‘OZONE SCIENCE & ENGINEERING 0191951288 $5.00 +00 Vol. 10, pp. 367-378 International Ozone Assecsion Printed inthe U.A. Copyright © 1988 Ozone Generation From Oxygen And Air: charge Physics And Reaction Mechanisms U. Kogelschatz, B, Eliasson and M. Hirth ASEA BROWN BOVERI Corporate Research 5450 Baden, Switzerland Received for Review : 9 November 1987 ‘Accepted for Publication : 7 May 1988 Abstract Industrial ozone generation uses a special high pressure, low temperature electrical discharge which is’ referred to as the dielee the barrier discharge or alent dacharge. “The lamentay strcture Gf this discharge, andthe properties of individual microdischarges ate discussed. The. main ‘reaction paths for the excled atomic And molecular species in. oxygen and air are. identified. Possible approeres to, cain mig power denies high ozone” generating eliiciencies oF high ozone concentrations are’ discussed Introduction During the past decade, industrial ozone generation has been improved in several aspects, Three areas of improvement can be clearly identified: A. Higher power densities, B. Higher ozone generating efficiencies, C. Higher ozone concentrations. ‘The maximum power density (measured in kW/m? of electrode area) determines the otal electrode area necessary 1 produce a required amount of ozone, and thus determines the size of the ozone. generator, Today's ‘medium frequency ozone generators reach power densities of 2.5 KWim?, which is considerably higher than the 0.203 kW/m= typical for the older S0/60 Hz ozone generators. This step has resulted in a Grastic reduction in the size Of ozone generating’ equipment with a corresponding reduction of investment costs. The ozone generating efficiency can be measured in kilograms of ozone produced per kilowatt: hour of electrical energy. 367368 ——U. Kogelschatz et al. In the technical literature, the reciprocal value is preferred: the specific power consumption measured in kilowatthour per kilogram ozone, produced. For many of the older installations, typical values were 10-25 kWhikg. ‘These values depend very much on the feed gas (air or oxygen) and on the desired ozone concentration. Modern ozone generators approach values of 10 kWh/kg in air and 4 kWhikg in oxygen at low ozone concen- trations. Much of this progress is due to a better understanding of the discharge physics and of the complex chemistry of ozone formation. Microdischarge Properties It is well established that the dielectric barrier discharge in air or Giygen “at_near” atmospheric ‘pressure is far. from being. homogencous. ‘The current flow through the ‘dscharge gap is brought about bya large umber of. statstically® distibuted mcradecharges. "The. most. stiking manifestations of these, microdischarges are Lichtenberg figures. Figure Tshows the “footprints" of individaal, microdiseharges on a. photographic plate which was in contact with the discharge fora short time’ (about 1 Inilisecond), Figure 1. Photographie Lichtenberg figure. showing the “footprins™ of sta microdiseharges (Original size:""7 cm x. 10 More detailed information about these microdischarges was collected by fast image intensifier recordings (Tanaka et al, 1978; Heuser, 1985) and detailed current and charge measurements (Hirth '1979, Hirth et al, 1983), Since ozone is formed only in these microdischarges and not in the Space between, it is essential to understand and optimize the condi- tions in the micfodischarge channels. Today's understanding of the Imicrodischarges can be summarized as follows:OZONE GENERATION FROM OXYGEN AND AIR 369 Each microdischarge lasts only for a few nanoseconds (Figure 2), much shorter than was assumed in the older literature (Honda & Naito, 1955; Gobrecht et al, 1964) AIR Figure 2. Microdischarge current in oxygen and in air (Amplitude: 40 mA/small division, time: 2 ns/small division). The microdischarge has an almost cylindrical channel of roughly 100 zm radius and spreads into a much wider surface discharge on the dielectric. The current dps in the, mirodscharge, channel ean reach, values of 100-1000 A/em?. "Due to the very shops duratign of microdischarges, the transported. charge is of the order 10-19 - 10 coulomb, and iis. energy density is of the order 10 mJ/em3. ‘The microdischarge’ channel can be considered as a transient glow discharge with electron temperature of approximately $0,000°K and gas temperature close to room temperature, ‘The efficiency of ozone production in such a microdischarge depends very much on its strength, which can be influenced by the gap spacing, the pressure, the dielectric, the properties of the metal electrode and, to some extent, also on the electrical circuit (pulsed ozone generators). Also, the humidity of the feed gas has a drastic effect on the microdis- charge properties and on the chemical reaction paths. For this reason, the feed gas normally is dried to dew point below -60" Discharge Modelling ‘A volume clement of feed gas traveling through the discharge gap will fe “exposed” to" ange’ nuner ‘of misrodseharges.” “The phase. and Chemical changes. in’ & microdischarge channel cat be tteated by soWing fay complex’ reaction schemes. (Gibalov et aly” 198; Eliasson et aly 1985; 1986a). “When’ the reaklown voltage is ‘reuched, avery’ fast310 U. Kogelschatz et al. jonization process generates the charge carriers necessary for current flow. ‘In pure oxygen, O*, Op, O', Op", and Os" ions afe obtained in addition’ electrons (Figure 3).’ “Their relative importance depends on the strength of the mierouischarge. 10 k1o-© | oO 2 4 8 10 12 14 16 18 20 TIME (ns) Figure 3. Numerical simulation of the charge carriers in a_microdis- charge channel.” All particle ‘densities are normalized ig the gas density in the discharge gap (ng = 24 x 10 m3), ‘Also the partition of the discharge energy between electrons and ions depends very much on the strength of the microdischarge. In weak microdischarges, a considerable fraction of the energy is. dissipated by ions. “In stronger microdischarges, almost the entire discharge energy can be fed into the electrons. ‘The strength of a microdischarge can be characterized by the energy deposition in the microdischarge channel, or by the relative concentration of onygen atoms ((OY[Op)) Feached in the channel ‘at the termination fof the microdischarge. “Recent investigations (Eliasson et al., 1985; 1986a) revealed that this quantity is several orders of magnitude’ higher than was assumed in previous publications (Yagi et al, 1979b; Gibalov etal, 1981). The strength of the microdischarge has an’ essential influence on the chemical reactions leading to ozone formation and. the ozone generating efficiency.371 Main Reactions In Oxygen In 3, search for, optimum condions for ozone formation, a, computer Bode ‘resting 70 reactions among 16 particle species was used (Eliasson Pal, Wks}: Tae main rate of these cautions can be suman 1) Ozone is formed mainly from oxygen atoms by the reaction: 0 + 024M => 03" +M-—-> 03 +M ir where Mis third collision partner (02, 03, in air also Np). 2) In pure oxygen the principal reactions resuking in oxygen atoms are 6 +02 => © + OYA But) —-> © + OCP) + OCP) [2] and e+ 02 e+ YB 38y) —-> © + OCP) + OCD) B} (The terms in brackets are spectroscopic notations used to characterize excited states of the atoms and molecules involved). 3) Tonic processes contribute only negligibly to ozone formation. 4) There is an optimum microdischarge strength for efficient ozone generation. Ir the microdscharge is too weak, ions consime considerable portion Of the ishorge energy, which this is not tied for orone formation On the other ‘hands the chemistry of ozone formation imposes upper Timit'on the strength of the microdischarge. In. very "weak ‘microus charges, every oxygen atom leads to the formation of one dzone molecule, sceonting 10 Reaction {I}. This no longer true at higher oxygen 0m concentrations, when’ Additional reactions involving Oxygen atoms gin importance. ‘The main competing reactions are O+04+4M—> 24M ro} 0 + 03 > 202 fo 0 + 037 —> 203 (6) 03° stands for an excited transient ozone species which is the initial product ‘of Reaction [Ij Figure 4. demonstates that the ‘ozone. eld per oxygen atom, and thus the efficiency of ozone generation, drops Grastically if the’ microdischarges become too strong. ‘The optimum ricrodischarge strength is a compromise between avoiding energy losses to ions and sill obtaining a reasonable conversion efficiency. It is of the order [OV[O2] ~ 10U. Kogelschatz et al. am = Z © s = 08 S 06 2 os s & oe 8 7 7 = 2 ot 40° 40% 10 10 10 RELATIVE ATOM CONCENTRATION [0] /[02] Figure 4. Number of ozone molecules formed per oxygen atom as a function of oxygen atom concentration, Main Reactions In Air Ozone generation in air is much more gompliated than it is in. pure coxygen. "Additional ionie species (N*, No*) and the excitation and. diso- ciation of nitrogen ‘molecules adds to the complexity of the chemical reactions. “Two striking experimental observations hive. been explained recently: ‘A. The presence of nitrogen apparently provides additonal renetion paths for ozone formation; B. At very high specific energies, the performance of the discharge Changes in a drastic way "namely ‘ozone formation breaks down completely, and all previously generated ozone is destroyed (state of discharge poisoning, ozone-less mode). The clue to these phenomena i the presence of traces of nitrogen oxides. that ean be detected in the output of aitfed ‘ozone generators Meastremenis of the sum parameter NOx = NO + NOp + NOg*s 2N2Os huve Been presented by diferent authors (Yagi et al; 19992; Okazakl et ol, 1988). More detailed measurements of the ‘trogen “oxides NO, No3,’NzO5 and N70 recently have been published (Gibalov et aly, 1085! Kogelstits &'Baesier, 1986, Samoiovich & Gitalow, 1986). A piper on the detection of the last missing. spesis, nitrogen’ trioxide (NOS, was presented by Eliasson and. Kogelschatz (1587) ‘The kinetics of NOx formation can be summarized as follows. The nitrous oxide N20 and the nitric oxide NO are the initial oxides formed ‘withinOZONE GENERATION FROM OXYGEN AND AIR 373 100 ns after the initiation of a microdischarge (Bliasson & Kogelschatz, 19860). “The main teaction leading 10 N20 formation involves. the meta: stable excited No(A $y") molecule: Nz (A) + 02 —> N20 + 0 a Nitric oxide is produced mainly from two reactions involving nitrogen atoms: N + O2 No +0 8] N + 03 —> NO + 02 P) Reaction [8] results in additional oxygen atoms that can finally form There are two more such additional reactions paths (Eliasson et al, 1984): N + NO > N20 (0) Nz (AB) + 02 > Nz + 20 (uy In the presence of ozone and oxygen atoms, NO is oxidized via NO> tnd NOS‘To the highest oxidation atte Noe. There are many reaction paths aigong the ‘diferent nitrogen oxides” ‘The’ complexity of the NOy Einetics is demonstrated: by Figure Sy which shows a numeral simulation Of the action of a. series of 400 identical microdicharges.in_ a mixture Ot Sie Np and. 209%. Op (Eliason & Kogelschat, 198). The reaction ene thet Schema reactions ong, 30 testing pele, nd can Simulate the major experimental tends of ozone and ‘NOx formation In fie Apareny He sie of dheharge powonie ia which tone formation treaks down, chn be predicted by such a model aso Conclusion And Engineering Aspects Understanding of the ozone formation process in oxygen and in air has improved considerably during the last decade. Detailed experimental investigations into the properties of microdischarges, exact measurements ‘of ozone and different NOx species under different operating conditions, fand computer modelling of the various processes in the discharge gap have led to an almost quantitative understanding of the major processes. Ie turns out that these. investigations are not only of scientific merit, but also have an, essential influence on the engineering of advanced ozone generators. The conditions in the microdischarges can be influenced and controlled by the composition of the feed gas, the gap spacing, the pressure, the dielectric, the metal electrode, the power supply, and the Pooling circuit, Today, we are in a position to tailor an ozone’ generator to the needs of the customer. ‘The overall parameters: power density, efficiency and high ozone concen tation are," in certain respects, conflicting requirements. ‘The best374 U. Kogelschatz et al. compromise depends on the specie application. The requitements for zone in driaking water. of waste, water treatment may be ute diferent from the requirements of ozone wers in the ‘chemical or pharmacesticat industries, or when ozone is used for bleaching Kaolin Or paper pulp; 40000 4000 400 40 CONCENTRATION (ppm) o4 0.01 0.004 0.04 O4 40 SPECIFIC ENERGY(eV/MOLECULE) Figure 5. Comparison of calculated and measured ozone and nitrogen oxide concentrationg. Assumptions: Energy per microdis. charge: 5.4 mJ/em’; time between microdischarges: 3 ms Measurements: 0 ozone, NOx, A N30. Every ozone generator with fixed operating conditions can be characterized by its efieeney versus concentration. cive, "As Figure 6 shows, wih pet engineering, we do have quite a bit of infvence on the ‘curve high elfiienciesat low concentations are. demanded, an OzONe. gene: ator performing according to curve I would be the Gisice, ite See, toplction"reaures eny” hgh rene “Conenttions we woul cera prefer an ozone generat which performs according to cune Il, Concer. ations high 2 (oy mig) nar on over 209m engen can he reached. "Although this Yast value & higher than the explosion hint gen in ‘the literature" (13-17% onone. by weight in" onygen}, we, have fever Observed explosive Unstabites in our laborstory experiments For larger ozone generating systems, a careful evaluation of the compo- sition and preparation of the feed gas, type of ozone generator, handlin Of process gas (once-through or recycling) will be necessary io. speci the “best. system parameters. Tt has been “a long way from the’ first investigations into the nature of microdischarge properties to. the engi:OZONE GENERATION FROM OXYGEN AND AIR 375 neering of large ozone generating plants. The performance of today’s adianced ozone generating systems! certainly proves that was worth ¢ effort, 20; I 2 G10 3 & r 0 10. 20 OZONE CONCENTRATION (%) Figure 6, Efficiency versus concentration characteristics of different esigns Of “ozone generators” (00% efficiency ‘corresponds toa spestic power consumption ‘of O82 kWh). References ELIASSON, Bg KOGELSCHATZ, Us BAESSLER, P., 198, "Dissociation of (Op in Noir Matures J Phys, Bs At. Mol. Phys. 17.797 = L8O1. ELIASSONB.HIRTH, Mz KOGELSCHATZ, U,, 1585, "Ozone Formation in Dose’ Bart ‘Dactargs Ones, 9 ac Tham posium-on Plasma Chemistry, Eindhoven, pp, 339-34 ELIRSSON, Br ROGELSCHATZ, Uy 1980) testron impact Dissociation in Open’. Pins. Be At. Mol, Bays: 13401247, ELIASSOR, By HIRTH, AM; KOGELSCHATZ, U 986, “Ozone Syothess From, Oxygen in. Dielectric Bartier Discharges? BBC’ Research’ Report No KERR M40C. J. Pye: Ds Appl, Phys, 21421-1437 (1987) ELINSSON: By KOGELSCHIATZ, Ur 19860 "30 Formation in Gronizers’ J. Chem. Phys. 83:279-282. ELIASSON, B; KOGELSCHATZ, U., 1987, "Nitrogen Oxide Formation in Ozonizers io Poet Symposin an Plsina Chemists TOky9, 736-740, a GIBALOV, V.; SAMOILOVICH, V.G;, PHILIPPOV, Y.V., 1981, "Physical Chemisty ‘of Electrosynthesis'of Ozone. ‘The Resulis of Numerical Experiments", Russ. J. Phys. Chem. 55:471-479,376 U. Kogelschatz et al GIBALOV, V.L; SAMOILOVICH, V.G.; WRONSKI, M, 1985, "Electrosynthesis ‘of Nitrogen’ Oxides and zine in Ozonizer’, in’ Proc. 7th Intl Sym= a ma. Chemist, Pindhoven, po, a01-40e GOBRECHTH: MEINHARDY, O: HEIN E064 "Ober de Suite Ena. ‘ung in Ozonisatoren’, Ber. d. Bunsenges. f” phys. Chem. 68:55-63 HEUSER, C, 1985, "Zur Ozonerzeugung in Elektrschen Casentladungen’, Dissertation, RWTH Aachen. HIRTH, M,_ 1981, "Teilprozesse_ bei der Ozonerzeugung Mittels_Stiller Elektrischer Entiadung’, Beitr. Plasmaphys. 20:1-27 HIRTH, M, KOGELSCHATZ, U; ELIASSON, By, 1983, “The structure of the Microdischarges in Ozonizers and Theif, Influence on the Reaction Kinetics", in Prot. 6th Intl Symposium on Plasma Chemistry, Montreal, Bp. 663-668. HONDA, Ks NAITO, ¥.. 1955, "On the Nature of Silent Electrical Dis- charge", J. Phys. Soc, Japan ‘10:1007-1011 KOGELSCHATZ, "Us BAESSLER, P, 1986, "Determination of Nitrous nitrogen Pentoxide ‘Concentrations. in the Output. of Fed High Power Density Ozone Generators’, in 5 on_Ozone —+_Ulta-Violet “Water Treatment, Aquatech, Amsterdam, ASEASIS, See alba Orne Source, Engnceiig 198 206 (1987) OKAZAKI, 'S; KUBO, S; NIWA, HL; KOGOMA, Mz SUGIMITSU, fi MORIWAKI, “Ts INOMATA, "T., "1988, "Ozone Formation From the Reactions of Op-Activated No Molecules and a New Type Ozone Generator With Fine Wire Electrode’, Ozone: Sci. Engrg. "10(2)137- 151 SAMOILOVICH, V.G.; GIBALOV, V.1, 1986, "Kinetics of the Synthesis of ‘Ozone and Nitrogen Oxides in a Barrier Discharge, Russ. J. Phys. Chem, 60:1107-1116. TANAKA, Mx YAGI, Sz TABATA, N,, 1978, "The Observation of Silent Discharge by Image intensifier (in “Japancse)’, Trans. IEE of Japan 98A:57-62. YAGI, S; TANAKA, M; TABATA, N, 1979, "Generation of NOx in Ozonizers", Trans. IEE of Japan 99:41:48 YAGI, S; TANAKA, M,_1979b, “Mechanism of Ozone Generation in ‘AitFed Ozonizers’, J. Bhys. D: Appl. Phys. 12:1509-1520 Key Words Ozone, Ozone Generation From Oxygen & Air, Discharge Physics of Ozone’ Generation, Reaction Mechanisms of Ozone’ Generation, Generation of Nitrogen Oxides During Ozone Generation From Air, Engineering Aspects of Ozone Generation Résumé [La production industrielle dozone requiert Tullisation une décharge Gecttgue. spéciale A haute, pression et baste température: la decharge Sllenciewse. "La structure. de’ vette écharge et let propretés ‘des micto- Sécharges élémentaves sont i) présentées. On ident. les principals Noles ‘de réaclons pour les divers aiomes et molectles exces, dans Fonygene et dans Tain, On expose les: possiblités obtenir de. hautesOZONE GENERATION FROM OXYGEN AND AIR 377 ensités de puissance, des rendements élevés de production ozone ou des concentrations élevées d'ezone, ‘Zusammenfassung Die industrielle Ozonherstellung basiert auf einer speziellen Hochdruck- Niedertemperatur-Gasentladung: der stillen Entladung. Die Filamentstruk- tur dieser Entladung und die Eigenschaften einzelner Teilentladung werden diskutiert, Die wichtigsten Reaktionspfade fur die verschiedenen angeregten Atom- und Molekulzustande werden sowohl im Sauerstoft als auch in Luft identifiziert. Ferner werden Moglichkeiten zur Erreichung hoher Leistungsdichten, hoher Witkungsgrade oder ober Ozonkonzentra= tionen diskutirt