臺灣博碩士論文加值系統

酯化/部份氧化雙功能Pd / SDB( styrene-divinyl benzene copolymer)觸媒可將含水酒精催化反應生成乙酸乙酯，部份氧化反應會造成鈀金屬的聚集，酯化反應從自發性乙酸解離再藉由質子催化產生，並且酸觸媒的加入有利於酯化反應的產生，反應後並沒有直接証據証明氧化反應發生是由於吸收氧氣形成Pd —O。此外，伴隨著Pd的濾取，我們發現會因此而增加鈀金屬的聚集，Pd-Pd配位數會從原來的3.0增加到7.9，且觸媒上鈀的含量從1.0 wt%減少到0.55 wt%，然而酸性觸媒如Amberlyst 15的加入，可改善此種情形，但仍無法達到我們的要求，因此我們發展出雙功能Pd / Zeolite觸媒。為了了解觸媒結構對催化性質的影響，我們應用了EXAFS (Extended X — Ray Absorption Fine Structure )對觸媒進行特性分析。為了往後的商業應用，我們對觸媒進行了長期老化及再生實驗，並且應用TGA (Thermal Gravity Analysis )及TPO(Temperature Programmed Oxidation)來尋找最佳的再生溫度，在進行了三個多月的長期老化實驗後，我們發現乙醇的轉化率仍可維持在58 %，而乙酸乙酯的選擇率仍可維持大約在90 %，這顯示觸媒在長時間的反應後仍可維持非常好的穩定性及活性，且再生後觸媒其活性才約略的下降而已。

Catalyzed by styrene-divinyl benzene copolymer (SDB)-supported Pd (Pd/SDB) catalysts, ethyl acetate can be formed from water-containing ethanol via concomitant partial oxidation and esterification reaction. The partial oxidation reaction is carried out over palladium clusters on the catalysts. The esterification reaction is catalyzed by protons formed from the spontaneous dissociation of acetic acid and can be enhanced by addition solid acid catalysts. After the reaction, there is no evidence of palladium oxide formation suggesting that the oxidation reaction takes place via the adsorbed oxygen. In addition, concomitantly with Pd leaching, increase of average Pd cluster size was observed. Pd-Pd coordination number increases from 3.0 to 7.9 and the Pd content decreases from 1.0 to 0.55 wt%. Addition of solid acid catalysts such as Amberlyst 15, slightly reduces leaching and growth of Pd clusters but the yield pattern of the solid-acid-promoted Pd/SDB catalyst system were still not satisfied. Therefore, zeolite supported metal catalysts with bifunctional catalytic properties were developed. In order to understand the relationship between structure and catalytic properties, EXAFS (Extended X — Ray Absorption Fine structure) spectroscopy was used to characterize the catalysts. For considering the utilization of the catalysts in commercial plant, aging tests were performed and then followed with regeneration experiments. TGA (Thermal Gravity Analysis ) and TPO ( Temperature Programmed Oxidation ) were used to investigate optimal regeneration temperature. The testing results indicated the catalysts present very good stability maintenance and the activity is only slightly loss after regeneration; after four months run the ethanol conversion still keep 58 % , and ethyl acetate selectivity also keep about 90 %.

第一章 緒論............................................1
1.1 乙酸乙酯簡介.......................................1
1.2 乙酸乙酯製程簡介...................................2
1.3 各製程比較.........................................5
1.4 研究目的...........................................6
第二章 觸媒、催化反應、特性分析.......................14
2.1 觸媒選擇..........................................14
2.2 藥品及氣體........................................15
2.3 反應設備..........................................15
2.4 觸媒床填充........................................16
2.5 實驗步驟及產物分析................................16
2.6 觸媒特性分析......................................18
第三章 實驗結果與討論.................................34
3.1 前言..............................................34
3.2 Pd / SDB之EXAFS特性分析...........................38
3.3 Pd — X / Zeolite與Pd / SDB +Amberlyst 15比較.....41
3.4 Pd / Zeolite之EXAFS特性分析.......................45
3.5 Pd — X / Zeolite 長期老化實驗....................48
3.6 觸媒再生..........................................51
第四章 總結與未來展望.................................86

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