Characterization and Design of Zeolite Catalysts (eBook)

Preface 6
Contents 8
Chapter 1 Introduction to Zeolite Science and Catalysis 12
1.1 General Trend of the Zeolite Acid Catalyst: Species, Structure, and Industrial Application 12
1.2 Property of Zeolite Catalyst: Acidity, Shape Selectivity, and Loading Property 16
1.3 Intention of the Publication with the Background of the Zeolite Chemistry 17
References 19
Chapter 2 Solid Acidity of Zeolites 20
2.1 Multiple Characterization Techniques 20
2.1.1 Physical Properties 20
2.1.2 Chemical Properties 21
2.2 Fundamentals for the TPD of Ammonia 22
2.2.1 Experimental Apparatus of the TPD Method 22
2.2.2 Identification of the Desorption, l- and h-Peaks 24
2.2.3 Identification of Ammonia Desorbed from Y Zeolite 25
2.3 Theory for the TPD of Ammonia 26
2.3.1 Conditions of the Equilibrium 26
2.3.2 Derivation of a Fundamental Equation 28
2.3.3 Determination of .H and Constancy of .S (Desorption) 30
2.4 Practical Measurements of Ammonia TPD 31
2.4.1 Curve Fitting Method to Measure the Strength of Acid Site 31
2.4.2 .H on Various Zeolites with Different Concentrations of Acid Site 32
2.5 Number of Acid Sites on Various Zeolites 35
2.5.1 Number of Acid Sites Correlated with Al Concentration 35
2.5.2 In Situ and Ex Situ Prepared H-type Zeolites 37
References 38
Chapter 3 IRMS-TPD Measurements of Acid Sites 39
3.1 Measurement Method 39
3.1.1 What Is Obtained from the TPD Measurement 39
3.1.2 Experimental Methods 39
3.1.3 Required Corrections, IR Band Position and S 41
3.2 Proton Form Zeolite 42
3.2.1 H-Mordenite 42
3.2.2 H-Y and H-Chabazite 44
3.3 Modified Zeolites 49
3.3.1 Multivalent Cation-Modified Zeolite 49
3.3.2 Ultrastable Y (USY) Zeolite 51
3.4 Distribution of Brønsted Acid Sites Dependent on the Concentration 53
3.5 Relationship Between Stretching Frequency and Ammonia Desorption Heat of OH Group 55
3.6 Distorted Structure of Zeolite and Related Material with Lewis Acidity and Broad Distribution of Acid Strength 57
3.7 Measurements of Metal Oxide Overlayer 62
3.8 Extinction Coefficients of NH4+ and NH3 Adsorbed on Brønsted and Lewis Acid Sites, Respectively 65
References 69
Chapter 4 DFT Calculation of the Solid Acidity 70
4.1 DFT Calculation 70
4.1.1 DFT Calculation Applied to the Study on Brønsted Acidity 70
4.1.2 Embedded Cluster and Periodic Boundary Conditions 71
4.2 Application to Chabazite, a Simple Zeolite 72
4.2.1 Brønsted Acid Sites in Chabazite Based on the Models Within the Periodic Boundary Conditions 72
4.2.2 Brønsted Acid Site in an Embedded Cluster Model 74
4.3 Application to Other Zeolites 74
4.3.1 FAU, MOR, and BEA Calculated Under the Conditions of the Embedded Cluster and the Periodic Boundary 74
4.3.2 MFI, FER, and MWW Calculated Under the Embedded Cluster Model 76
4.4 Modified Zeolites 78
4.4.1 Divalent Cation-Exchanged Y Zeolites Based on the Embedded Cluster Model 78
4.4.2 Modified Brønsted OH in Y Zeolite Based on the Periodic Boundary Conditions 80
4.5 Dependence of Brønsted Acid Strength on Local Geometry 81
References 87
Chapter 5 Catalytic Activity and Adsorption Property 88
5.1 Paraffin Cracking 88
5.1.1 Evaluation of Intrinsic Activity of Acid Site 88
5.1.2 Dependence of Activity on Acid Strength 90
5.1.3 Thermodynamic Description on Correlation Between Activation Energy and Ammonia Desorption Heat 95
5.1.4 Behavior of Acid Sites in 8- and 12-Rings of Mordenite 97
5.2 Adsorption of Aromatic Hydrocarbons 98
5.3 Friedel--Crafts Alkylation on Ga-MCM-41 102
5.4 Amination of Phenol into Aniline on Ga/ZSM-5 106
References 109
Chapter 6 CVD of Silica for the Shape Selective Reaction 111
6.1 Reactants and Products Shape Selectivity, Concept and Definition 111
6.2 Chemical Vapor Deposition of Silica and the Procedure 112
6.3 Formation of Silica Overlayer on the External Surface 116
6.3.1 Method of Benzene-Filled Pore for the Measurement of External Surface Area 116
6.3.2 Mechanism of CVD to form the Silica Overlayer 117
6.3.3 Formation of Silica Overlayer on Zeolite and Metal Oxide, and Its Function 118
6.4 Fine Control of Pore-Opening Size 119
6.4.1 Mordenite 120
6.4.2 MFI Zeolite 121
6.4.3 A Zeolite 122
6.4.4 Y Zeolite 127
6.5 Characterization of Deposited Oxide 128
6.5.1 XPS Measurements 128
6.5.2 EXAFS of the Deposited Germanium 129
6.5.3 TEM Observation 131
6.6 External Surface Acidity: Measurements and Inactivation 132
References 135
Chapter 7 Application of the CVD of Silica to the Shape Selective Reaction 136
7.1 Selective Formation of Para-Dialkylbenzene 136
7.1.1 Principle of the Shape Selectivity 136
7.1.2 CVD Zeolite to Produce the Para-Dialkylbenzene 138
7.1.3 In Situ Production of CVD Zeolites 142
7.1.4 HZSM-5 In Situ and Ex Situ Prepared for the CVD of Silicon Alkoxide 143
7.1.5 CLD of Silica for the Shape Selective Adsorption 143
7.2 Selective Cracking of Linear Alkane (Dewaxing) 146
7.3 Various Applications 148
7.3.1 Preferential Production of Dimethylamine from Methanol and Ammonia 148
7.3.2 Improvement of the Life and the Activity of Catalysts 149
7.3.3 Selective Removal of Undesired Products 151
7.3.4 Applications to Zeolites from Various View-Points 151
References 153
Chapter 8 Zeolite Loading Property for Active Sites and XAFS Measurements 155
8.1 EXAFS and XANES Measurements of Loaded Metals 155
8.1.1 DXAFS and QXAFS Analysis 155
8.1.2 Formation of Molecular-Like PdO Through the Interaction with Acid Sites of Zeolites 156
8.1.3 Reversible Cluster Formation Through the Interaction with Acid Sites of Zeolites 158
8.2 In Situ QXAFS Studies on the Dynamic Coalescence and Dispersion Processes of Pd in USY Zeolite 160
8.3 Formation of the Atomically Dispersed Pd0 Through H2 Bubbling in o-Xylene: XAFS Measurements of Metals in the Liquid 163
References 168
Chapter 9 Catalytic Reaction on the Palladium-Loaded Zeolites 169
9.1 Combustion of Hydrocarbons Over Pd-Supported Catalysts 169
9.1.1 Toluene Combustion 170
9.1.2 Methane Combustion 171
9.2 Selective Reduction of NO with Methane in the Presence of Oxygen 175
9.2.1 Improvement in the Activity Derived by the Combined Effect of Adsorbent of Aromatic Acids 176
9.3 Cross-Coupling Reactions Over Pd Loaded on FAU-Type Zeolites 178
9.3.1 Heck Coupling Reactions Over Pd Loaded on H-Y Zeolites 178
9.3.2 Remarkable Enhancement of Catalytic Activity Induced by the H2 Bubbling in Suzuki--Miyaura Coupling Reactions 179
9.3.3 A Possible Mechanism for the Formation of Active Pd Species in o-Xylene 182
References 184
Index 186