸媒活性的影響………………………………90
    4.2-5 反應溫度對觸媒活性的影響………………………………97
    4.2-6 Au/TiO2觸媒與銅、鈀、鉑觸媒在甲醇部分氧化反應上之分析結果比較………………………………………………………..100
    第五章?結論……………………………………………103
    參考文獻……………………………………………………107
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    Date of Submission 2005-07-11

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