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Microwaves in Catalysis: Methodology and Applications

Microwaves in Catalysis: Methodology and Applications

Satoshi Horikoshi , Nick Serpone

ISBN: 978-3-527-68814-2

Sep 2015

454 pages

$164.99

Description

A comprehensive overview covering the principles and preparation of catalysts, as well as reactor technology and applications in the field of organic synthesis, energy production, and environmental catalysis.
Edited and authored by renowned and experienced scientists, this reference focuses on successful reaction procedures for applications in industry. Topics include catalyst preparation, the treatment of waste water and air, biomass and waste valorisation, hydrogen production, oil refining as well as organic synthesis in the presence of heterogeneous and homogeneous catalysts and continuous-flow reactions.
With its practical relevance and successful methodologies, this is a valuable guide for chemists at universities working in the field of catalysis, organic synthesis, pharmaceutical or green chemistry, as well as researchers and engineers in the chemical industry.

List of Contributors XVII

Preface XXI

1 General Introduction to Microwave Chemistry 1
Satoshi Horikoshi and Nick Serpone

1.1 ElectromagneticWaves and Dielectric Materials 1

1.2 Microwave Heating 2

1.3 The Various Types of Microwave Heating Phenomena 4

1.3.1 Conduction Loss Heating (Eddy Current Loss and Joule Loss) 5

1.3.2 Dielectric Heating 5

1.3.3 Magnetic Loss Heating (Eddy Current Loss and Hysteresis Loss Heating) 6

1.3.4 Penetration Depth of Microwaves 6

1.4 Fields of Applications with Microwave Heating 9

1.5 Microwaves in Solid Material Processing 11

1.6 Microwaves in Organic Syntheses 12

1.7 Microwave Chemical Equipment 12

1.8 Chemical Reactions Using the Characteristics of Microwave Heating 17

1.9 Microwave Frequency Effect in Chemical Syntheses 21

1.10 Summary 25

References 25

Part I Fundamentals 29

2 Loss Mechanisms and Microwave-Specific Effects in Heterogeneous Catalysis 31
A.E. Stiegman

2.1 Introduction 31

2.2 Heterogeneous Catalyst Systems 33

2.3 Physics of Microwave Absorption 33

2.4 Microwave Loss Processes in Solids 35

2.4.1 Dielectric Loss 35

2.4.2 Charge Carrier Processes 36

2.4.2.1 Conduction Loss 36

2.4.2.2 Space–Charge Recombination 37

2.4.2.3 Dipolar Loss 38

2.4.3 Magnetic Loss Processes 40

2.5 Loss Processes and Microwave-Specific Catalysis: Lessons from Gas–Carbon Reactions 41

2.5.1 Thermochemical Considerations 42

2.6 Final Comments on Microwave-Specific Effects in Heterogeneous Catalysis 45

Acknowledgments 45

References 46

3 Transport Phenomena and Thermal Property under Microwave Irradiation 49
Yusuke Asakuma

3.1 Introduction 49

3.2 Bubble Formation 50

3.3 Convection 53

3.4 Surface Tension 56

3.5 Discussion of Nonthermal Effect for Nanobubble Formation 58

References 59

4 Managing Microwave-Induced Hot Spots in Heterogeneous Catalytic Systems 61
Satoshi Horikoshi and Nick Serpone

4.1 What Are Hot Spots? 61

4.2 Microwaves in Heterogeneous Catalysis 61

4.3 Microwave-Induced Formation of Hot Spots in Heterogeneous Catalysis 63

4.3.1 Hot Spot Phenomenon 63

4.3.2 Mechanism(s) of Formation of Hot Spots 68

4.3.3 Particle Aggregation by Polarization of Activated Carbon Particulates 69

4.3.4 Control of the Occurrence of Hot Spots 73

References 75

Part II Applications – Preparation of Heterogeneous Catalysts 77

5 Preparation of Heterogeneous Catalysts by a Microwave Selective Heating Method 79
Satoshi Horikoshi and Nick Serpone

5.1 Introduction 79

5.2 Synthesis of Metal Catalysts on Carbonaceous Material Supports 79

5.3 Photocatalysts 81

5.3.1 Preparation of TiO2/AC Particles 83

5.3.2 Proposed Mechanism of Formation of TiO2/AC Particles 86

5.3.3 Photoactivity ofMW-Prepared TiO2/AC Composite Particles in the Degradation of Isopropanol 87

5.4 Microwave-Assisted Syntheses of Catalytic Materials for Fuel Cell Applications 88

5.4.1 Microwave-Assisted Synthesis of Pt/C Catalyst Particulates for a H2 Fuel Cell 89

5.4.2 Preparation of Nanocatalysts for a Methanol Fuel Cell 91

5.4.3 Effects of pH on Pt Particle Size and Electrocatalytic Activity of Pt/CNTs for Methanol Electro-oxidation 93

5.5 Other Catalysts Prepared by Microwave-Related Procedures 94

5.6 Concluding Remarks 103

References 103

Part III Applications – Microwave Flow Systems and Microwave Methods Coupled to Other Techniques 109

6 Microwaves in Cu-Catalyzed Organic Synthesis in Batch and Flow Mode 111
Faysal Benaskar, Narendra Patil, Volker Rebrov, Jaap Schouten, and Volker Hessel

6.1 Introduction 111

6.2 Microwave-Assisted Copper Catalysis for Organic Syntheses in Batch Processes 112

6.2.1 Bulk and Nano-structured Metals in a Microwave Field 112

6.2.1.1 Interaction of Bulk Metal with Microwaves 112

6.2.1.2 Metallic Catalyst Particle Size and Shape Effect on Microwave Heating 113

6.2.1.3 Polymetallic Systems in Microwave Chemistry 115

6.2.2 Microwave-Assisted Copper Catalysis for Chemical Synthesis 116

6.2.2.1 Bulk Copper Particles for Catalysis and Microwave Interaction 116

6.2.2.2 Microwave-Assisted Copper-Catalyzed Bond Formation Reactions 117

6.2.3 Supported Cu-Based Catalyst for Sustainable Catalysis in Microwave Field 120

6.2.3.1 Microwave Activation and Synthesis of Cu-Based Heterogeneous Catalysts 120

6.2.3.2 Cu-Supported Catalyst Systems for C–O, C–C, C–S, and C–N Coupling Reactions 121

6.3 Microwave-Assisted Copper Catalysis for Organic Syntheses in Flow Processes 122

6.3.1 Microwave-Assisted Catalyzed Organic Synthesis in Flow Processes 122

6.3.1.1 Microwave Heating in Homogeneously Catalyzed Processes 122

6.3.1.2 Microwave Energy Efficiency and Uniformity in Catalyzed Flow Processes 124

6.3.2 Structured Catalyst in Microwave-Assisted Flow Processing for Organic Reactions 130

6.3.2.1 Thin-Film Flow Reactors for Organic Syntheses 130

6.3.2.2 Structured Fixed-Bed Reactors for Flow Synthesis 131

6.3.2.3 Scale-Up of Microwave-Assisted Flow Processes 133

6.4 Concluding Remarks 136

References 136

7 Pilot Plant for Continuous Flow Microwave-Assisted Chemical Reactions 141
Mitsuhiro Matsuzawa and Shigenori Togashi

7.1 Introduction 141

7.2 Continuous Flow Microwave-Assisted Chemical Reactor 142

7.2.1 Basic Structure 142

7.3 Pilot Plant 145

7.3.1 Design ofWaveguide 145

7.3.2 Configuration of Pilot Plant 147

7.3.3 Water Heating Test 148

7.3.4 Sonogashira Coupling Reaction 151

7.4 Conclusions 153

Acknowledgment 154

References 154

8 Efficient Catalysis by Combining Microwaves with Other Enabling Technologies 155
Giancarlo Cravotto, Laura Rinaldi, and Diego Carnaroglio

8.1 Introduction 155

8.2 Catalysis with Hyphenated and Tandem Techniques 157

8.3 Microwave and Mechanochemical Activation 159

8.4 Microwave and UV Irradiation 162

8.5 Microwave and Ultrasound 164

8.6 Conclusions 166

References 166

Part IV Applications – Organic Reactions 171

9 Applications of Microwave Chemistry in Various Catalyzed Organic Reactions 173
Rick Arneil Desabille Arancon, Antonio Angel Romero, and Rafael Luque

9.1 Introduction 173

9.1.1 Homogeneous Catalysis 175

9.2 Microwave-Assisted Reactions in Organic Solvents 175

9.3 Microwave-Assisted Reactions inWater-Coupling Reactions 179

9.3.1 The Heck Reactions 180

9.3.2 The Suzuki Reaction 186

9.4 Conclusions and Prospects 190

Acknowledgments 190

References 191

10 Microwave-Assisted Solid Acid Catalysis 193
Hyejin Cho, Christian Schäfer, and Béla Török

10.1 Introduction 193

10.2 Microwave-Assisted Clay Catalysis 193

10.3 Zeolites in Microwave Catalysis 199

10.4 Microwave Application of Other Solid Acid Catalysts 205

10.4.1 Heteropoly Acids 205

10.4.2 Acidic Ion-Exchange Resins (Nafion-H, Amberlyst, Dowex) 206

10.4.2.1 Nafion-H 206

10.4.2.2 Amberlyst 207

10.4.2.3 Dowex 208

10.5 Conclusions and Outlook 209

References 209

11 Microwave-Assisted Enzymatic Reactions 213
Takeo Yoshimura, ShigeruMineki, and Shokichi Ohuchi

11.1 Introduction 213

11.2 Synthewave (ProLabo) 217

11.2.1 Lipase 217

11.2.2 Glucosidase 220

11.3 Discover Series (CEM) 220

11.3.1 Lipase (Synthesis, Esterification) 220

11.3.2 Enzymatic Resolution 228

11.3.3 β-Glucosidase, β-Galactosidase 232

11.3.4 Aldolase 233

11.4 Mechanism of the Microwave-Assisted Enzymatic Reaction 233

References 236

Part V Applications – Hydrogenation and Fuel Formation 239

12 Effects of Microwave Activation in Hydrogenation–Dehydrogenation Reactions 241
Leonid M. Kustov

12.1 Introduction 241

12.2 Specific Features of Catalytic Reactions Involving Hydrogen 242

12.3 Hydrogenation Processes under MWConditions 246

12.4 Dehydrogenation 250

12.5 Hydrogen Storage 252

12.6 Hydrogenation of Coal 254

Acknowledgment 254

References 254

13 Hydrogen Evolution from Organic Hydrides throughMicrowave Selective Heating in Heterogeneous Catalytic Systems 259
Satoshi Horikoshi and Nick Serpone

13.1 Situation of Hydrogen Energy and Feature of Stage Methods 259

13.2 Selection of Organic Hydrides as the Hydrogen Carriers 261

13.3 Dehydrogenation of Hydrocarbons with Microwaves in Heterogeneous Catalytic Media 262

13.3.1 Selective Heating by the Microwave Method 262

13.3.2 Dehydrogenation of Tetralin in a Pt/AC Heterogeneous Catalytic Dispersion Subjected to a Microwave Radiation Field 263

13.3.3 Effects of the Tetralin: Pt/AC Ratio on Tetralin Dehydrogenation 264

13.3.4 Dehydrogenation of an Organic Carrier in a Continuous Flow System 266

13.3.5 Dehydrogenation of Methylcyclohexane in a Microwave Fixed-Bed Reactor 269

13.3.6 Simulation Modeling for Microwave Heating of Pt/AC in the Methylcyclohexane Solution 271

13.4 Dehydrogenation of Methane with Microwaves in a Heterogeneous Catalytic System 272

13.5 Problems and Improvements of Microwave-Assisted Heterogeneous Catalysis 273

Acknowledgments 277

References 277

Part VI Applications – Oil Refining 281

14 Microwave-Stimulated Oil and Gas Processing 283
Leonid M. Kustov

14.1 Introduction 283

14.2 Early Publications 283

14.3 Use of Microwave Activation in Catalytic Processes of Gas and Oil Conversions 285

14.3.1 Hydrogen Production 285

14.3.2 CO2 Conversion 286

14.3.3 Synthesis Gas (Syngas) Production 286

14.3.4 Methane Decomposition 287

14.3.5 Methane Steam Reforming 288

14.3.6 Oxidative Coupling of Methane 288

14.3.7 Partial Oxidation and Other Hydrocarbon Conversion Processes 291

14.3.8 Oxidative Dehydrogenation 294

14.3.9 Oil Processing 295

14.4 Prospects for the Use of Microwave Radiation in Oil and Gas Processing 295

Acknowledgment 297

References 297

Part VII Applications – Biomass andWastes 301

15 Algal Biomass Conversion under Microwave Irradiation 303
Shuntaro Tsubaki, Tadaharu Ueda, and Ayumu Onda

15.1 Introduction 303

15.2 Microwave Effect on Hydrothermal Conversion – Analysis Using Biomass Model Compounds 304

15.2.1 Degradation Kinetics of Neutral Sugars under Microwave Heating 304

15.2.2 Effects of Ionic Conduction on Hydrolysis of Disaccharides under Hydrothermal Condition 308

15.3 Hydrolysis of Biomass Using Ionic Conduction of Catalysts 309

15.3.1 Hydrolysis of Starch and Crystalline Cellulose Using Microwave Irradiation and Polyoxometalate Cluster 309

15.3.2 Hydrolysis Fast-Growing Green Macroalgae Using Microwave Irradiation and Polyoxometalate Cluster 311

15.4 Dielectric Property of Algal Hydrocolloids inWater 313

15.4.1 Comparison of Dielectric Property of Aqueous Solution of Hydrocolloids Obtained from Algae and Land Plants 313

15.4.2 The Effects of the Degree of Substitution of Acidic Functional Groups on Dielectric Property of Aqueous Solution of Algal Hydrocolloids 315

15.4.3 The Correlation of Loss Tangent at 2.45 GHz and Other Physical Properties of Sodium Alginates and Carrageenans inWater 316

15.5 Summary and Conclusions 319

Acknowledgments 319

References 319

16 Microwave-Assisted Lignocellulosic Biomass Conversion 323
TomohikoMitani and TakashiWatanabe

16.1 Introduction 323

16.2 Lignocellulosic Biomass Conversion 324

16.3 Multi-mode Continuous Flow Microwave Reactor 325

16.4 Direct-Irradiation Continuous Flow Microwave Reactor 327

16.4.1 Concept of Reactor 327

16.4.2 Designing of Microwave Irradiation Section 327

16.4.3 Prototypes of Reactors 329

16.5 Pilot-Plant-Scale Continuous Flow Microwave Reactor 331

16.5.1 Concept of Reactor 331

16.5.2 Designing of Microwave Irradiation Section 331

16.5.3 Demonstration Experiments of Microwave Pretreatment 333

16.6 Summary and Conclusions 335

References 335

17 Biomass andWaste Valorization under Microwave Activation 337
Leonid M. Kustov

17.1 Introduction 337

17.2 Vegetable Oil and Glycerol Conversion 338

17.3 Conversion of Carbohydrates 339

17.4 Cellulose Conversion 340

17.5 Lignin Processing 342

17.6 Waste and Renewable Raw Material Processing 343

17.7 Carbon Gasification 347

17.8 Prospects for the Use of Microwave Irradiation in the Conversion of Biomass and Renewables 348

Acknowledgment 350

References 350

Part VIII Applications – Environmental Catalysis 355

18 Oxidative and Reductive Catalysts for Environmental Purification Using Microwaves 357
Takenori Hirano

18.1 Introduction 357

18.2 Microwave Heating of Catalyst Oxides Used for Environmental Purification 358

18.3 Microwave-Assisted Catalytic Oxidation of VOCs, Odorants, and Soot 361

18.4 Microwave-Assisted Reduction of NOx and SO2 364

18.5 Conclusions 367

References 367

19 Microwave-/Photo-Driven Photocatalytic Treatment of Wastewaters 369
Satoshi Horikoshi and Nick Serpone

19.1 Situation ofWastewater Treatment by Photocatalytic Classical Methods 369

19.2 Experimental Setup of an Integrated Microwave/Photoreactor System 370

19.3 Microwave-/Photo-Driven PhotocatalyticWastewater Treatment 371

19.3.1 Degradation of Rhodamine B Dye 371

19.3.2 Change of TiO2 Surface Condition under a Microwave Field 376

19.3.3 Specific Nonthermal Microwave Effect(s) in TiO2 Photoassisted Reactions 377

19.3.4 Microwave Frequency Effects on the Photoactivity of TiO2 379

19.3.5 Increase in Radical Species on TiO2 under Microwave Irradiation 380

19.3.6 Microwave Nonthermal Effect(s) as a Key Factor in TiO2 Photoassisted Reactions 382

19.4 Microwave Discharge Electrodeless Lamps (MDELs) 386

19.4.1 The Need for More Efficient UV Light Sources 386

19.4.2 Purification ofWater Using TiO2-Coated MDEL Systems in Natural Disasters 387

19.5 Summary Remarks 389

References 389

Index 393