鈀金/二氧化矽蛋殼型觸媒之製備與應用

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姓名

何嘉茵(Chia-Yin Ho) 查詢紙本館藏

畢業系所

化學工程與材料工程學系

論文名稱

鈀金/二氧化矽蛋殼型觸媒之製備與應用
(Au-Pd@SiO2 catalyst with egg-shell structure and its application in reaction)

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摘要(中)

本研究中目的是要開發核-殼鈀金二氧化矽蛋殼型觸媒，使用蛋殼型觸媒和粉末觸媒進行對氯硝基苯氫化反應活性測試，所使用的蛋殼型觸媒是由三種不同方法來製備(先鹼處理再浸漬金屬溶液、先浸漬金屬溶液再鹼處理與浸漬金屬溶液後乾燥再鹼處理)。以光學顯微鏡、X光繞射儀、穿透式顯微鏡、高解析穿透式顯微鏡及X光光電子能譜儀，著重於蛋殼型觸媒加入不同比例的鈀與金來分析觸媒之物理、化學特性及表面性質，利用液相選擇性對氯硝基苯氫化反應來測試觸媒的活性與選擇性，使用的反應器為半批式反應器，反應溫度298K，氫氣分壓為0.6 MPa，反應器攪拌速率為300 rpm。
在製備蛋殼型觸媒時，增加鹼性溶液的濃度會增加金屬的厚度，製備步驟中先加鹼性溶液能降低金屬厚度；金屬的平均顆粒很小，且均勻分布於二氧化矽擔體上。在反應結果顯示，由方法一(先鹼處理再浸漬金屬溶液)所製備的蛋殼型觸媒擁有最薄厚度而對-氯苯胺的選擇率高，另一方面粉末觸媒擁有最高的活性，但兩種觸媒的對-氯苯胺選擇率並沒明顯差距，然而，在鈀與金不同比例的觸媒比較中，加入少量的鈀和多量的金可以達到較高的活性和選擇性，表示添加金可以有效提高對-氯苯胺的選擇率。使用三種不同的製備方法皆可成功地製備出蛋殼型觸媒。

摘要(英)

Nano-sized palladium and gold catalysts have high activity for hydrogenation reaction. Since very small amount of metals are used, usually metals are deposited on the support. SiO2 is used for the reaction since it can resist in acidic condition. In liquid phase hydrogenation, pore diffusion is always a rate-limiting step. It is desired to deposit metals on the shell of SiO2 beads. The objective of this study was to develop a method to prepare bimetallic catalyst with core-shell structure. Three different pathways were used to prepare the egg-shell catalysts. All the egg-shell catalysts were characterized by optical microscope, X-ray diffraction, transmission electron microscopy, high resolution transmission electron microscopy and X-ray photoelectron spectroscopy. Liquid phase hydrogenation of p-chloronitrobenzene to p-chloroaniline was used as the test reaction. The reaction was carried out at 298K, 0.6 MPa partial pressure of H2 and 300 rpm of stirring rate in a batch reactor. In order to obtain the kinetic data, powder catalysts were also prepared and tested for reaction.
The results show that increasing the concentration of NaOH in preparation process increased the thickness of the shell. The average particle size of the metals wass in nanosize and all metals were homogeneously dispersed in the shell of catalysts. The egg-shell catalyst made by method 1 had the smallest thickness of shell had the highest selectivity of p-chloroaniline. On the other hand, the powder catalysts had a higher activity, but selectivity of p-chloroaniline was not significantly different compared with the egg-shell catalysts. The catalysts with lower Pd loadings and higher Au loadings had high activity and selectivity. It suggests that adding gold can effectively increase the selectivity of p-CAN. In this study, the catalyst with egg-shell structure was successfully prepared which can be applied in industry for various reactions.

關鍵字(中)

★ 蛋殼型觸媒
★ 液相氫化反應
★ 對氯硝基苯
★ 對氯苯胺

關鍵字(英)

★ egg-shell catalyst
★ palladium
★ gold
★ bimetallic catalysts
★ liquid-phase hydrogenation
★ p-chloronitrobenzene
★ p-chloroaniline

論文目次

中文摘要 I
Abstract II
List of Tables VI
List of Figures VII
List of Schemes X
Chapter 1 Introduction 1
Chapter 2 Literature review 4
2.1 Palladium catalyst 4
2.1.1 The size effect for palladium catalysts 5
2.1.2 The effect of bimetallic palladium catalysts 6
2.1.3 The applications of bimetallic palladium catalysts 8
2.2 Preparations of supported metal catalysts 13
2.2.1 Impregnation method 14
2.2.2 Precipitation method 15
2.2.3 Coprecipitation method 16
2.3 Liquid-phase hydrogenation of p-chloronitrobenzene 17
Chapter 3 Experimental 20
3.1 Materials 20
3.2 Preparation of catalysts 20
3.2.1. Preparation of egg-shell structure Au-Pd/SiO2 spherical catalyst 20
3.2.2. Preparation of Au-Pd/SiO2 powder catalyst 21
3.3 Characterization of catalysts 21
3.3.1 Optical microscope (OM) 22
3.3.2 X-ray diffraction (XRD) 22
3.3.3 Transmission electron microscopy (TEM) 23
3.3.4 High-resolution transmission electron microscopy (HRTEM) 24
3.3.5 X-ray photoelectron spectroscopy (XPS) 25
3.4 Hydrogenation reaction 26
Chapter 4 Hydrogenation of p-CNB and synthesis vinyl acetate monomer on Au-Pd/SiO2 catalysts 28
4.1 Introduction 28
4.2 Results and discussion 30
4.2.1 OM 30
4.2.2 XRD 37
4.2.3 TEM 41
4.2.4 HRTEM 45
4.2.5 XPS 51
4.2.6 Reaction test 63
4.2.7 Kinetic study 67
4.3 Conclusion 89
Reference 91

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審核日期

2018-6-21

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