臺灣博碩士論文加值系統

甘油為製造生質柴油過程中所衍生之副產物。隨著生質柴油需求量的增加，甘油之產量也與日俱增。然而傳統甘油之使用途徑，例如做為食品添加劑或民生用品等用途已無法與廢甘油之成長速率相匹配。過剩的廢甘油多採儲藏之方式處理，造成環境污染與增加生質柴油製造之成本。如何利用生產生質柴油所衍生的過剩甘油已成為迫切的課題。本研究以鉑、鑭錳波洛斯凱特及鉑擔載於鑭錳波洛斯凱特之蜂巢狀觸媒，以毫秒範圍之接觸時間下轉化甘油為合成氣。反應過程中無需提供額外之熱源(熱自發)。反應條件操控於甘油與氧之碳/氧比於0.8至1.2間；水蒸氣與甘油比值介於0至4/3。研究顯示，鑭錳波洛斯凱特擁有良好的反應活性，但對於合成氣之選擇率較低。相對的，鉑催化劑在合成氣選擇率的表現最佳，但反應性較差。結合鉑與鑭錳波洛斯凱特於碳/氧比值為0.8且水蒸氣與甘油比值於2/3之條件下可達到最佳的轉化率與合成氣之選擇率。由連續28小時的觸媒壽期測試結果、以及XRD與FE-SEM探討反應前後之觸媒形貌變化，證實鉑擔載於鑭錳波洛斯凱特擁有最佳化的表現是由於鑭錳波洛斯凱特有抑制鉑高溫燒結之能力。

關鍵字： 甘油、氫氣、合成氣、部分氧化、波洛斯凱特

Glycerol and glycerol/water solution were converted to syngas over Pt-, LaMnO3-, and Pt/LaMnO3-coated monoliths under autothermal partial oxidation. XRD and SEM were used to characterize the phase compositions and surface morphologies of freshly prepared and postreaction catalysts. A continuous fixed-bed design, without an upstream vaporizer or external heat supply, was operated at millisecond contact times. Among the catalysts used in this study, Pt was the least reactive, and its activity was found to be reduced by sintering. Pt also tended to produce nonequilibrium products such as ethylene and acetaldehyde in fuel-rich environments. In contrast, LaMnO3 was found to favor glycerol combustion, producing fewer minor products and generating sufficient heat to sustain autothermal operations in fuel- and steam-rich regimes. Pt supported on LaMnO3 showed a synergistic effect of Pt sintering suppression and a broad H2/CO distribution in the resulting syngas. This effect can be correlated to the interaction between Pt and LaMnO3.

Keyword：Glycerol；Hydrogen；Syngas；Partial oxidation；Perovskite

目錄
摘要 I
Abstract II
目錄 III
表目錄 VI
圖目錄 VII
第一章 前言 1
1.1 引言 1
1.2 研究動機 4
第二章 文獻回顧 5
2.1甘油產氫相關反應 5
2.1.1 裂解 5
2.1.2 蒸氣重組 7
2.1.3 部分氧化和自供熱重組 8
2.1.4 液相重組 10
2.2 甘油之催化反應 11
2.2.1 蒸氣重組 11
2.2.2 部分氧化與熱自發重組 22
2.2.3 液相重組 26
2.2.4 結論 34
2.3 蜂巢狀陶瓷載體 36
2.4 波洛斯凱特觸媒特性 38
第三章 實驗 40
3.1 Ｘ光繞射儀 40
3.2 掃描式電子顯微鏡 41
3.3 全自動程序升溫化學吸附儀 42
3.3.1 氫程溫還原反應(H2-TPR) 43
3.3.2 氧程溫氧化反應(O2-TPO) 44
3.3.3 氧程溫脫附反應(O2-TPD) 45
3.4 氣相層析儀原理 46
3.5 氣體產物定性與定量分析 49
3.6 氣相層析質譜儀原理 52
3.7 液體產物定性與定量分析 54
3.8 觸媒製備 56
3.9 觸媒活性測試 60
3.10 實驗藥品與設備 64
第四章 結果與討論 66
4.1 貴金屬鉑與鑭錳波洛斯凱特觸媒之研究 66
4.1.1 觸媒XRD 物性鑑定 66
4.1.2 觸媒SEM 物性鑑定 68
4.1.3 雙層觸媒反應活性測試 70
4.1.4 單層觸媒反應活性測試 79
4.1.5 觸媒活性壽期測試 86
4.1.6 討論 88
4.2 改變鑭系波洛斯凱特B-side (B=Mn, Ni)研究 91
4.2.1 觸媒XRD 物性鑑定 91
4.2.2 觸媒SEM和EDX物性鑑定 93
4.2.3 氫程溫還原反應測試 95
4.2.4 雙層觸媒反應活性測試 97
4.2.5 單層觸媒反應活性測試 101
4.2.6 甘油熱裂解與蒸氣重組之活性測試 105
4.2.7 Water-Gas Shift Reaction (WGS)活性測試 109
4.2.8 反應性討論 111
4.3 甘油脫水氧化反應製備丙烯酸之初步研究 113
4.3.1 甘油熱裂解測試 114
4.3.2 LaMnO3活性測試和老化測試 116
第五章 結論 119
第六章 未來方向 120
參考文獻 121
發表文獻 132
附件一 133
附件二 147
附件三 163

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