Plasma Chemistry and Catalysis in Gases and Liquids

Filling the gap for a book that not only covers gases but also plasma methods in liquids, this is all set to become the standard reference on the topic. It considers the central aspects in plasma chemistry and plasma catalysis by focusing on the green and environmental applications, while also taking into account their practical and economic viability.
With the topics addressed by an international group of major experts, this is a must-have for researchers, PhD students and postdocs specializing in the field.

Preface XIII

List of Contributors XVII

1 An Introduction to Nonequilibrium Plasmas at Atmospheric Pressure 1
Sander Nijdam, Eddie van Veldhuizen, Peter Bruggeman, and Ute Ebert

1.1 Introduction 1

1.1.1 Nonthermal Plasmas and Electron Energy Distributions 1

1.1.2 Barrier and Corona Streamer Discharges – Discharges at Atmospheric Pressure 2

1.1.3 Other Nonthermal Discharge Types 3

1.1.3.1 Transition to Sparks, Arcs, or Leaders 4

1.1.4 Microscopic Discharge Mechanisms 4

1.1.4.1 Bulk Ionization Mechanisms 4

1.1.4.2 Surface Ionization Mechanisms 6

1.1.5 Chemical Activity 6

1.1.6 Diagnostics 8

1.2 Coronas and Streamers 9

1.2.1 Occurrence and Applications 9

1.2.2 Main Properties of Streamers 11

1.2.3 Streamer Initiation or Homogeneous Breakdown 14

1.2.4 Streamer Propagation 15

1.2.4.1 Electron Sources for Positive Streamers 15

1.2.5 Initiation Cloud, Primary, Secondary, and Late Streamers 16

1.2.6 Streamer Branching and Interaction 18

1.3 Glow Discharges at Higher Pressures 20

1.3.1 Introduction 20

1.3.2 Properties 21

1.3.3 Studies 22

1.3.4 Instabilities 25

1.4 Dielectric Barrier and Surface Discharges 26

1.4.1 Basic Geometries 26

1.4.2 Main Properties 29

1.4.3 Surface Discharges and Packed Beds 30

1.4.4 Applications of Barrier Discharges 31

1.5 Gliding Arcs 32

1.6 Concluding Remarks 34

References 34

2 Catalysts Used in Plasma-Assisted Catalytic Processes: Preparation, Activation, and Regeneration 45
Vasile I. Parvulescu

2.1 Introduction 45

2.2 Specific Features Generated by Plasma-Assisted Catalytic Applications 46

2.3 Chemical Composition and Texture 47

2.4 Methodologies Used for the Preparation of Catalysts for Plasma-Assisted Catalytic Reactions 49

2.4.1 Oxides and Oxide Supports 49

2.4.1.1 Al2O3 49

2.4.1.2 SiO2 50

2.4.1.3 TiO2 51

2.4.1.4 ZrO2 52

2.4.2 Zeolites 52

2.4.2.1 Metal-Containing Molecular Sieves 53

2.4.3 Active Oxides 55

2.4.4 Mixed Oxides 56

2.4.4.1 Intimate Mixed Oxides 56

2.4.4.2 Perovskites 56

2.4.5 Supported Oxides 59

2.4.5.1 Metal Oxides on Metal Foams and Metal Textiles 61

2.4.6 Metal Catalysts 62

2.4.6.1 Embedded Nanoparticles 62

2.4.6.2 Catalysts Prepared via Electroplating 62

2.4.6.3 Catalysts Prepared via Chemical Vapor Infiltration 64

2.4.6.4 Metal Wires 64

2.4.6.5 Supported Metals 65

2.4.6.6 Supported Noble Metals 66

2.5 Catalysts Forming 67

2.5.1 Tableting 67

2.5.2 Spherudizing 69

2.5.3 Pelletization 69

2.5.4 Extrusion 70

2.5.5 Foams 72

2.5.6 Metal Textile Catalysts 73

2.6 Regeneration of the Catalysts Used in Plasma Assisted Reactions 73

2.7 Plasma Produced Catalysts and Supports 74

2.7.1 Sputtering 76

2.8 Conclusions 76

References 77

3 NOx Abatement by Plasma Catalysis 89
G´erald Dj´ega-Mariadassou, Fran¸cois Baudin, Ahmed Khacef, and Patrick Da Costa

3.1 Introduction 89

3.1.1 Why Nonthermal Plasma-Assisted Catalytic NOx Remediation? 89

3.2 General deNOx Model over Supported Metal Cations and Role of NTP Reactor: ‘‘Plasma-Assisted Catalytic deNOx Reaction’’ 90

3.3 About the Nonthermal Plasma for NOx Remediation 96

3.3.1 The Nanosecond Pulsed DBD Reactor Coupled with a Catalytic deNOx Reactor: a Laboratory Scale Device Easily Scaled Up at Pilot Level 97

3.3.2 Nonthermal Plasma Chemistry and Kinetics 100

3.3.3 Plasma Energy Deposition and Energy Cost 102

3.4 Special Application of NTP to Catalytic Oxidation of Methane on Alumina-Supported Noble Metal Catalysts 105

3.4.1 Effect of DBD on the Methane Oxidation in Combined Heat Power (CHP) Conditions 106

3.4.1.1 Effect of Dielectric Material on Methane Oxidation 106

3.4.1.2 Effect of Water on Methane Conversion as a Function of Energy Deposition 106

3.4.2 Effect of Catalyst Composition on Methane Conversion as a Function of Energy Deposition 107

3.4.2.1 Effect of the Support on Plasma-Catalytic Oxidation of Methane 107

3.4.2.2 Effect of the Noble Metals on Plasma-Catalytic Oxidation of Methane in the Absence of Water in the Feed 108

3.4.2.3 Influence of Water on the Plasma-Assisted Catalytic Methane Oxidation in CHP Conditions 109

3.4.3 Conclusions 111

3.5 NTP-Assisted Catalytic NOx Remediation from Lean Model Exhausts Gases 112

3.5.1 Consumption of Oxygenates and RNOx from Plasma during the Reduction of NOx According to the Function F3: Plasma-Assisted Propene-deNOx in the Presence of Ce0.68Zr0.32O2 112

3.5.1.1 Conversion of NOx and Total HC versus Temperature (Light-Off Plot) 112

3.5.1.2 GC/MS Analysis 113

3.5.2 The NTP is Able to Significantly Increase the deNOx Activity, Extend the Operating Temperature Window while Decreasing the Reaction Temperature 114

3.5.2.1 TPD of NO for Prediction of the deNOx Temperature over Alumina without Plasma 115

3.5.2.2 Coupling of a NTP Reactor with a Catalyst (Alumina) Reactor for Catalytic-Assisted deNOx 116

3.5.3 Concept of a ‘‘Composite’’ Catalyst Able to Extend the deNOx Operating Temperature Window 117

3.5.4 Propene-deNOx on the ‘‘Al2O3 /// Rh–Pd/Ce0.68Zr0.32O2 /// Ag/Ce0.68Zr0.32O2’’ Composite Catalyst 118

3.5.4.1 NOx and C3H6 Global Conversion versus Temperature 118

3.5.4.2 GC/MS Analysis of Gas Compounds at the Outlet of the Catalyst Reactor 119

3.5.5 NTP Assisted Catalytic deNOx Reaction in the Presence of a Multireductant Feed: NO (500 ppm), Decane (1100 ppmC), Toluene (450 ppmC), Propene (400 ppmC), and Propane (150 ppmC), O2 (8% vol), Ar (Balance) 119

3.5.5.1 Conversion of NOx and Global HC versus Temperature 119

3.5.5.2 GC/MS Analysis of Products at the Outlet of Associated Reactors 120

3.6 Conclusions 124

Acknowledgments 125

References 125

4 VOC Removal from Air by Plasma-Assisted Catalysis-Experimental Work 131
Monica Magureanu

4.1 Introduction 131

4.1.1 Sources of VOC Emission in the Atmosphere 131

4.1.2 Environmental and Health Problems Related to VOCs 132

4.1.3 Techniques for VOC Removal 133

4.1.3.1 Thermal Oxidation 133

4.1.3.2 Catalytic Oxidation 134

4.1.3.3 Photocatalysis 134

4.1.3.4 Adsorption 135

4.1.3.5 Absorption 135

4.1.3.6 Biofiltration 135

4.1.3.7 Condensation 136

4.1.3.8 Membrane Separation 136

4.1.3.9 Plasma and Plasma Catalysis 136

4.2 Plasma-Catalytic Hybrid Systems for VOC Decomposition 137

4.2.1 Nonthermal Plasma Reactors 137

4.2.2 Considerations on Process Selectivity 139

4.2.3 Types of Catalysts 140

4.2.4 Single-Stage Plasma-Catalytic Systems 141

4.2.5 Two-Stage Plasma-Catalytic Systems 141

4.3 VOC Decomposition in Plasma-Catalytic Systems 142

4.3.1 Results Obtained in Single-Stage Plasma-Catalytic Systems 142

4.3.2 Results Obtained in Two-Stage Plasma-Catalytic Systems 150

4.3.3 Effect of VOC Chemical Structure 154

4.3.4 Effect of Experimental Conditions 155

4.3.4.1 Effect of VOC Initial Concentration 155

4.3.4.2 Effect of Humidity 155

4.3.4.3 Effect of Oxygen Partial Pressure 156

4.3.4.4 Effect of Catalyst Loading 157

4.3.5 Combination of Plasma Catalysis and Adsorption 159

4.3.6 Comparison between Catalysis and Plasma Catalysis 160

4.3.7 Comparison between Single-Stage and Two-Stage Plasma Catalysis 161

4.3.8 Reaction By-Products 162

4.3.8.1 Organic By-Products 162

4.3.8.2 Inorganic By-Products 163

4.4 Concluding Remarks 164

References 165

5 VOC Removal from Air by Plasma-Assisted Catalysis: Mechanisms, Interactions between Plasma and Catalysts 171
Christophe Leys and Rino Morent

5.1 Introduction 171

5.2 Influence of the Catalyst in the Plasma Processes 172

5.2.1 Physical Properties of the Discharge 172

5.2.2 Reactive Species Production 174

5.3 Influence of the Plasma on the Catalytic Processes 174

5.3.1 Catalyst Properties 174

5.3.2 Adsorption 175

5.4 Thermal Activation 177

5.5 Plasma-Mediated Activation of Photocatalysts 178

5.6 Plasma-Catalytic Mechanisms 179

References 180

6 Elementary Chemical and Physical Phenomena in Electrical Discharge Plasma in Gas–Liquid Environments and in Liquids 185
Bruce R. Locke, Petr Lukes, and Jean-Louis Brisset

6.1 Introduction 185

6.2 Physical Mechanisms of Generation of Plasma in Gas–Liquid Environments and Liquids 188

6.2.1 Plasma Generation in Gas Phase with Water Vapor 188

6.2.2 Plasma Generation in Gas–Liquid Systems 189

6.2.2.1 Discharge over Water 189

6.2.2.2 Discharge in Bubbles 191

6.2.2.3 Discharge with Droplets and Particles 192

6.2.3 Plasma Generation Directly in Liquids 193

6.3 Formation of Primary Chemical Species by Discharge Plasma in Contact with Water 199

6.3.1 Formation of Chemical Species in Gas Phase with Water Vapor 199

6.3.1.1 Gas-Phase Chemistry with Water Molecules 201

6.3.1.2 Gas-Phase Chemistry with Water Molecules, Ozone, and Nitrogen Species 206

6.3.2 Plasma-Chemical Reactions at Gas–Liquid Interface 210

6.3.3 Plasma Chemistry Induced by Discharge Plasmas in Bubbles and Foams 213

6.3.4 Plasma Chemistry Induced by Discharge Plasmas in Water Spray and Aerosols 215

6.4 Chemical Processes Induced by Discharge Plasma Directly in Water 217

6.4.1 Reaction Mechanisms of Water Dissociation by Discharge Plasma in Water 217

6.4.2 Effect of Solution Properties and Plasma Characteristics on Plasma Chemical Processes in Water 222

6.5 Concluding Remarks 224

Acknowledgments 224

References 225

7 Aqueous-Phase Chemistry of Electrical Discharge Plasma in Water and in Gas–Liquid Environments 243
Petr Lukes, Bruce R. Locke, and Jean-Louis Brisset

7.1 Introduction 243

7.2 Aqueous-Phase Plasmachemical Reactions 243

7.2.1 Acid–Base Reactions 245

7.2.2 Oxidation Reactions 251

7.2.2.1 Hydroxyl Radical 252

7.2.2.2 Ozone 253

7.2.2.3 Hydrogen Peroxide 254

7.2.2.4 Peroxynitrite 255

7.2.3 Reduction Reactions 256

7.2.3.1 Hydrogen Radical 256

7.2.3.2 Perhydroxyl/Superoxide Radical 257

7.2.4 Photochemical Reactions 257

7.3 Plasmachemical Decontamination of Water 259

7.3.1 Aromatic Hydrocarbons 260

7.3.1.1 Phenol 260

7.3.1.2 Substituted Aromatic Hydrocarbons 263

7.3.1.3 Polycyclic and Heterocyclic Aromatic Hydrocarbons 265

7.3.2 Organic Dyes 267

7.3.2.1 Azo Dyes 268

7.3.2.2 Carbonyl Dyes 270

7.3.2.3 Aryl Carbonium Ion Dyes 271

7.3.3 Aliphatic Compounds 275

7.3.3.1 Methanol 275

7.3.3.2 Dimethylsulfoxide 277

7.3.3.3 Tetranitromethane 279

7.4 Aqueous-Phase Plasma-Catalytic Processes 279

7.4.1 Iron 280

7.4.1.1 Catalytic Cycle of Iron in Plasmachemical Degradation of Phenol 282

7.4.2 Platinum 284

7.4.2.1 The Role of Platinum as a Catalyst in Fenton’s Reaction 285

7.4.3 Tungsten 286

7.4.4 Titanium Dioxide 288

7.4.5 Activated Carbon 290

7.4.6 Silica Gel 291

7.4.7 Zeolites 291

7.5 Concluding Remarks 292

Acknowledgments 293

References 293

8 Biological Effects of Electrical Discharge Plasma in Water and in Gas–Liquid Environments 309
Petr Lukes, Jean-Louis Brisset, and Bruce R. Locke

8.1 Introduction 309

8.2 Microbial Inactivation by Nonthermal Plasma 310

8.2.1 Dry Gas Plasma 311

8.2.2 Humid Gas Plasma 313

8.2.3 Gas Plasma in Contact with Liquids 313

8.2.3.1 Discharge over Water and Hydrated Surfaces 313

8.2.3.2 Discharge with Water Spray 314

8.2.3.3 Gas Discharge in Bubbles 314

8.2.4 Plasma Directly in Water 314

8.2.5 Kinetics of Microbial Inactivation 315

8.2.5.1 Comments on Sterilization and Viability Tests 316

8.3 Chemical Mechanisms of Electrical Discharge Plasma Interactions with Bacteria in Water 317

8.3.1 Bacterial Structure 319

8.3.2 Reactive Oxygen Species 320

8.3.2.1 Hydroxyl Radical 320

8.3.2.2 Hydrogen Peroxide 321

8.3.3 Reactive Nitrogen Species 324

8.3.3.1 Peroxynitrite 325

8.3.4 Post-discharge Phenomena in Bacterial Inactivation 327

8.4 Physical Mechanisms of Electrical Discharge Plasma Interactions with Living Matter 330

8.4.1 UV Radiation 331

8.4.2 X-Ray Emission 332

8.4.3 Shockwaves 332

8.4.4 Thermal Effects and Electrosurgical Plasmas 334

8.4.5 Electric Field Effects and Bioelectrics 335

8.5 Concluding Remarks 336

Acknowledgments 337

References 337

9 Hydrogen and Syngas Production from Hydrocarbons 353
Moritz Heintze

9.1 Introduction: Plasma Catalysis 353

9.2 Current State of Hydrogen Production, Applications, and Technical Requirements 354

9.2.1 Steam Reforming: SR 355

9.2.2 Partial Oxidation: POX 356

9.2.3 Dry Carbon Dioxide Reforming: CDR 357

9.2.4 Pyrolysis 357

9.3 Description and Evaluation of the Process 358

9.3.1 Materials Balance: Conversion, Yield, and Selectivity 358

9.3.2 Energy Balance: Energy Requirement and Efficiency 359

9.4 Plasma-Assisted Reforming 360

9.4.1 Steam Reforming 360

9.4.1.1 Conversion of Methane 360

9.4.1.2 Conversion of Higher Hydrocarbons 362

9.4.1.3 Conversion of Oxygenates 363

9.4.2 Partial Oxidation 365

9.4.2.1 Conversion of Methane 365

9.4.2.2 Conversion of Higher Hydrocarbons 367

9.4.3 Carbon Dioxide Dry Reforming 369

9.4.3.1 Reforming of Methane to Syngas 369

9.4.3.2 Coupling to Higher Hydrocarbons 372

9.4.3.3 Reforming of Higher Hydrocarbons 372

9.4.4 Plasma Pyrolysis 373

9.4.4.1 Methane Pyrolysis to Hydrogen and Carbon 373

9.4.4.2 Production of Acetylene 374

9.4.4.3 Pyrolysis of Oxygenates 377

9.4.5 Combined Processes 377

9.4.5.1 Autothermal Reforming of Methane 378

9.4.5.2 Autothermal Reforming of Liquid Fuels 378

9.4.5.3 Reforming with Carbon Dioxide and Oxygen 381

9.4.5.4 Reforming with Carbon Dioxide and Steam 381

9.4.5.5 Other Feedstock 381

9.5 Summary of the Results and Outlook 382

References 384

Index 393

Vasile I. Parvulescu received his master's degree in Catalysis from the Polytechnic University of Bucharest in 1979 and in 1986 gained his PhD in Chemistry from the same university, where he investigated the selectivity of bi- and multimetal catalysts in hydrogenation of aromatic hydrocarbons. After several years as high-signor researcher at the Institute of Inorganic and Rare Metals, in 1992 he joined the University of Bucharest, where he become full professor in 1999. His current interest concerns the study of heterogeneous catalysts for green and fine chemistry and environmental protection. He authored more than 230 papers, 25 patents, and 4 books. He was awarded in 1990 with the price of the Romanian Academy and in 2008 Proclaimed Knight of the National Order for Merit by the Romanian President.

Dr. Monica Magureanu is a senior researcher in the National Institute for Laser, Plasma and Radiation Physics (NILPRP) in Bucharest, Romania. She received her M.Sc. degree from the University of Bucharest, Faculty of Physics in 1996. In 1995 she joined NILPRP. Between 2000 and 2002 she was with the Institute for Low Temperature Plasma Physics (INP) Greifswald, Germany for her PhD studies on methane conversion into higher hydrocarbons in microwave plasma and she received her PhD degree from Ernst-Moritz-Arndt University, Greifswald in 2002. Her present research interests include non-equilibrium plasma at atmospheric pressure and applications to air and water pollution abatement.

Dr. Petr Lukes is a Senior Researcher at the Institute of Plasma Physics at the Department of Pulse Plasma Systems at the Academy of Sciences of the Czech Republic in Prague, Czech Republic. He has over 15 years research experience in the field of chemical and physical processes induced by non-thermal plasma in water and gas/liquid environments and their environmental and biomedical applications. He received his M.Sc. and Ph.D. degrees in chemical and environmental engineering from the Institute of Chemical Technology, Prague, Czech Republic, in 1995 and 2002, respectively. In 2003 he was awarded a NSF-NATO Postdoctoral Fellowship in Science and Engineering and performed postdoctoral research at Florida State University, Tallahassee, USA. He is the author of numerous journal papers and conference presentations in the field of plasmachemistry in water. In 1995 he received the Czech Chemical Society Award, and in 2006 the Otto Wichterle Award from the Academy of Sciences CR.

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