Plasma chemistry and catalysis in gases and liquids

Edited by Vasile I Parvulescu, Monica Magureanu, and Petr Lukes Plasma Chemistry and Catalysis in Gases and Liquids Related Titles Rauscher, H., Perucca, M., Buyle, G (eds.) Plasma Technology for Hyperfunctional Surfaces Food, Biomedical, and Textile Applications 2010 Hardcover ISBN: 978-3-527-32654-9 Kawai, Y., Ikegami, H., Sato, N., Matsuda, A., Uchino, K., Kuzuya, M., Mizuno, A (eds.) Industrial Plasma Technology Applications from Environmental to Energy Technologies 2010 Hardcover ISBN: 978-3-527-32544-3 Heimann, R B Plasma Spray Coating Principles and Applications 2008 Hardcover ISBN: 978-3-527-32050-9 Hippler, R., Kersten, H., Schmidt, M., Schoenbach, K H (eds.) Low Temperature Plasmas Fundamentals, Technologies and Techniques 2008 Hardcover ISBN: 978-3-527-40673-9 d’Agostino, R., Favia, P., Kawai, Y., Ikegami, H., Sato, N., Arefi-Khonsari, F (eds.) Advanced Plasma Technology 2008 Hardcover ISBN: 978-3-527-40591-6 Edited by Vasile I Parvulescu, Monica Magureanu, and Petr Lukes Plasma Chemistry and Catalysis in Gases and Liquids The Editors Prof Dr Vasile I Parvulescu University of Bucharest Faculty of Chemistry Regina Elisabetha Bld 4-12 030016 Bucharest Romania Dr Monica Magureanu Nat Inst for Lasers, Plasma and Radiation Physics Atomistilor Str 409 077125 Bucharest-Magurele Romania Dr Petr Lukes Institute of Plasma Physics AS CR, v.v.i Dept of Pulse Plasma Systems Za Slovankou 182 00 Prague Czech Republic All books published by Wiley-VCH are carefully produced Nevertheless, authors, editors, and publisher not warrant the information contained in these books, including this book, to be free of errors Readers are advised to keep in mind that statements, data, illustrations, procedural details or other items may inadvertently be inaccurate Library of Congress Card No.: applied for British Library Cataloguing-in-Publication Data A catalogue record for this book is available from the British Library Bibliographic information published by the Deutsche Nationalbibliothek The Deutsche Nationalbibliothek lists this publication in the Deutsche Nationalbibliografie; detailed bibliographic data are available on the Internet at © 2012 Wiley-VCH Verlag & Co KGaA, Boschstr 12, 69469 Weinheim, Germany All rights reserved (including those of translation into other languages) No part of this book may be reproduced in any form – by photoprinting, microfilm, or any other means – nor transmitted or translated into a machine language without written permission from the publishers Registered names, trademarks, etc used in this book, even when not specifically marked as such, are not to be considered unprotected by law Cover Design Formgeber, Eppelheim Typesetting Laserwords Private Limited, Chennai, India Printing and Binding Markono Print Media Pte Ltd, Singapore Print ISBN: 978-3-527-33006-5 ePDF ISBN: 978-3-527-64955-6 ePub ISBN: 978-3-527-64954-9 mobi ISBN: 978-3-527-64953-2 oBook ISBN: 978-3-527-64952-5 V Contents Preface XIII List of Contributors 1.1 1.1.1 1.1.2 1.1.3 1.1.3.1 1.1.4 1.1.4.1 1.1.4.2 1.1.5 1.1.6 1.2 1.2.1 1.2.2 1.2.3 1.2.4 1.2.4.1 1.2.5 1.2.6 1.3 1.3.1 1.3.2 1.3.3 1.3.4 1.4 1.4.1 1.4.2 XVII An Introduction to Nonequilibrium Plasmas at Atmospheric Pressure Sander Nijdam, Eddie van Veldhuizen, Peter Bruggeman, and Ute Ebert Introduction Nonthermal Plasmas and Electron Energy Distributions Barrier and Corona Streamer Discharges – Discharges at Atmospheric Pressure Other Nonthermal Discharge Types Transition to Sparks, Arcs, or Leaders Microscopic Discharge Mechanisms Bulk Ionization Mechanisms Surface Ionization Mechanisms Chemical Activity Diagnostics Coronas and Streamers Occurrence and Applications Main Properties of Streamers 11 Streamer Initiation or Homogeneous Breakdown 14 Streamer Propagation 15 Electron Sources for Positive Streamers 15 Initiation Cloud, Primary, Secondary, and Late Streamers 16 Streamer Branching and Interaction 18 Glow Discharges at Higher Pressures 20 Introduction 20 Properties 21 Studies 22 Instabilities 25 Dielectric Barrier and Surface Discharges 26 Basic Geometries 26 Main Properties 29 VI Contents 1.4.3 1.4.4 1.5 1.6 Surface Discharges and Packed Beds 30 Applications of Barrier Discharges 31 Gliding Arcs 32 Concluding Remarks 34 References 34 Catalysts Used in Plasma-Assisted Catalytic Processes: Preparation, Activation, and Regeneration 45 Vasile I Parvulescu Introduction 45 Specific Features Generated by Plasma-Assisted Catalytic Applications 46 Chemical Composition and Texture 47 Methodologies Used for the Preparation of Catalysts for Plasma-Assisted Catalytic Reactions 49 Oxides and Oxide Supports 49 Al2 O3 49 SiO2 50 TiO2 51 ZrO2 52 Zeolites 52 Metal-Containing Molecular Sieves 53 Active Oxides 55 Mixed Oxides 56 Intimate Mixed Oxides 56 Perovskites 56 Supported Oxides 59 Metal Oxides on Metal Foams and Metal Textiles 61 Metal Catalysts 62 Embedded Nanoparticles 62 Catalysts Prepared via Electroplating 62 Catalysts Prepared via Chemical Vapor Infiltration 64 Metal Wires 64 Supported Metals 65 Supported Noble Metals 66 Catalysts Forming 67 Tableting 67 Spherudizing 69 Pelletization 69 Extrusion 70 Foams 72 Metal Textile Catalysts 73 Regeneration of the Catalysts Used in Plasma Assisted Reactions 73 Plasma Produced Catalysts and Supports 74 Sputtering 76 2.1 2.2 2.3 2.4 2.4.1 2.4.1.1 2.4.1.2 2.4.1.3 2.4.1.4 2.4.2 2.4.2.1 2.4.3 2.4.4 2.4.4.1 2.4.4.2 2.4.5 2.4.5.1 2.4.6 2.4.6.1 2.4.6.2 2.4.6.3 2.4.6.4 2.4.6.5 2.4.6.6 2.5 2.5.1 2.5.2 2.5.3 2.5.4 2.5.5 2.5.6 2.6 2.7 2.7.1 Contents 2.8 Conclusions 76 References 77 NOx Abatement by Plasma Catalysis 89 G´erald Dj´ega-Mariadassou, Fran¸cois Baudin, Ahmed Khacef, and Patrick Da Costa Introduction 89 Why Nonthermal Plasma-Assisted Catalytic NOx Remediation? 89 General deNOx Model over Supported Metal Cations and Role of NTP Reactor: ‘‘Plasma-Assisted Catalytic deNOx Reaction’’ 90 About the Nonthermal Plasma for NOx Remediation 96 The Nanosecond Pulsed DBD Reactor Coupled with a Catalytic deNOx Reactor: a Laboratory Scale Device Easily Scaled Up at Pilot Level 97 Nonthermal Plasma Chemistry and Kinetics 100 Plasma Energy Deposition and Energy Cost 102 Special Application of NTP to Catalytic Oxidation of Methane on Alumina-Supported Noble Metal Catalysts 105 Effect of DBD on the Methane Oxidation in Combined Heat Power (CHP) Conditions 106 Effect of Dielectric Material on Methane Oxidation 106 Effect of Water on Methane Conversion as a Function of Energy Deposition 106 Effect of Catalyst Composition on Methane Conversion as a Function of Energy Deposition 107 Effect of the Support on Plasma-Catalytic Oxidation of Methane 107 Effect of the Noble Metals on Plasma-Catalytic Oxidation of Methane in the Absence of Water in the Feed 108 Influence of Water on the Plasma-Assisted Catalytic Methane Oxidation in CHP Conditions 109 Conclusions 111 NTP-Assisted Catalytic NOx Remediation from Lean Model Exhausts Gases 112 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 Ce0.68 Zr0.32 O2 112 Conversion of NOx and Total HC versus Temperature (Light-Off Plot) 112 GC/MS Analysis 113 The NTP is Able to Significantly Increase the deNOx Activity, Extend the Operating Temperature Window while Decreasing the Reaction Temperature 114 TPD of NO for Prediction of the deNOx Temperature over Alumina without Plasma 115 Coupling of a NTP Reactor with a Catalyst (Alumina) Reactor for Catalytic-Assisted deNOx 116 3.1 3.1.1 3.2 3.3 3.3.1 3.3.2 3.3.3 3.4 3.4.1 3.4.1.1 3.4.1.2 3.4.2 3.4.2.1 3.4.2.2 3.4.2.3 3.4.3 3.5 3.5.1 3.5.1.1 3.5.1.2 3.5.2 3.5.2.1 3.5.2.2 VII VIII Contents 3.5.3 3.5.4 3.5.4.1 3.5.4.2 3.5.5 3.5.5.1 3.5.5.2 3.6 4.1 4.1.1 4.1.2 4.1.3 4.1.3.1 4.1.3.2 4.1.3.3 4.1.3.4 4.1.3.5 4.1.3.6 4.1.3.7 4.1.3.8 4.1.3.9 4.2 4.2.1 4.2.2 4.2.3 4.2.4 4.2.5 4.3 4.3.1 4.3.2 4.3.3 4.3.4 4.3.4.1 Concept of a ‘‘Composite’’ Catalyst Able to Extend the deNOx Operating Temperature Window 117 Propene-deNOx on the ‘‘Al2 O3 /// Rh–Pd/Ce0.68 Zr0.32 O2 /// Ag/Ce0.68 Zr0.32 O2 ’’ Composite Catalyst 118 NOx and C3 H6 Global Conversion versus Temperature 118 GC/MS Analysis of Gas Compounds at the Outlet of the Catalyst Reactor 119 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 Conversion of NOx and Global HC versus Temperature 119 GC/MS Analysis of Products at the Outlet of Associated Reactors 120 Conclusions 124 Acknowledgments 125 References 125 VOC Removal from Air by Plasma-Assisted Catalysis-Experimental Work 131 Monica Magureanu Introduction 131 Sources of VOC Emission in the Atmosphere 131 Environmental and Health Problems Related to VOCs 132 Techniques for VOC Removal 133 Thermal Oxidation 133 Catalytic Oxidation 134 Photocatalysis 134 Adsorption 135 Absorption 135 Biofiltration 135 Condensation 136 Membrane Separation 136 Plasma and Plasma Catalysis 136 Plasma-Catalytic Hybrid Systems for VOC Decomposition 137 Nonthermal Plasma Reactors 137 Considerations on Process Selectivity 139 Types of Catalysts 140 Single-Stage Plasma-Catalytic Systems 141 Two-Stage Plasma-Catalytic Systems 141 VOC Decomposition in Plasma-Catalytic Systems 142 Results Obtained in Single-Stage Plasma-Catalytic Systems 142 Results Obtained in Two-Stage Plasma-Catalytic Systems 150 Effect of VOC Chemical Structure 154 Effect of Experimental Conditions 155 Effect of VOC Initial Concentration 155 Contents 4.3.4.2 4.3.4.3 4.3.4.4 4.3.5 4.3.6 4.3.7 4.3.8 4.3.8.1 4.3.8.2 4.4 5.1 5.2 5.2.1 5.2.2 5.3 5.3.1 5.3.2 5.4 5.5 5.6 6.1 6.2 6.2.1 6.2.2 6.2.2.1 6.2.2.2 6.2.2.3 6.2.3 6.3 6.3.1 6.3.1.1 Effect of Humidity 155 Effect of Oxygen Partial Pressure 156 Effect of Catalyst Loading 157 Combination of Plasma Catalysis and Adsorption 159 Comparison between Catalysis and Plasma Catalysis 160 Comparison between Single-Stage and Two-Stage Plasma Catalysis 161 Reaction By-Products 162 Organic By-Products 162 Inorganic By-Products 163 Concluding Remarks 164 References 165 VOC Removal from Air by Plasma-Assisted Catalysis: Mechanisms, Interactions between Plasma and Catalysts 171 Christophe Leys and Rino Morent Introduction 171 Influence of the Catalyst in the Plasma Processes 172 Physical Properties of the Discharge 172 Reactive Species Production 174 Influence of the Plasma on the Catalytic Processes 174 Catalyst Properties 174 Adsorption 175 Thermal Activation 177 Plasma-Mediated Activation of Photocatalysts 178 Plasma-Catalytic Mechanisms 179 References 180 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 Introduction 185 Physical Mechanisms of Generation of Plasma in Gas–Liquid Environments and Liquids 188 Plasma Generation in Gas Phase with Water Vapor 188 Plasma Generation in Gas–Liquid Systems 189 Discharge over Water 189 Discharge in Bubbles 191 Discharge with Droplets and Particles 192 Plasma Generation Directly in Liquids 193 Formation of Primary Chemical Species by Discharge Plasma in Contact with Water 199 Formation of Chemical Species in Gas Phase with Water Vapor 199 Gas-Phase Chemistry with Water Molecules 201 IX X Contents 6.3.1.2 6.3.2 6.3.3 6.3.4 6.4 6.4.1 6.4.2 6.5 7.1 7.2 7.2.1 7.2.2 7.2.2.1 7.2.2.2 7.2.2.3 7.2.2.4 7.2.3 7.2.3.1 7.2.3.2 7.2.4 7.3 7.3.1 7.3.1.1 7.3.1.2 7.3.1.3 7.3.2 7.3.2.1 7.3.2.2 7.3.2.3 7.3.3 7.3.3.1 7.3.3.2 7.3.3.3 Gas-Phase Chemistry with Water Molecules, Ozone, and Nitrogen Species 206 Plasma-Chemical Reactions at Gas–Liquid Interface 210 Plasma Chemistry Induced by Discharge Plasmas in Bubbles and Foams 213 Plasma Chemistry Induced by Discharge Plasmas in Water Spray and Aerosols 215 Chemical Processes Induced by Discharge Plasma Directly in Water 217 Reaction Mechanisms of Water Dissociation by Discharge Plasma in Water 217 Effect of Solution Properties and Plasma Characteristics on Plasma Chemical Processes in Water 222 Concluding Remarks 224 Acknowledgments 224 References 225 Aqueous-Phase Chemistry of Electrical Discharge Plasma in Water and in Gas–Liquid Environments 243 Petr Lukes, Bruce R Locke, and Jean-Louis Brisset Introduction 243 Aqueous-Phase Plasmachemical Reactions 243 Acid–Base Reactions 245 Oxidation Reactions 251 Hydroxyl Radical 252 Ozone 253 Hydrogen Peroxide 254 Peroxynitrite 255 Reduction Reactions 256 Hydrogen Radical 256 Perhydroxyl/Superoxide Radical 257 Photochemical Reactions 257 Plasmachemical Decontamination of Water 259 Aromatic Hydrocarbons 260 Phenol 260 Substituted Aromatic Hydrocarbons 263 Polycyclic and Heterocyclic Aromatic Hydrocarbons 265 Organic Dyes 267 Azo Dyes 268 Carbonyl Dyes 270 Aryl Carbonium Ion Dyes 271 Aliphatic Compounds 275 Methanol 275 Dimethylsulfoxide 277 Tetranitromethane 279 References 45 46 47 48 49 50 51 52 53 methane conversion into synthetic fuels using microplasma reactor Chem Eng J., 166 (1), 288–293 Tsai, C.-H., Hsieh, T.-H., Shih, M., Huang, Y.-J., and Wei, T.-C (2005) Partial oxidation of methane to synthesis gas by a microwave plasma torch AIChE J., 51 (10), 2853–2858 Horng, R.-F., Chang, Y.-P., Huang, H.-H., and Lai, M.-P (2006) A study of the hydrogen production from a small plasma converter Fuel, 86 (1–2), 81–89 (Volume Date 2007) Luche, J., Aubry, O., Khacef, A., and Cormier, J.-M (2009) Syngas production from methane oxidation using a non-thermal plasma: experiments and kinetic modelling Chem Eng J., 149 (1–3), 35–41 Lee, D.H., Kim, K.-T., Cha, M.S., and Song, Y.-H (2010) Plasma-controlled chemistry in plasma reforming of methane Int J Hydrogen Energy, 35 (20), 10967–10976 Sreethawong, T., Thakonpatthanakun, P., and Chavadej, S (2007) Partial oxidation of methane with air for synthesis gas production in a multistage gliding arc discharge system Int J Hydrogen Energy, 32 (8), 1067–1079 Horng, R.-F., Huang, H.-H., Lai, M.-P., Wen, C.-S., and Chiu, W.-C (2008) Characteristics of hydrogen production by a plasma-catalyst hybrid converter with energy saving schemes under atmospheric pressure Int J Hydrogen Energy, 33 (14), 3719–3727 Heintze, M and Pietruszka, B (2004) Plasma catalytic conversion of methane into syngas: the combined effect of discharge activation and catalysis Catal Today, 89 (1–2), 21–25 Khassin, A.A., Pietruszka, B.L., Heintze, M., and Parmon, V.N (2004) The impact of a dielectric barrier discharge on the catalytic oxidation of methane over Ni-containing catalyst React Kinet Catal Lett., 82 (1), 131–137 Kim, S.C and Chun, Y.N (2008) Experimental study on partial oxidation of methane to produce hydrogen using low-temperature plasma in AC Glidarc 54 55 56 57 58 59 60 discharge Int J Energy Res., 32 (13), 1185–1193 Horng, R.-F., Lai, M.-P., Huang, H.-H., and Chang, Y.-P (2009) Reforming performance of a plasma-catalyst hybrid converter using low carbon fuels Energy Convers Manage., 50 (10), 2632–2637 Horng, R.-F., Lai, M.-P., Chang, Y.-P., Yur, J.-P., and Hsieh, S.-F (2009) Plasma-assisted catalytic reforming of propane and an assessment of its applicability on vehicles Int J Hydrogen Energy, 34 (15), 6280–6289 Gallagher, M.J., Geiger, R., Polevich, A., Rabinovich, A., Gutsol, A., and Fridman, A (2010) On-board plasma-assisted conversion of heavy hydrocarbons into synthesis gas Fuel, 89 (6), 1187–1192 Bibikov, M.B., Demkin, S.A., Zhivotov, V.K., Konovalov, G.M., Moskovskii, A.S., Potapkin, B.V., Smirnov, R.V., and Strelkova, M.I (2007) Partial oxidation of kerosene in plume microwave discharge High Energy Chem., 41 (5), 361–365 Nikipelov, A.A., Popov, I.B., Correale, G., Rakitin, A.E., and Starikovskii, A.Y (2010) Compact catalyst-free liquid fuel to syngas reformer with plasma-assisted flame stabilization 48th AIAA Aerospace Sciences Meeting Including the New Horizons Forum and Aerospace Exposition, Art No 2010-1343 Hartvigsen, J., Czernichowski, P., Hollist, M., Frost, L., Elangovan, S., and Nickens, A (2010) Scale-up of plasma catalyzed logistics fuel reformer for navy shipboard fuel cell systems 2010 Fuel Cell Seminar and Exposition – Henry B Gonzalez Convention Center, San Antonio, TX, October 18–21 The 2009 Spring National Meeting, Tampa, FL session #17 Fuel Processing for Hydrogen Production From Fossil Fuels: Plasma Reforming (TB001) http:// aiche.confex.com/aiche/s09/ techprogram/MEETING.HTM (accessed March 2011) 387 388 Hydrogen and Syngas Production from Hydrocarbons 61 Song, L., Li, X., and Zheng, T (2008) 62 63 64 65 66 67 68 69 70 Onboard hydrogen production from partial oxidation of dimethyl ether by spark discharge plasma reforming Int J Hydrogen Energy, 33 (19), 5060–5065 Czernichowski, A., Czernichowski, M., and Sessa, John P (2008) Waste glycerol conversion into syngas Prepr Symp -Am Chem Soc., Div Fuel Chem., 53 (1), 427–428 Istadi, I and Amin, N.A.S (2006) Co-generation of synthesis gas and C2+ hydrocarbons from methane and carbon dioxide in a hybrid catalytic-plasma reactor: A review Fuel, 85 (5–6), 577–592 Ghorbanzadeh, A.M., Norouzi, S., and Mohammadi, T (2005) High energy efficiency in syngas and hydrocarbon production from dissociation of CH4-CO2 mixture in a non-equilibrium pulsed plasma J Phys D: Appl Phys., 38 (20), 3804–3811 Oberreuther, T., Wolff, C., and Behr, A (2003) Volumetric plasma chemistry with carbon dioxide in an atmospheric pressure plasma using a technical scale reactor IEEE Trans Plasma Sci., 31 (1), 74–78 Behr, A., Wolff, C., and Oberreuther, T (2004) Erzeugung von synthesegas durch trockenes plasma-reforming Chem Ing Tech., 76 (7), 951–955 Oberreuther, T., Wolff, C., and Behr, A (2004) Volumetric plasma chemistry in a technical scale: producing synthesis gas from carbon dioxide and hydrocarbons Galvanotechnik, 95 (2), 438–443 Behr, A., Oberreuther, T., and Wolff, C (2004) Groòtechnisches konzept făur die erzeugung von synthesegas durch trockenes plasma-reforming Chem Ing Tech., 76 (7), 946–950 Long, H., Shang, S., Tao, X., Yin, Y., and Dai, X (2008) CO2 reforming of CH4 by combination of cold plasma jet and Ni/g-Al2O3 catalyst Int J Hydrogen Energy, 33 (20), 5510–5515 Tao, X., Qi, F., Yin, Y., and Dai, X (2008) CO2 reforming of CH4 by combination of thermal plasma and 71 72 73 74 75 76 77 78 79 catalyst Int J Hydrogen Energy, 33 (4), 1262–1265 Tsai, H.-L and Wang, C.-S (2008) Thermodynamic equilibrium prediction for natural gas dry reforming in thermal plasma reformer J Chin Inst Eng., 31 (5), 891–896 Wang, Q., Cheng, Y., and Jin, Y (2009) Dry reforming of methane in an atmospheric pressure plasma fluidized bed with Ni/γ-Al2O3 catalyst Catal Today, 148 (3–4), 275–282 Wang, Q., Yan, B.-H., Jin, Y., and Cheng, Y (2009) Dry reforming of methane in a dielectric barrier discharge reactor with Ni/Al2O3 catalyst: interaction of catalyst and plasma Energy Fuels, 23 (8), 4196–4201 Sekine, Y., Yamadera, J., Kado, S., Matsukata, M., and Kikuchi, E (2008) High-efficiency dry reforming of biomethane directly using pulsed electric discharge at ambient condition Energy Fuels, 22 (1), 693–694 Sekine, Y., Yamadera, J., Matsukata, M., and Kikuchi, E (2010) Simultaneous dry reforming and desulfurization of biomethane with non-equilibrium electric discharge at ambient temperature Chem Eng Sci., 65 (1), 487–491 Tao, X., Bai, M., Li, X., Long, H., Shang, S., Yin, Y., and Dai, X (2011) CH4-CO2 reforming by plasma – challenges and opportunities Prog Energy Combust Sci., 37 (2), 113–124 Liu, C.-J., Xue, B., Eliasson, B., He, F., Li, Y., and Xu, G.-H (2001) Methane conversion to higher hydrocarbons in the presence of carbon dioxide using dielectric-barrier discharge plasmas Plasma Chem Plasma Process., 21 (3), 301–310 Kraus, M., Efli, W., Haffner, K., Eliasson, B., Kogelschatz, U., and Wokaun, A (2002) Investigation of mechanistic aspects of the catalytic CO2 reforming of methane in a dielectric-barrier discharge using optical emission spectroscopy and kinetic modelling Phys Chem Chem Phys., 4, 668–675 Sentek, J., Krawczyk, K., Młotek, M., Kalczewska, M., Kroker, T., Kolb, T., Schenk, A., Gericke, K.-H., References 80 81 82 83 84 85 86 87 88 89 and Schmidt-Szałowski, K (2010) Plasma-catalytic methane conversion with carbon dioxide in dielectric barrier discharges Appl Catal., B Environ., 94 (1–2), 19–26 Goujard, V., Tatibouet, J.-M., and Batiot-Dupeyrat, C (2009) Use of a non-thermal plasma for the production of synthesis gas from biogas Appl Catal., A Gen., 353 (2), 228–235 Bo, Z., Yan, J., Li, X., Chi, Y., and Cen, K (2008) Plasma assisted dry methane reforming using gliding arc gas discharge: effect of feed gases proportion Int J Hydrogen Energy, 33 (20), 5545–5553 Futamura, S and Annadurai, G (2005) Plasma reforming of aliphatic hydrocarbons with CO2 IEEE Trans Ind Appl., 41 (6), 1515–1521 Futamura, S and Annadurai, G (2008) Effects of temperature, voltage properties, and initial gas composition on the plasma reforming of aliphatic hydrocarbons with CO2 IEEE Trans Ind Appl., 44 (1), 53–60 Zhang, X., Zhu, A., Li, X., and Gong, W (2004) Oxidative dehydrogenation of ethane with CO2 over catalyst under pulse corona plasma Catal Today, 89 (1–2), 97–102 Bauer, M., Schwarz-Selinger, T., Kang, H., and von Keudell, A (2005) Control of the plasma chemistry of a pulsed inductively coupled methane plasma Plasma Sources Sci Technol., 14, 543–548 Bakken, J.A., Jensen, R., Monsen, B., Raaness, O., and Waernes, N (1998) Thermal plasma process development in Norway Pure Appl Chem., 70 (6), 1223–1228 Cho, W., Kim, Y.C., and Kim, S.-S (2010) Conversion of natural gas to C2 product, hydrogen and carbon black using a catalytic plasma reaction J Ind Eng Chem., 16 (1), 20–26 Jasinski, M., Dors, M., Nowakowska, H., and Mizeraczyk, J (2008) Hydrogen production via methane reforming using various microwave plasma sources Chem Listy, 102, 1332–1337 Jasinski, M., Dors, M., and Mizeraczyk, J (2009) Application of atmospheric 90 91 92 93 94 95 96 97 pressure microwave plasma source for production of hydrogen via methane reforming Eur Phys J D, 54, 179–183 Stoknes, P.E and Dohmen, J.R (2009) Gasplas low energy microwave plasma reactors Poster on the Conference Hydrogen and Fuel Cells in the Nordic Countries, Oslo, November 24–26, 2009 http://www.gasplas.com/w3/index.php (accessed 27 January 2011) Leins, M., Schaefer, T., Baumgăartner, K.-M., Walker, M., Schulz, A., Schumacher, U., and Stroth, U (2008) Methane pyrolysis with a microwave plasma source for application in space The Eleventh International Conference on Plasma Surface Engineering -PSE 2008 – Garmisch Partenkirchen, September 15–19, 2008, Poster 1028 http://www.pse2008.net (accessed March 2011) ă J and Li, Z (2010) Conversion of LU, natural gas to C2 hydrocarbons via cold plasma technology J Nat Gas Chem., 19 (4), 375–379 Fridman A., Babaritskyi A., Jivotov V., Dyomkin S., Nester S., and Rusanov V (1991) Methane conversion in acetylene in the nonequilibrium MCW-discharge Proceedings of ISPC-10 (ed U Ehlemann, H.G Lergon, and K Wiesemann Bochum), pp 1–6 http://134.147.148.178/ispcdocs/ispc10 /DB2.html (accessed March 2011) Yao, S.L., Suzuki, E., Meng, N., and Nakayama, A (2002) A high-efficiency reactor for the pulsed plasma conversion of methane Plasma Chem Plasma Process., 22 (2), 225–237 Yao, S., Nakayama, A., and Suzuki, E (2001) Acetylene and hydrogen from pulsed plasma conversion of methane Catal Today, 71 (1–2), 219–223 Heintze, M and Magureanu, M (2002) Methane conversion into acetylene in a microwave plasma: optimization of the operating parameters J Appl Phys., 92 (5), 2276–2283 Heintze, M., Magureanu, M., and Kettlitz, M (2002) Mechanism of C-2 hydrocarbon formation from methane in a pulsed microwave plasma J Appl Phys., 92 (12), 7022–7031 389 390 Hydrogen and Syngas Production from Hydrocarbons 98 Heintze, M and Magureanu, M 99 100 101 102 103 104 105 106 (2002) Efficient methane conversion to acetylene in a microwave plasma Proceeding 8th International Symposium on High Pressure Low Temperature Plasma Chemistry (HAKONE 8) at Păuhajăarve ESTONIA, July 2125, 2002, p 3.6 Schmidt-Szałowski, K., Krawczyk, K., and Mlotek, M (2007) Catalytic effects of metals on the conversion of methane in gliding discharges Plasma Processes Polym., (7–8), 728–736 Lee, H and Sekiguchi, H (2011) Plasma-catalytic hybrid system using spouted bed with a gliding arc discharge: CH4 reforming as a model reaction J Phys D: Appl Phys, 44 (27), 274008 Heintze, M and Magureanu, M (2002) Methane conversion into aromatics in a direct plasma-catalytic process J Catal., 206 (1), 91–97 Li, X.-S., Shi, C., Xu, Y., Wang, K.-J., and Zhu, A.-M (2007) A process for a high yield of aromatics from the oxygen-free conversion of methane: combining plasma with Ni/HZSM-5 catalysts Green Chem., (6), 647–653 Rico, V.J., Hueso, J.L., Cotrino, J., and Gonz´alez-Elipe, A.R (2010) Evaluation of different dielectric barrier discharge plasma configurations as an alternative technology for green C1 chemistry in the carbon dioxide reforming of methane and the direct decomposition of methanol J Phys Chem A, 114 (11), 4009–4016 Zhu, X., Hoang, T., Lobban, L.L., and Mallinson, R.G (2009) Plasma reforming of glycerol for synthesis gas production Chem Commun., 20, 2908–2910 Ouni, F., Khacef, A., and Cormier, J.M (2006) Effect of oxygen on methane steam reforming in a sliding discharge reactor Chem Eng Technol., 29 (5), 604–609 Kim, S.C and Chun, Y.N (2008) Production of hydrogen by partial oxidation with thermal plasma Renewable Energy, 33 (7), 1564–1569 107 Pietruszka, B and Heintze, M (2004) 108 109 110 111 112 113 114 115 Methane conversion at low temperature: the combined application of catalysis and non-equilibrium plasma Catal Today, 90 (1–2), 151–158 Nair, S.A., Nozaki, T., and Okazaki, K (2007) Methane oxidative conversion pathways in a dielectric barrier discharge reactor-Investigation of gas phase mechanism Chem Eng J., 132 (1–3), 85–95 Petitpas, G., Rollier, J.-D., Darmon, A., Gonzalez-Aguilar, J., Metkemeijer, R., and Fulcheri, L (2007) A comparative study of non-thermal plasma assisted reforming technologies Int J Hydrogen Energy, 32 (14), 2848–2867 Rollier, J.-D., Gonzalez-Aguilar, J., Petitpas, G., Darmon, A., Fulcheri, L., and Metkemeijer, R (2008) Experimental study on gasoline reforming assisted by nonthermal arc discharge Energy Fuels, 22 (1), 556–560 Rollier, J.-D., Petitpas, G., Gonzalez-Aguilar, J., Darmon, A., Fulcheri, L., and Metkemeijer, R (2008) Thermodynamics and kinetics analysis of gasoline reforming assisted by arc discharge Energy Fuels, 22 (3), 1888–1893 Gonzalez-Aguilar, J., Petitpas, G., Lebouvier, A., Rollier, J.-D., Darmon, A., and Fulcheri, L (2009) Three stages modeling of n-octane reforming assisted by a nonthermal arc discharge Energy Fuels, 23 (10), 4931–4936 Rueangjitt, N., Akarawitoo, C., Sreethawong, T., and Chavadej, S (2007) Reforming of CO2 -containing natural gas using an ac gliding arc system: effect of gas components in natural gas Plasma Chem Plasma Process., 27 (5), 559–576 Rueangjitt, N., Sreethawong, T., and Chavadej, S (2008) Reforming of CO2 -containing natural gas using an ac gliding arc system: effects of operational parameters and oxygen addition in feed Plasma Chem Plasma Process., 28 (1), 49–67 Rueangjitt, N., Jittiang, W., Pornmai, K., Chamnanmanoontham, J., Sreethawong, T., and Chavadej, S (2009) Combined reforming and partial References oxidation of CO2 -containing natural gas using an ac multistage gliding arc discharge system: effect of stage number of plasma reactors Plasma Chem Plasma Process., 29 (6), 433–453 116 Chun, Y.N., Yang, Y.C., and Yoshikawa, K (2009) Hydrogen generation from biogas reforming using a gliding arc plasma-catalyst reformer Catal Today, 148 (3–4), 283–289 117 Shchedrin, A.I., Levko, D.S., Chernyak, V.Y., Yukhimenko, V.V., and Naumov, V.V (2008) Effect of air on the concentration of molecular hydrogen in the conversion of ethanol by a nonequilibrium gas-discharge plasma JETP Lett., 88 (2), 99–102 118 Chernyak, V.Y., Olszewski, S.V., Yukhymenko, V.V., Solomenko, E.V., Prysiazhnevych, I.V., Naumov, V.V., Levko, D.S., Shchedrin, A.I., Ryabtsev, A.V., Demchina, V.P., Kudryavtsev, V.S., Martysh, E.V., and Verovchuck, M.A (2008) Plasma-assisted reforming of ethanol in dynamic plasma-liquid system: experiments and modelling 119 120 121 122 123 IEEE Trans Plasma Sci., 36 (6), 2933–2939 Van Oost, G., Hrabovsky, M., Kopecky, V., Konrad, M., Hlina, M., and Kavka, T (2008) Pyrolysis/gasification of biomass for synthetic fuel production using a hybrid gas-water stabilized plasma torch Vacuum, 83 (1), 209–212 Dollard, J (2010) Hot fix for renewable energy Pollut Eng., 42 (9), 22–29 Pourali, M (2010) Application of plasma gasification technology in waste to energy – challenges and opportunities IEEE Trans Sustainable Energy, (3), 125–130 Galeno, G., Minutillo, M., and Perna, A (2011) From waste to electricity through integrated plasma gasification/fuel cell (IPGFC) system Int J Hydrogen Energy, 36 (2), 1692–1701 Gutsol, A., Rabinovich, A., and Fridman, A (2011) Combustion-assisted plasma in fuel conversion J Phys D: Appl Phys, 44 (27), 274001 391 393 Index a absorption, for VOCs removal 135 acetylene production 374–377 acid–base reactions 244–251 – conductivity changes 246–251 – pH changes 246–251 activated carbon (AC) 290–291 active oxides, in catalysts preparation 55–56 adsorption 175–177 – for VOCs removal 135 aerosols, plasma chemistry induced by discharge plasmas in 215–217 aliphatic compounds 275–279 – dimethylsulfoxide 277–279 – methanol 275–277 – tetranitromethane 279 alumina (Al2 O3 ), in catalysts preparation 49–50 – flame hydrolysis 49 – neutralization 49 – spray pyrolysis 49 – transition alumina synthesis by thermal treatment 49 aluminum phosphate (APO) 53 anode directed streamers 13 aqueous-phase chemistry of electrical discharge plasma 243–293, See also organic dyes; plasmachemical decontamination of water – aliphatic compounds 275–279 – in water and in gas–liquid environments 243–293 aqueous-phase plasma-catalytic processes 279–292 – activated carbon (AC) 290–291 – iron 280–284 – platinum 284–286 – silica gel 291 – titanium dioxide 288–290 – tungsten 286–288 – zeolites 291–292 aqueous-phase plasmachemical reactions 243–259 – acid–base reactions 244–251 – oxidation reactions 244, 251–256 – photochemical reactions 245, 257–259 – reduction reactions 244, 256–257 aromatic hydrocarbons 260–267 – phenol 260–263 aryl carbonium ion dyes 271–275 – diarylmethanes 271 – malachite green (MG) 271–272 – methylene blue (MB) 273 – triphenylmethanes 271 atmospheric pressure glow discharges (APGDs) 21 attrition milling 59 autothermal reforming 356 – of liquid fuels 378–381 – of methane 378 – reforming with carbon dioxide and oxygen 381 azo dyes 268–270 b background ionization 16 bacterial inactivation, post-discharge phenomena in 327–330 – temporal post-discharge reaction phenomenon 327 ball-formed catalysts 68 ball-milling-assisted hydrothermal synthesis 59 barrier discharges 2–3 – discharges at atmospheric pressure Plasma Chemistry and Catalysis in Gases and Liquids, First Edition Edited by Vasile I Parvulescu, Monica Magureanu, and Petr Lukes © 2012 Wiley-VCH Verlag GmbH & Co KGaA Published 2012 by Wiley-VCH Verlag GmbH & Co KGaA 394 Index bioelectrics 335–336 biofiltration, for VOCs removal 135 biological effects of electrical discharge plasma 309–337 – microbial inactivation by nonthermal plasma 310–317 – in water and in gas–liquid environments 309–337 Birkeland–Eyde process 207 branching, streamers 18–20 breakdown field bubbles, plasma chemistry induced by discharge plasmas in 214–215 bulk ionization mechanisms 4–5 c capillary impregnation 60 carbon dioxide dry reforming 369–373 – coupling to higher hydrocarbons 372 – of higher hydrocarbons 372–373 – of methane to syngas 369–372 carbon dioxide reforming (CDR) 357, 381 carbon nanotubes 74 carbonyl dyes 270–271 catalysis and plasma catalysis, comparison 160–161 catalysts forming 67–73 – ball-formed catalysts 68 – extrusion 70–72 – foams 72 – metal textile catalysts 73 – pelletization 69–70 – spherudizing 69 – tableting 67–68 catalytic NOx remediation from lean model exhausts gases, NTP-assisted 112–123 – composite catalyst concept 117 – consumption of oxygenates and RNOx 112–114 – – conversion of NOx and total HC versus temperature 112–113 – – GC/MS analysis 113–114 – NTP advantages 114–117 – NTP reactor coupling with catalyst reactor for catalytic-assisted deNOx 116–117 catalytic processes 45–77, See also plasma-assisted catalytic processes – oxidation, for VOCs removal 134 cathode directed streamers 13 chemical energy efficiency 360 chemical mechanisms of electrical discharge plasma 317–330 – interactions with bacteria in water 317–330 – – bacterial structure 319–320 – – peroxynitrite 325–327 – – reactive nitrogen species 324–327 – – reactive oxygen species 320–324 chemical processes induced by discharge plasma directly in water 217–224 – issues in 221–222 – plasma characteristics effect 222–224 – solution properties effect 222–224 – water dissociation by discharge plasma in water 217–221 chemical vapor infiltration (CVI) 64 Chick–Waston approach 316 cold atmospheric pressure (CAP) plasma 27 cold nonthermal discharge colony forming unit (CFU) 311 combined heat powers (CHPs) 90 – DBD effect on methane oxidation in 106–107 complex package 61 composite catalyst concept 117–119 – propene-deNOx on ‘Al2 O3 /// Rh–Pd/ Ce0.68 Zr0.32 O2 /// Ag/Ce0.68 Zr0.32 O2 ’ composite catalyst 118–119 – – GC/MS analysis of gas compounds at the outlet of catalyst reactor 119 – – NOx and C3 H6 global conversion versus temperature 118–119 condensation, for VOCs removal 136 conventional solid state reaction 59 conversion 139 coprecipitation-impregnation 59, 61 coprecipitation method 57, 59 – coupled with reactive grinding 58 coprecipitation-sedimentation 61 corona discharges 137 corona streamer discharges 2–3 coronas 9–20 – applications 9–11 – continuous corona discharges 10 – DC corona discharges 10 – occurrence 9–11 – positive-polarity-pulsed corona 11 – pulsed corona 11 d deNOx reaction, plasma-assisted 90–96 – NTP-assisted deNOx reaction 95 – release of N2 90 – – function F1 91 – – function F2 90 – – function F3 90, 93 – three-function catalyst model 90 – – THC D TNO 92 Index – – THC − TNO 91 – – THC × TNO 94 density functional theory (DFT) 277 deposition by electroless plating 61 deposition–precipitation method 66 diarylmethanes 271 dichloroacetyl chloride (DCAC) 162 dielectric barrier discharges (DBDs) 4, 26–32, 89, 173, 353 – applications of 31–32 – basic geometries 26–28 – effect on methane oxidation 106–107 – main properties 29–30 diffusional impregnation 60 dimethylsulfoxide 277–279 discharge with water spray 314 discharges at atmospheric pressure – barrier discharges 2–3 – corona streamer discharges 2–3 dry carbon dioxide reforming 357 dry gas plasma 311–313 dry mixing 61 e electric field effects 335–336 electrical discharge plasma in gas–liquid environments and in liquids 185–224, See also aqueous-phase chemistry of electrical discharge plasma – in bubbles and foams 214–215 – chemical processes induced by discharge plasma directly in water 217–224, See also individual entry – electrode configurations 186 – elementary chemical phenomena in 185–224 – elementary physical phenomena in 185–224 – gas-phase chemistry with water molecules 201–210 – – emission spectra 205 – – hydroxyl radicals in 204–205 – – optical emissions spectroscopy 205 – in gas phase with water vapor 188–189 – – discharge in bubbles 191–192 – – discharge with droplets and particles 192–193 – – in gas–liquid systems 189–193 – – point-to-plane discharge 191 – plasma-chemical reactions at gas–liquid interface 210–214 – plasma generation – – discharge over water 189–191 – – in gas–liquid environments and liquids 188–199 – – physical mechanisms 188–199 – plasma generation directly in liquids 193–199 – – physical observations 198 – – point-to-plane discharge 195–196 – – thermal energy balance 197–199 – primary chemical species formation by discharge plasma in contact with water 199–217 – – chemical species in gas phase with water vapor 199–210 – in water spray and aerosols 215–217 electrical discharge plasma in water and in gas–liquid environments 309–337 – biological effects of 309–337, See also under biological effects electrical discharge plasma interactions with living matter 330–336 electron energy distributions 1–2 electroplating 62–64 electroporation 335 electrostatic precipitator (ESP) 10 electrosurgical plasmas 334–335 Eley–Rideal mechanism 284 embedded nanoparticles 62 extracorporeal shockwave lithotripsy (ESWL) 333 extrusion 70–72 – cylinders 71 – honeycombs 71 – miniliths 71 f Fenton’s process 280–281, 285–286 flame hydrolysis 49–51 foams 72 – plasma chemistry induced by discharge plasmas in 214–215 fuel production efficiency 359 full width at half maximum (FWHM) pulses 98 fullerenes 74 g gas discharge in bubbles 314 gas hourly space velocity (GHSV) 108, 356, 360–361 gas–liquid interface, plasma-chemical reactions at 210–214 – emissions spectroscopy of 212 – glow discharge electrolysis 211 – hydrogen peroxide formation 213 395 396 Index gas–liquid interface, plasma-chemical reactions at (contd.) – laser-induced fluorescence (LIF) spectroscopy of 212 – reactions of ozone 213 gas to liquid hydrocarbon fuels (GTL) 355 gliding arc plasma reactor 376 gliding arcs 32–34 global warming 132 glow discharge plasma electrolysis 364 glow discharges at higher pressures 4, 20–26 – glow-to-spark transition 20 – high-pressure glow discharges 21 – instabilities 25–26 – low-pressure glow discharge 20 – properties 21–22 – spark/arc formation 20 – studies 22–25 – – DC glow 23 – – microglow discharges 23 – – microplasmas 24 – – nanosecond-pulsed discharges 25 – – Townsend mode glycerol 377 h Haber-Weiss process 282 heterocyclic aromatic hydrocarbons 265–267 homogeneous breakdown 14 Hăuls process 358, 374375 humid gas plasma 313 hybrid models 14 hydrocarbons, hydrogen and syngas production from 353–384 – autothermal reforming 356 – description and evaluation of the process 358–360 – dry carbon dioxide reforming 357 – energy balance 359–360 – – efficiency 359–360 – – energy requirement 359–360 – materials balance 358–359 – – conversion 358–359 – – selectivity 358–359 – – yield 358–359 – partial oxidation (POX) 356–357 – plasma-assisted reforming 360–382 – – autothermal reforming of liquid fuels 378–381 – – autothermal reforming of methane 378 – – carbon dioxide dry reforming 369–373 – – combined processes 377–382 – – partial oxidation 365–369 – – plasma pyrolysis 373–377 – – steam reforming 360–365 – pyrolysis 357–358 – steam reforming (SR) 355–356 hydrogen peroxide 254, 321–324 – OH radical attack on proteins 322 hydrogen production from hydrocarbons 353–384 – current state of 354–358 hydrogen radical 256–257 hydrothermal reactions 48, 51–53, 56, 59 hydroxyl radical 252–253, 320–321 i ignition method 59 impact ionization 4–5 impregnation 59, 61, 66 – capillary 60 – diffusional 60 – incipient wetness impregnation 60 – wet impregnation 60 inception voltage 14 incipient wetness impregnation 60 initiation cloud 16–18 in-plasma catalysis (IPC) 97, 141, 171 interaction, streamers 18–20 intimate mixed oxides 56 iron 280–284 – catalytic cycle, in plasmachemical degradation of phenol 282–284 l Langmuir–Hinshelwood (LH) model 179 late streamers 16–18 living matter, electrical discharge plasma interactions with 330–336 – electric field effects and bioelectrics 335–336 – physical mechanisms of 330–336 – – shockwaves 332–334 – – UV radiation 331–332 – – x-ray emission 332 – thermal effects and electrosurgical plasmas 334–335 local field approximation lumped resistor approach 22 m malachite green (MG) 271–272 mechanical mixing 59, 61 Index membrane separation, for VOCs removal 136 metal catalysts 62–67 – preparation – – via chemical vapor infiltration 64 – – via electroplating 62–64 – embedded nanoparticles 62 – metal wires 64–65 – nanowires 65 – supported metals 65–66 – supported noble metals 66–67 metal-containing molecular sieves 53–55 metal oxides on metal foams and metal textiles 61–62 metal textile catalysts 73 metal wires 64–65 methane catalytic oxidation, NTPs in 105–112, See also under nonthermal plasmas (NTPs) – effect of catalyst composition 107–110 – – effect of support 107–108 – – effect of noble metals 108–109 – – palladium-based catalysts 108–109 – – platinum-based catalysts 109 – influence of water in CHP conditions 109–110 – – coupled plasma–Pt(X)/Al2 O3 or plasma–Pd(X)/Al2 O3 110 – – influence of wet mixture on support 110 – – on palladium-based catalysts 110 – – on platinum based catalysts 110 methanol 275–277 – methanol pyrolysis 377 methylene blue (MB) 273–274 microbial inactivation by nonthermal plasma 310–317 – bacterial inactivation – – by DBD plasma 312 – – by glow discharge plasma 312 – – by microwave plasma 311 – dry gas plasma 311–313 – gas plasma in contact with liquids 313–314 – – discharge over water and hydrated surfaces 313–314 – – discharge with water spray 314 – – gas discharge in bubbles 314 – humid gas plasma 313 – kinetics of 315–317 – – sterilization 316–317 – – viability tests 316–317 – plasma directly in water 314–315 microdischarges 29, 96 microscopic discharge mechanisms 4–6 – bulk ionization mechanisms 4–5 – surface ionization mechanisms microwave discharge minimal streamers 17 mixed oxides, in catalysts preparation 56–59 – intimate mixed oxides 56 – perovskites 56–59 Monte Carlo model 14 moving boundary models 14 multi-walled nanotubes (MWCNTs) 75 n N-acetylglycosamine (NAG) 319 N-acetylmuramic acid (NAM) 319 nanosecond pulsed DBD reactor coupled with a catalytic deNOx reactor 97–99 nanowires 65 neutralization 49 noble metal catalysts, in VOCs removal 140 nonequilibrium plasmas at atmospheric pressure 1–34, See also microscopic discharge mechanisms – barrier discharges 2, See also dielectric barrier discharges (DBDs); surface discharge – corona streamer discharges 2, See also coronas; streamers – electron energy distributions 1–2 – gliding arcs 32–34 – glow discharges at higher pressures 20–26, See also individual entry – nonthermal plasmas 1–2, See also nonthermal discharges nonthermal discharges 1–2 – barrier discharges – chemical activity 6–8 – – ozone production 6–7 – cold nonthermal discharge – corona streamer discharges – diagnostics 8–9 – – nitrogen-containing discharges – – optical emission spectroscopy – glow discharges – microwave discharge – Townsend discharge – transient discharges – transition to sparks, arcs, or leaders nonthermal plasmas (NTPs) 89, 137–139 – catalytic NOx remediation from lean model exhausts gases 112–123, See also individual entry – chemistry 100–102 – for environmental applications 89 397 398 Index nonthermal plasmas (NTPs) (contd.) – kinetics 100–102 – methane catalytic oxidation on alumina-supported noble metal catalysts 105–112 – – DBD effect in CHP conditions 106–107 – – effect of catalyst composition 107–110 – – effect of dielectric material 106 – – effect of water 106 – microbial inactivation by 310–317 – NOx remediation 89–90, 96–105 – – nanosecond pulsed DBD reactor coupled with a catalytic deNOx reactor 97–99 – – UHCs presence, importance 96–97 – NTP assisted catalytic deNOx reaction in presence of multireductant feed 119–123 – – conversion of NOx and global HC versus temperature 119–120 – – GC/MS analysis 120–123 – NTP-assisted deNOx reaction 95 – plasma energy deposition and energy cost 102–105 NOx abatement by plasma catalysis 89–125 – general deNOx model over supported metal cations 90–96, See also deNOx reaction, plasma-assisted – nonthermal plasma-assisted catalytic NOx remediation 89–90, See also nonthermal plasmas (NTPs) o organic dyes 267–275 – aryl carbonium ion dyes 271–275 – azo dyes 268–270 – carbonyl dyes 270–271 oxidation reactions 251–256 – hydrogen peroxide 254 – hydroxyl radical 252–253 – organic radicals 253 – ozone 253–254 – peroxynitrite 255–256 oxides and oxide supports, in catalysts preparation 49–52, See also alumina (Al2 O3 ); silica (SiO2 ); titanium dioxide (TiO2 ); zirconium oxide (ZrO2 ) oxygen, reforming with 381 ozone 253–254 p packed-bed discharges 30–31, 138 palladium-based catalysts 108–109 partial oxidation (POX) 356–357, 365–369 – conversion of higher hydrocarbons 367–369 – conversion of methane 365–367 pelletization 69–70 perhydroxyl radical (HOž ) 257 perovskites 56–59 – attrition milling 59 – conventional solid state reaction 59 – coprecipitation 57, 59 – – coupled with reactive grinding 58 – hydrothermal synthesis 59 – – ball-milling-assisted 59 – ignition method 59 – reactive grinding of single oxides 58 – sol–gel route 57 – solid state reaction of mixed oxides 57 – sol-precipitation method 59 – spray pyrolysis 57 peroxone process 254 peroxynitrite 255–256, 325–327 – reactivity with lipids 326 phenol 260–263 – nitration of 263 – nitrosation of 263 – OHž radical attack on phenol ring 261 – ozone radical attack on phenol ring 261 photocatalysis, for VOCs removal 134 photochemical reactions 245, 257–259 – photolysis of ozone 258 – use of UV radiation 258 photochemical smog 132 photo-Fenton reaction 282 photoionization 15–16 placed postplasma (PPC) 97 plasma-activated water (PAW) 327 plasma-assisted catalytic processes 45–77, See also catalysts forming; metal catalysts – activation 45–77 – catalysts preparation methodologies 49–67 – – active oxides 55–56 – – mixed oxides 56–59 – – oxides and oxide supports 49–52 – – supported oxides 59–62 – – zeolites 52–55 – chemical composition and texture 47–48 – – hydrothermal syntheses 48 – – precipitation 48 – – template-assisted syntheses 48 – elements used 48 – features generated by 46–47 – plasma discharge, catalysts changes generated by 46–47 – preparation 45–77 – regeneration 45–77 Index – – – – – of catalysts 73 single-stage plasma catalysis reactor 47 sputtering processing 47 VOC removal from air by 131–165, See also volatile organic compounds (VOCs) plasma bullets 28 plasma display panel (PDP) 27 plasma-driven catalysis (PDC) 141 plasma produced catalysts and supports 74–76 – sputtering 76 plasma pyrolysis 373–377 – acetylene production 374–377 – methane pyrolysis to hydrogen and carbon 373–374 – pyrolysis of oxygenates 377 plasmachemical decontamination of water 259–279 – aromatic hydrocarbons 260–267 – – heterocyclic 265–267 – – phenol 260–263 – – polycyclic 265–267 – – substituted 263–265 plasmajet platinum 284–286 – as catalyst in Fenton’s reaction 285–286 platinum-based catalysts 109 polychlorinated biphenyl (PCB) compound 266 polycyclic aromatic hydrocarbons 265–267 positive-polarity-pulsed corona 11 positive streamer propagation 15–16 – background ionization 16 – electron sources for 15–16 – photoionization 15–16 post-discharge phenomena in bacterial inactivation 327–330 postplasma catalysis configuration (PPC) 97, 171 precipitation 48, 50 primary streamers 16–18 pulsed corona 11 pyrogenic titania 52 pyrolysis 357–358, See also plasma pyrolysis – of oxygenates 377 r Raether–Meek criterion 14 reactive grinding 58 reactive nitrogen species (RNS) 310, 324–327 reactive oxygen species (ROS) 310, 320–324 – hydrogen peroxide 321–324 – hydroxyl radical 320–321 reduction reactions 244, 256–257 – hydrogen radical 256–257 – perhydroxyl/superoxide radical 257 s secondary streamers 16–18 – physical mechanism of 18 selective catalytic reduction (SCR) 89 separate package 61 shockwaves 332–334 silica (SiO2 ), in catalysts preparation 50–51 – flame hydrolysis 50–51 – hydrothermal reactions 51 – precipitation 50 – sol–gel methodology 50 – sol–gel processes 50 silica gel 291 silicalite 51 silicon-aluminum phosphate (SAPO) 53 single-stage plasma catalysis reactor 47 single-stage plasma-catalytic systems 141–150 – acetone 143 – benzene 144–145 – dichloromethane 144 – formaldehyde 143 – isopropanol 143 – noble metal catalysts 147–148 – phenol 145 – propane 143 – TiO2 147 – toluene 145–146 – transition metal oxides 148 – trichloroethylene 144 – and two-stage plasma catalysis, comparison,161–162 single-walled nanotubes (SWCNTs),75 sol–gel processes 50, 57, 59 sol-precipitation method 59 specific input energy (SIE) 139 spherudizing 69 spray pyrolysis 49, 57 sputtering 76 steam reforming (SR) 355–356, 360–365 – conversion of higher hydrocarbons 362–363 – conversion of methane 360–362 – conversion of oxygenates 363–365 – microwave plasma 363 – toluene 363 sterilization 316–317 streamers 9–20 – applications 9–11 399 400 Index streamers (contd.) – – gas and water cleaning 10 – – ozone generation 10 – – particle charging 10 – branching 18–20 – homogeneous breakdown 14 – initiation 14 – initiation cloud 16–18 – interaction 18–20 – late streamers 16–18 – negative streamers 12–13 – occurrence 9–11 – positive streamers 12 – primary streamers 16–18 – propagation 15–16, See also positive streamer propagation – properties 11–14 – – hybrid models 14 – – Monte Carlo model 14 – – moving boundary models 14 – secondary streamers 16–18 substituted aromatic hydrocarbons 263–265 superoxide radical 257 supported metals 65–66 supported noble metals 66–67 – deposition–precipitation method 66 – impregnation 66 supported oxides, in catalysts preparation 59–62 – complex package 61 – coprecipitation 59–60 – coprecipitation-impregnation 59, 61 – coprecipitation-sedimentation 61 – dry mixing 61 – impregnation 59 – mechanical mixing 59, 61 – metal oxides on metal foams and metal textiles 61–62 – separate package 61 – sol–gel 59 – wet mixing 61 surface discharge 26–32 – basic geometries 26–28 – main properties 29–30 – and packed beds 30–31 surface ionization mechanisms syngas production from hydrocarbons 353–384 t tableting 67–68 technical scale plasma reactor 370 temperature-programmed desorption (TPD) 90 template-assisted syntheses 48 temporal post-discharge reaction phenomenon 327 tetranitromethane (TNM) 256, 279 thermal activation 177–178 thermal oxidation, for VOCs removal 133–134 thermal treatment, transition alumina synthesis by 49 three-function catalyst model 89–91 titanium dioxide (TiO2 ) 51–52, 288–290 Townsend discharge Townsend impact ionization coefficient transient discharges transition metal oxides, in VOCs removal 140 trichloroacetaldehyde (TCAA) 162 triphenylmethanes 271 tungsten 286–288 two-stage plasma-catalytic systems 141–142, 150–153 – adsorbent materials 153 – benzene 151 – butyl acetate 151 – cyclohexane 151 – dichloromethane 151 – ozone role 150 – propane 151 – toluene 151–152 – transition metal oxides 150 – trichloroethylene 151 u unburned hydrocarbons (UHCs) 89, 96–97 UV radiation 331–332 v viability tests 316–317 volatile organic compounds (VOCs) 131–165 – decomposition in plasma-catalytic systems 142–164 – – catalyst loading effect 157–159 – – chemical structure, effect of 154 – – experimental conditions, effect of 155–159 – – humidity effect 155–156 – – inorganic by-products 163–164 – – organic by-products 162–163 – – oxygen partial pressure effect 156–157 – – plasma catalysis and adsorption combination 159–160 – – reaction by-products 162–164 – – single-stage plasma-catalytic systems 142–150, See also individual entry Index – – – – – – – – – – – – – – – – – – – – – – – – – – – – – – VOC initial concentration, effect of 155 emission in atmosphere, sources 131 – anthropogenic 131 – biogenic 131 environmental problems related to 132–133 – global warming 132 – photochemical smog 132 health problems related to 132–133 – chronic effects 132 – eye and respiratory tract irritation 132 plasma-catalytic hybrid systems for VOC decomposition 137–142 – catalysts types 140–141 – corona discharges 137 – noble metal catalysts 140 – nonthermal plasma reactors 137–139 – packed-bed discharges 138 – process selectivity considerations 139 – single-stage plasma-catalytic systems 141 – transition metal oxides 140 – two-stage plasma-catalytic systems 141–142, 150–153, See also individual entry removal from air by plasma-assisted catalysis 131–165, 171–180 – adsorption 175–177 – catalyst influence in plasma processes 172–174 – catalyst properties 174–175 – interactions between plasma and catalysts 171–180 – mechanisms 171–180 – physical properties of discharge 172–174 – plasma influence on catalytic processes 174–177 – plasma–catalyst combinations 172 – – plasma-catalytic mechanisms 179–180 – – plasma-mediated activation of photocatalysts 178–179 – – reactive species production 174 – – thermal activation 177–178 – removal techniques 133–137 – – absorption 135 – – adsorption 135 – – biofiltration 135 – – catalytic oxidation 134 – – condensation 136 – – membrane separation 136 – – photocatalysis 134 – – thermal oxidation 133–134 w water gas shift (WGS) reaction 355 water spray, plasma chemistry induced by discharge plasmas in 215–217 wet impregnation 60 wet mixing 61 wetness impregnation 62 x x-ray emission 332 z Zeldovich mechanism 207 zeolites 291–292 – in catalysts preparation 52–55 – – hydrothermal method 53 – – hydrothermal synthesis 52 – – metal-containing molecular sieves 53–55 – – structure of 54–55 zirconium oxide (ZrO2 ), in catalysts preparation 52 – flame hydrolysis 52 – precipitating agents 52 401 ... Catalyst Loading 157 Combination of Plasma Catalysis and Adsorption 159 Comparison between Catalysis and Plasma Catalysis 160 Comparison between Single-Stage and Two-Stage Plasma Catalysis 161... precipitator (ESP) and is used in the utility, iron/steel, paper manufacturing, and cement and ore-processing industries Similar charging methods are used in copying machines and laser printers [4, 65]... Gas-Phase Chemistry with Water Molecules, Ozone, and Nitrogen Species 206 Plasma- Chemical Reactions at Gas–Liquid Interface 210 Plasma Chemistry Induced by Discharge Plasmas in Bubbles and Foams 213 Plasma