Plasma-Assisted Nitrogen Fixation for Sustainable Process Industries

Enables readers to use plasma technology in the ammonia and NOx production process for greater efficiency, resiliency, and sustainability Bridging the gap between chemistry, physics, and engineering, Plasma-Assisted Nitrogen Fixation for Sustainable Process Industries provides in-depth insights into plasma-assisted nitrogen fixation, plasma technology, plasma reactors, and ammonia and NOx production, covering fundamental principles, advanced topics, economic viability, and emerging trends. Real-world applications and case studies are included throughout to elucidate key concepts and help readers put theory into practice in order to increase efficiency, sustainability, and industrial resilience. Plasma-Assisted Nitrogen Fixation for Sustainable Process Industries discusses: Reactor designs and industrial feasibility, including decentralized production to make nitrogen fixation accessible to remote areas and smaller-scale operations The Haber-Bosch process and its limitations and alternatives and plasma generation, ionization, and applications Plasma-assisted NOx synthesis with a focus on reaction pathways, energy efficiency, and the role of catalysts Cutting-edge innovations such as microplasma technology, plasma-liquid interactions for nitrogen fixation, and plasma-electrochemistry for nitrate-to-ammonia conversion Plasma-based fertilizer applications and analytical methods in plasma diagnostics as a tool to enable innovation Plasma-Assisted Nitrogen Fixation for Sustainable Process Industries is an essential reference on the subject for engineers, plant managers, and decision-makers seeking to optimize their ammonia and NOx manufacturing processes.

About the Editors xiii List of Contributors xv Preface xxi Part I Fundamentals of Nitrogen Fixation 1 1 Fundamentals of Ammonia Production 3 Kevin Rouwenhorst and Leon Lefferts 1.1 Introduction to Nitrogen Fixation 3 1.2 The Haber-Bosch Process 4 1.3 Production Pathways to Ammonia 5 1.4 Novel Methods for Ammonia Synthesis 9 1.5 Applications of Ammonia 11 1.6 Conclusions 14 References 14 2 Fundamentals of No X Production 21 Filippo Buttignol, Alberto Garbujo, Raffaele Ostuni, Michal Bialkowski, and Pierdomenico Biasi 2.1 Introduction 21 2.2 The Ostwald Process 22 2.2.1 Catalytic Oxidation of Ammonia 22 2.2.1.1 Reaction Mechanism and Kinetics 23 2.2.1.2 Reaction Engineering and Parameter Effect 24 2.2.1.3 Catalyst: Pt and New Development 25 2.2.2 NO Oxidation to NO 2 27 2.2.2.1 Reaction Mechanism and Kinetics 28 2.2.2.2 Process Implementation Exploiting the Catalytic Oxidation of NO 29 2.2.3 Nitrogen Oxides Absorption and HNO 3 Production 30 2.3 Type of Processes 32 2.3.1 Weak Nitric Acid 32 2.3.1.1 General Process Description 35 2.3.2 Concentrated Nitric Acid 35 2.4 Environmental Protection and Treatment of Exhaust Gases 37 2.4.1 Control of No X Emissions 38 2.4.2 Control of N 2 O Emissions 41 2.4.2.1 Primary Measures 41 2.4.2.2 Secondary Measures 42 2.4.2.3 Ternary Measures 42 2.5 Future Trends 46 2.6 Conclusions 47 References 48 Part II Plasma-Assisted Nitrogen Fixation 51 3 Introduction to Plasma Technology 53 Anthony B. Murphy 3.1 Fundamental Concepts 53 3.1.1 Types of Plasma 53 3.1.2 Scaling Parameters 54 3.2 Plasma Generation 58 3.3 Plasma Chemistry 62 3.3.1 Inelastic Collisions Between Electrons and Heavy Particles 62 3.3.2 Inelastic Collisions Between Heavy Particles 64 3.3.3 Equilibrium in Plasmas 66 3.4 Plasma Technology 68 3.4.1 Low-Pressure Plasma Applications 69 3.4.2 Non-equilibrium Atmospheric-Pressure Plasma Applications 70 3.4.3 Thermal Plasma Applications 74 3.5 Role of Plasma in Ammonia and No X Synthesis 77 3.6 Conclusions 79 References 81 4 Plasma Reactors 85 Evgeny Rebrov 4.1 Introduction 85 4.2 Microwave and RF Plasma 87 4.2.1 Microwave Plasma Torch 87 4.2.2 Surfaguide-Type Discharge 90 4.2.3 RF Plasma Torch 92 4.3 Spark and High-frequency Pulsed Discharges 94 4.4 Gliding Arc 95 4.5 Propeller Arc 100 4.6 Glow Discharge 102 4.6.1 Triboelectric Nanogenerator 103 4.7 Dielectric Barrier Discharge 105 4.7.1 Micro-DBD Reactors 105 4.7.2 DBD Reactors for N 2 /Water Plasma 107 4.8 Conclusions and Outlook 109 References 111 5 Plasma-Assisted Ammonia Synthesis 119 Mateo Ruiz-Martín, Adrián Megías-Sánchez, Servando Marín-Meana, Manuel Oliva-Ramírez, Agustín R. González-Elipe, and Ana Gómez-Ramírez 5.1 Introduction 119 5.2 Advanced Plasma Technologies for Ammonia Synthesis 120 5.2.1 Ammonia Synthesis Reactions and Plasma Types 121 5.2.1.1 MW Reactions 122 5.2.1.2 RF Discharge Reactions 122 5.2.1.3 Plasma-Electrochemistry 123 5.2.1.4 Gliding Arc Reactions 123 5.2.2 Effects of Plasma Reactor Operational Conditions 124 5.2.2.1 Carrier Gas 127 5.2.2.2 Gases Proportion 127 5.2.2.3 Residence Time and Gas Flow Regime 127 5.2.2.4 Driving Voltage and Frequency 128 5.2.2.5 Barrier Materials and Catalysts 128 5.3 Plasma-Catalysis of Ammonia: Seeking Synergies to Improving Energy Efficiency 129 5.3.1 Plasma-Catalysis: A Brief Introduction 129 5.3.2 Barrier Materials and Catalysts in Packed-Bed Plasma Reactors for NH 3 Synthesis 131 5.3.2.1 Barrier Materials 131 5.3.2.2 Catalyst: Active Phase and Support 132 5.3.3 New Paradigms in Plasma-Catalysis for Ammonia Synthesis 136 5.4 Conclusions 138 References 140 6 Plasma-assisted No X Synthesis 147 Tianyu Li, Haoxuan Jiang, Rusen Zhou, Jing Sun, and Renwu Zhou 6.1 Introduction 147 6.2 The Mechanism of Plasma-Assisted Nitrogen Oxidation 151 6.3 Nitrogen Oxidation Achieved by Different Types of Plasma 156 6.4 Plasma–Water-Based Nitrogen Fixation 163 6.5 Conclusion and Outlook 168 References 170 Part III Mechanisms of Nitrogen Fixation 181 7 Ammonia Synthesis with Plasma Catalysis: Mechanisms 183 Kevin Rouwenhorst and Leon Lefferts 7.1 Introduction 183 7.2 Methods to Study Mechanisms in Catalysis 183 7.3 Experimental Kinetics: From Catalysis to Plasma Catalysis 185 7.4 Beyond Equilibrium and Reverse Reactions 187 7.5 Effect of Catalyst on Plasma 189 7.6 Kinetics of Plasma-Catalytic Ammonia Synthesis 190 7.7 Mechanism of Plasma-Catalytic Ammonia Synthesis 191 7.7.1 Dominant Pathway: Catalytic Dissociation of Excited N 2 191 7.7.2 Dominant Pathway: N 2 Dissociation in Plasma 193 7.7.3 Surface Intermediate Species 194 7.7.4 Other Mechanisms 196 7.8 Energy Efficiency 196 7.9 Conclusions 198 References 199 8 Mechanisms of Plasma-driven No X Synthesis 203 Weitao Wang and Xin Tu 8.1 Introduction 203 8.2 No X Synthesis Without a Catalyst 204 8.2.1 Plasma Physics Relevant to No X Formation 204 8.2.2 Plasma Chemistry and Key Reaction Mechanisms 208 8.2.2.1 Electrons Induced Reactions 208 8.2.2.2 Formation and Loss Processes of NO and NO 2 208 8.2.2.3 The Key Role of the Zeldovich Mechanism 212 8.2.3 Factors Influencing Reaction Pathways 213 8.2.3.1 Impact of Plasma Types 213 8.2.3.2 Impact of Gas Composition 215 8.2.3.3 Impact of Pressure 217 8.2.3.4 Impact of Pulsed Discharge 218 8.2.4 Mechanistic Insights from Experimental Studies 221 8.3 Plasma-catalytic No X Synthesis 223 8.4 Conclusion and Outlook 228 References 230 Part IV Environmental and Economic Viability 237 9 Environmental Impact and Sustainability Aspects of Plasma-Based Nitrogen Fixation 239 Nam Nghiep Tran, Nguyen Van Duc Long, Muhammad Yousaf Arshad, Jose Luis Osorio Tejada, and Volker Hessel 9.1 Introduction 239 9.2 Environmental Benefits of PANF 241 9.2.1 Carbon Footprint Analysis 243 9.2.2 Comparison with the HB Process 244 9.2.3 Energy Efficiency and Consumption 245 9.2.4 Reduction in GHG Emissions 246 9.2.5 Integration with Renewable Energy Sources 246 9.3 Circular Economy Considerations 248 9.3.1 PANF Within the Circular Economy Model 249 9.3.2 Resource Utilization and Waste Minimization 249 9.3.3 Closed-Loop Systems and Recycling Opportunities 250 9.3.4 Decentralization via Small-Scale Production 252 9.4 Life Cycle Assessment 253 9.4.1 LCA of PANF: Overview 253 9.4.2 Benchmarking Against the HB Process 254 9.4.3 Environmental Impact Analysis (Including CO 2 Emissions and Pollutants) 255 9.5 Perspectives for Sustainable Plasma-Based Nitrogen Fixation 259 9.6 Conclusion and Outlook 260 References 261 10 Industrial Applications and Economic Viability of Plasma-Based Nitrogen Fixation 271 Magnus Nyvold and Rune Ingels 10.1 Introduction 271 10.2 Overview of The Reactive Nitrogen Industry 274 10.3 Conventional Nitrogen Fixation 275 10.3.1 Fossil-Based Ammonia Production 276 10.3.2 Electricity-Based Ammonia Production 278 10.3.3 Nitric Acid Production 279 10.3.4 Overall Performance of Nitrate Production 281 10.4 Plasma-Based Nitrate Production 281 10.4.1 Stand-alone Nitric Acid Process 283 10.4.2 Integrated Nitric Acid Process 284 10.4.3 Nitrate Enrichment of Organic Substrates 286 10.4.4 Other Avenues 288 10.5 Economic Comparison 289 10.6 Competitive Landscape 293 10.7 Conclusion 294 References 295 Part V Advanced Processes of Nitrogen Fixation 299 11 Microplasma for Nitrogen Fixation 301 Liangliang Lin 11.1 Introduction 301 11.2 Microplasma Configurations for Nitrogen Fixation 306 11.3 Microplasma-Based Process for Nitrogen Fixation 309 11.3.1 No X 309 11.3.2 Nh 3 313 11.3.3 Nitride, Carbonitride, and Oxynitride Nanomaterials 318 11.3.4 N-Doped Nanomaterials 320 11.4 Challenges and Perspectives for Microplasma Nitrogen Fixation 324 11.5 Conclusions 326 Acknowledgments 326 References 327 12 Plasma–Liquid Interaction for Nitrogen Fixation 337 Tianqi Zhang, Jungmi Hong, and Patrick Cullen 12.1 Introduction 337 12.2 Plasma Systems for Plasma–Liquid Discharges 338 12.3 Mechanisms of Nitrogen Fixation in Plasma–Liquid Systems 342 12.3.1 Physical Aspects of Plasma–Liquid Interactions 342 12.3.1.1 Breakdown Mechanism of Plasma–Liquid Discharges 342 12.3.1.2 Solvation of Plasma Species Through Plasma–Liquid Interface 345 12.3.2 Chemical Aspect of Plasma–Liquid Interactions 346 12.3.2.1 Effect of Water Content in Gas-Phase Plasma Discharge 347 12.3.2.2 Production and Loss of Short-lived Species in Liquid 348 12.3.2.3 Important Pathway of Long-lived Species Formation in Liquid 349 12.3.3 Mass Transport Through the Plasma–Liquid Interface 350 12.4 Key Challenges 351 12.4.1 Diagnostics 351 12.4.2 Modeling 353 12.5 Conclusion 355 References 356 13 Plasma Electrochemistry for Nitrogen Fixation 363 Susanta Bera, Dimitrios Zagoraios, and Mihalis N. Tsampas 13.1 Introduction 363 13.2 Motivation for Plasma-Enabled N 2 Oxidation Followed by Electrochemical Reduction 365 13.3 Conventional and Plasma-enabled No X Feedstock 367 13.4 Definition of Performance Metrics 367 13.5 Electrochemical Conversion of No X to Nh 3 – Eno X Rr 368 13.5.1 Electrochemical Conversion with No X in Liquid-phase Stream 370 13.5.2 Electrochemical Conversion with No X in Gas-phase Or Catholyte-Free Stream 373 13.5.3 Overview of the Eno X Rr Studies 374 13.6 Plasma-enabled Electrochemical Studies for No X Conversion To Nh 3 – Pnor-eno X Rr 375 13.6.1 Pnor-eno X Rr Integration Approaches 377 13.6.1.1 Liquid-phase-based Pnor-eno X Rr 377 13.6.1.2 Gas-phase-based Pnor-eno X Rr 378 13.6.2 Alternative Plasma Electrochemical Systems 378 13.6.3 Experimental Pnor-eno X Rr Studies 379 13.6.3.1 Gas-phase No X Generation 379 13.6.3.2 Liquid-phase No X Generation 380 13.6.4 Overview of Pnor-eno X Rr Systems 381 13.7 Implementation at Industrial Level 383 13.8 Key Challenges and Future Outlook 383 13.8.1 Electrochemical Systems 383 13.8.2 Operational Considerations 384 13.8.3 Product Separation 384 13.8.4 Scalability and Process Integration 385 13.9 Conclusions 385 References 386 14 Analytical Techniques for Plasma Catalysis 393 Christopher Hardacre, Sarayute Chansai, and Shanshan Xu 14.1 Optical Spectroscopy 393 14.1.1 Introduction 393 14.1.2 Experimental Setup 396 14.1.3 OES Spectrum and Interpretation for Ammonia Synthesis 397 14.1.4 OES Analysis and Proposed Reaction Mechanism for Ammonia Synthesis 400 14.1.5 OES Analysis for Plasma Dynamics 401 14.1.6 TDLAS Analysis for Plasma Dynamics and Kinetics 405 14.2 Infrared Spectroscopy 406 14.2.1 Introduction 406 14.2.2 In situ Plasma-IR/DRIFTS Cell Designs and Setups 408 14.2.3 In-plasma in Situ Drifts Analysis for No X Reduction 411 14.2.4 Post Plasma in situ IR Analysis for Ammonia Synthesis 411 14.3 Summary 413 References 416 15 Perspectives in Plasma-Based Nitrogen Fixation for Fertilizer Applications 423 Yury Gorbanev and Annemie Bogaerts 15.1 Nitrogen Compounds Used for Soil Fertilization 423 15.2 Fertilizer Production: Haber-Bosch-Ostwald Process and Plasma for Nitrogen Fixation 425 15.3 Metrics of Various Pathways of Plasma-Based Nitrogen Fixation 429 15.4 Perspectives of NH 4 NO 3 Production by Plasma-Based Nitrogen Fixation 434 15.4.1 Pathway Through NH 3 Synthesis: Plasma Reduction Followed by Oxidation 434 15.4.2 Pathway Through Both Nh 3 and No X Synthesis: Combined Plasma Reduction and Plasma Oxidation 435 15.4.3 Pathway Through No X Synthesis: Plasma Oxidation Followed by Reduction 436 15.5 Plasma-Based Nitrogen Fixation for Reduction of NH 3 Emissions and Simultaneous Fertilizer Production 438 15.6 Conclusion and Outlook: Challenges and Perspectives of Plasma-Based Nitrogen Fixation 439 References 441 Index 451