含鈀雙金屬觸媒在對氯硝基苯氫化反應之研究

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廖鈺雯(Yu-wen Liao) 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

含鈀雙金屬觸媒在對氯硝基苯氫化反應之研究

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摘要(中)

奈米鈀觸媒在對-氯硝基苯的氫化反應上有很好的催化活性且相較於其他貴金屬觸媒有較低的材料成本，唯獨對目標產物對-氯苯胺的選擇性較低。本研究中，首先探討奈米鈀觸媒與不同的金屬形成雙金屬觸媒後，用於對-氯硝基苯的氫化化反應上造成反應選擇率的差異。再來製備不同比例之鈀銅雙金屬觸媒擔載於二氧化鈦上，找出對本反應有最適化之反應活性與選擇性的鈀銅金屬觸媒。所使用的雙金屬觸媒，皆使用含浸法來製備，在進行反應前使用硼氫化鈉還原之。觸媒鑑定部分，以X光繞射儀(XRD)、穿透式電子顯微鏡(TEM)、高解析度穿透式電子顯微鏡(HRTEM)、X光光電子能譜儀(XPS)等來鑑定觸媒之物理、化學特性和表面性質；觸媒催化反應部分，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，使用之反應器為半批式反應器(Parr Reactor 4842)，反應條件設定：反應溫度303K；氫氣分壓為0.55 MPa；反應器攪拌速率300 rpm.，反應物起始濃度為0.2M (2.54 g對-氯硝基苯粉末溶於80 ml甲醇)；使用0.5 g觸媒進行反應，直到反應完全。反應結果顯示鈀與銅形成奈米鈀銅雙金屬觸媒擔載在二氧化鈦擔體上之反應催化效果最佳，此觸媒可降低反應條件，達到在低壓與常溫下發生反應，且加入少量的銅可以大幅提升奈米鈀觸媒對此氫化反應之目標產物對-氯苯胺的選擇率、保有奈米鈀觸媒本身對氫化反應有相當高的反應活性之特性。加入銅金屬之後可降低奈米鈀觸媒的氧化態、增加反應活性點且銅的氧化物可保護鈀顆粒避免氧化。利用鈀觸媒的良好反應活性與銅觸媒對反應的高選擇性可使觸媒應用更廣泛。

摘要(英)

Nano-palladium catalyst has been reported to have high activity for hydrogenation reaction due to its excellent absorb ability of hydrogen. Comparing with other noble metals (Pt, Ru, Au etc.), Pd has relativity low cost. In this study, palladium-containing bimetals were loaded on titanium dioxide. Bimetallic Pd catalysts have been prepared and tested for p-chlornitrobenzene (p-CNB) hydrogenation reaction. All of the catalysts were prepared by incipient-wetness impregnation method using NaBH4 to reduce the metal cations. These catalysts were characterized by X–ray diffraction (XRD), transmission electron microscopy (TEM), high resolution transmission electron microscopy (HR-TEM), energy dispersive spectrometer (EDS), and X-ray photoelectron spectroscopy (XPS). The activity test of liquid-phase p-CNB hydrogenation reaction was carried out with following reaction condition: 303K, 0.55MPa H2? partial pressure, stirring rate under 300 rpm in a batch reactor. 0.2M p-CNB methanol solution (2.54g p-CNB dissolved in 80 ml MeOH) as the reactant and 0.5g palladium-containing catalyst were used to catalyze this reaction. During the run, the samples were withdrawn periodically and analyzed by a gas chromatography. The results revealed that adding copper as an additive into the catalyst would enhance the dispersion of Pd.. The selectivity of main product, p-chloroaniline (p-CAN), was more than 90%. Palladium catalyst could operate in mild the reaction conditions, i.e, hydrogenation reaction could be carried out at room temperature and low hydrogen pressure. Adding Cu into Pd catalyst slightly caused the activity to decrease but provided significantly increase in selectivity of p-CNB to p-CAN.

關鍵字(中)

★ 奈米鈀觸媒
★ 液相氫化反應
★ 對氯硝基苯
★ 對氯苯胺

關鍵字(英)

★ Palladium catalyst
★ CuPd nanoalloy
★ liquid-phase hydrogenation reaction
★ p-chloronitrobenzene
★ p-chloraniline

論文目次

中文摘要 i
Abstract ii
Table of Contents iii
List of Tables vi
List of Figures vii
List of Schemes ix
Chapter 1 Introduction 1
Chapter 2 literature review 4
2.1 Palladium catalyst 4
2.1.1 The size effect for Pd catalyst 5
2.1.2 The promoting effect of bimetallic palladium catalyst 5
2.1.3 The applications of bimetallic palladium catalyst 6
2.2 Preparations for supported metal catalysts 7
2.2.1 Impregnation 7
2.2.2 Precipitation methods 11
2.3 Hydrogenation 13
2.3.1 Liquid phase hydrogenation of p-chloronitrobenzene 14
Chapter3 Experimental 19
3.1 Materials 19
3.2 Preparation of catalysts 19
3.2.1 Preparation of M-Pd/TiO2 catalysts 19
3.2.2 Preparation of CuPd/TiO2 catalysts 19
3.3 The characterization of catalysts 20
3.3.1 X-ray diffraction (XRD) 20
3.3.2 Transmission electron microscopy (TEM) 21
3.3.3 High-resolution transmission electron microscopy (HRTEM) and energy dispersive spectrometer (EDS) 21
3.3.4 X-ray photoelectron spectroscopy (XPS) 22
3.4 Catalytic activity test 23
Chapter 4 Hydrogenation of p-Chloronitrobenzene on M-Pd/TiO2 catalysts 26
4.1 Introduction 26
4.2 Results and discussion 27
4.2.1 XRD 27
4.2.2 TEM 28
4.2.3 XPS 31
4.2.4 Reaction Test 37
4.2.5 Reaction rate constant 41
4.3 Conclusion 42
Chapter 5 Hydrogenation of p-chloronitrobenzene on Cu-Pd/TiO2 catalyst 44
5.1 Introduction 44
5.2 Results and discussion 45
5.2.1 XRD 45
5.2.2 TEM 47
5.2.3 HRTEM and EDS 51
5.2.4 XPS 55
5.2.5 Reaction test 63
5.2.6 Reaction rate constant 67
5.3 Conclusion 68
Chapter6 Summary 70
Appendix A Reaction rate constant 72
A.1 M-Pd/TiO2 catalysts 73
A.1.1 3Pd/TiO2 73
A.1.2 1Ag3Pd/TiO2 73
A.1.3 1Cu3Pd/TiO2 74
A.1.4 1Fe3Pd/TiO2 74
A.1.5 1Co3Pd/TiO2 75
A.1.6 1Ni3Pd/TiO2 75
A.2 Cu-Pd/TiO2 catalysts 76
A.2.1 0.5Cu3Pd/TiO2 76
A.2.2 0.75Cu3Pd/TiO2 76
A.2.3 1Cu3Pd/TiO2 77
A.2.4 1.25Cu3Pd/TiO2 77
A.2.5 1.5Cu3Pd/TiO2 78
Reference 79

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指導教授

陳郁文(Yu-wen Chen)

審核日期

2014-6-25

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