Effective Ozone Generation in Oxygen Using a Mesh Electrode in an Ozonizer with Variable Linear Velocity

Results of studies on ozone synthesis under discharges proceeding in a metal mesh-ceramic dielectric system have been presented. The experiments were carried out in the reactor with unique reaction space geometry, in which the reacting gas flew with consequently increasing linear velocity. The high voltage electrode was made of a metal mesh, which caused intensification of the gas mixing in the reaction space. Using a simple reactor with one-side cooling of the reaction space, high ozone maximum concentrations (100 g/Nm³) and energy efficiencies (180–200 g/kWh) were obtained at 25 °C.     

Technical and Economic Advantages of Producing and Applying Ozone At High Concentration

Today ozone can be produced in concentrations up to 3.5 wtJ (12 g/Nm³) in air and 7 wt% (92 g/Nm³) in oxygen with simultaneously low specific energy consumption. The high concentrations improve the transfer efficiency and the reaction kinetics of ozone. This is demonstrated with reference to the design basis of the water treatment plants of Los Angeles, Dordrecht and Jeddah. In all cases the overall costs per kilogram of ozone are minimized by choosing the appropriate ozone concentration between 2 wt% (24 g/Nm³) and 6 wt% (79 g/Nm³).     

Ozone Formation from the Reaction Of O2-Activated N2 Molecules and a New Type of Ozone Generator with Fine Wire Electrode

Experiments using an ozone generator which has a fine steel wire electrode are described. Various conditions of the wire electrode ozone generator such as wire diameter, volume density of wire electrode, applied voltage and the effects of SF₆ addition also are reported. The efficiency of the wire electrode ozone generator in air exceeded that of the usual ozone generator for 0.1 mm wire diameter and 0.156 g cm^?3 volume density of wire over the entire range of applied voltage. This efficiency increases by adding 0.08% SF₆ in air. Increase of ozone and NOX formation in the air ozone generator can be explained by the reactions of O₂ and activated N₂.     

Experimental Study of Ozone Generation by Negative Corona Discharge in Mixtures of N2 and O2

Ozone generation by negative DC corona discharge in N₂-O₂ mixtures has been experimentally investigated using a coaxial wire-cylinder corona reactor operating at room temperature and atmospheric pressure. The experiments have been carried out under different gas flows (15 cm³ min^?1 to 200 cm³ min^?1) and gas compositions (5% to 90% of O₂), and the effect of these parameters on the corona current, the ozone density and the efficiency of the ozone generator have been analyzed. The global rate coefficients for ozone formation and destruction have also been evaluated, and their values compared with those reported by other authors. The maximum efficiency for ozone production was found in gas mixtures with oxygen content about 70–80%.     

A Study of Ozone Generation by Negative Corona Discharge Through Different Plasma Chemistry Models

The Steady radial distribution of chemical species in a wire‐to‐cylinder ozone generator filled with pure oxygen has been computed by applying four different plasma chemistry models of increasing complexity. The most complete model considers ten species (e, O₂ ⁺, O₂ ^?, O₃ ^?, O^?, O₂, O₂(¹Δ_g), O₂(¹∑_g ⁺), O and O₃) and 79 reactions, including ionization by electron impact, electron attachment and detachment, electron-ion recombination, charge transfer, etc. The chemical model is coupled with the electrical model through Poisson's equation. The spatially averaged ozone density has been computed as a function of the current intensity and compared with the experimental values obtained by UV spectroscopy.     

The Benefits of Small Quantities of Nitrogen in the Oxygen Feed to Ozone Generators

This paper reports the ozone generation in pulsed multichannel dielectric barrier discharge. The influence of nitrogen addition (0.1%–10%) on ozone concentration and ozone generation efficiency in nitrogen–oxygen gas mixtures is studied. Results show that adding 0.1% N₂ would not seriously increase the ozone production. Meanwhile, 1% N₂ content exhibits the highest ozone production efficiency in low SIE (J/L, defined as the ratio of power to gas flow rate) region (0–200 J/L) while adding 0.3% N₂ would lead to the highest ozone generation efficiency in high SIE region (300–800 J/L). The increase of ozone production induced by N₂ addition is more significant in low SIE region compared with that in high SIE region. At 100 J/L, ozone production efficiency increases 26.9% to 201.6 g/kWh with 1% N₂ addition when compared with that in oxygen. At 18 J/L, the observed maximum ozone generation efficiency reaches 252 g/kWh at 1.3 g/Nm³ with 1% N₂ addition. An increase of ozone production can be obtained with 0.3%–2% N₂ addition in all explored SIE ranges.     

Modified Indigo Method For Gaseous And Aqueous Ozone Analyses

The indigo method developed by Bader and Hoigné for aqueous ozone analysis was modified to allow for both gaseous and aqueous ozone determination. Gas or water samples were extracted with a gas-tight syringe containing a known volume of indigo reagent. The modified procedure provided a more consistent basis for gaseous and aqueous ozone determination allowing for more accurate ozone mass balance calculations. Direct gaseous ozone UV absorbance with molar absorptivity of 3,000 M^?1cm^?1 at 258 nm was used as primary standard to determine the molar absorptivity of the indigo reagent. The molar absorptivity of indigo reagent, assuming a 1:1 stoichiometric ratio for the reaction between indigo and ozone, was determined to be 23,150 ± 80 M^?1cm^?1, or approximately 16 percent higher than that of 20,000 M^?1cm^?1 suggested by Bader and Hoigné. An independently calibrated membrane-electrode ozone monitor showed good correlation with indigo method results using the molar absorptivity value determined in this study. The apparent molar absorptivity of aqueous ozone at the wavelength of 258 nm measured by the modified indigo method increased from 2,400 to 3,600 M^?1cm^?1 in the investigated ozone concentration range of 0.4 to 11.0 mg/L. This variation might have been caused by the inherent interference of unidentified ozone byproducts, which presence was supported with scanning spectra in the wavelength range of 200 to 300 nm.     

Ozone Production in a High Frequency Dielectric Barrier Discharge Generator

Factors that affect the performance of an expanded-mesh dielectric barrier discharge ozone cell were investigated. A gas feed pf 94% O₂, 4% Ar and 1% N₂ was used. An improvement in the productivity (g ozone/kWh) of about 20 % was achieved by doubling the gas flow rate through the cell. Decreasing the cell operating frequency (in the range 72 kHz to 19 kHz) increased the productivity of the ozone generator at constant power. The ozone production increased approximately in proportion to the input power; however productivity did not vary significantly with power above a minimum level. As the cell voltage was increased the dependence of productivity on power or frequency was reduced. Changing the feed gas temperature between ? 5^°C and + 42^°C had no effect on productivity. Finer meshes drew more power than coarser ones for a given voltage. Using a thinner mesh for the centre electrode increased productivity. The best results were obtained with a 6 × 3 × 1.86 mm titanium mesh giving a productivity of 110 g ozone/kWhr at 30–60 W, 1500–1900V and 23 KHz.     

Higher Oxidation State Responsible for Ozone Decomposition at Room Temperature over Manganese and Cobalt Oxides: Effect of Calcination Temperature

The heterogeneous catalytic decomposition of ozone was investigated over unsupported manganese and cobalt oxide at room temperature. All catalysts were characterized by X-ray diffraction (XRD), N₂ adsorption–desorption (Brunauer–Emmet–Teller method), H₂-temperature programmed reduction (H₂-TPR) and X-ray photoelectron spectroscopy (XPS). The catalytic activity test indicated that these oxides had a good activity on ozone conversion meanwhile the catalysts remained highly active over time under reaction conditions. The treated temperature of the catalyst had a significant impact on the performance of ozone abatement and the samples treated at lower temperature showed higher activity. The surface area decreased obviously when developing the calcination temperature and H₂-TPR results demonstrated that much higher oxidation state of metal ions and active oxygen species were maintained on the surface under low treated temperature. XPS analysis showed that there were higher oxidation states of metal ions (Mn⁴⁺ and Co³⁺) and adsorbed oxygen species on the surface of catalysts treated at lower temperature, both of which play a significant role in ozone decomposition. However, the activity of manganese oxide was higher than that of cobalt oxide and the possible reason for this phenomenon was discussed.     

Large-Scale Experimental Validation of a Model for the Kinetics of Ozone and Hydroxyl Radicals with Natural Organic Matter

A unified model for the kinetics of O₃ and ^?OH with NOM was proposed, calibrated and validated based on large experimental data sets. Single-phase batch experiments were done on 11 water samples from seven resources. Seasonal variations were studied on three resources. Effects of reaction time with ozone, ozone dose, pH, temperature, radical scavenger adding, and NOM dilution were studied. The experiments represented more than 1200 and 900 concentration measurements, respectively, for ozone and pCBA (^?OH tracer). Mechanistic models were used for ozone self-decomposition and carbonate species kinetics. Results showed that the proposed model is robust and can handle different water characteristics and different experimental conditions: 75% of the experiments were modeled satisfactorily (for ozone and pCBA). Next, the domain of validity was determined: 6 ≤ pH ≤ 8; 1 meq.L^?1 ≤ alkalinity ≤ 6 meq.L^?1; 0–0.5 mgC.L^?1 ≤ TOC ≤ 3.1 mgC.L^?1. Only water samples with high organic (TOC > 2.4 mg.L^?1) and low inorganic contents (alkalinity < 0.3 meq.L^?1) could not be modeled adequately. Seasonal comparisons showed that the quality of the predictions decreases only for pCBA when having calibrated the model at another season. The model gave good results when using only 6 single batch experiments for calibration.     

Ozonation and Advanced Oxidation of Wastewater: Effect of O3 Dose,pH, DOM and HO•-Scavengers on Ozone Decomposition and HO• Generation

The decomposition of ozone in wastewater is observed starting 350 milliseconds after ozone addition. It seems not to be controlled by the autocatalytic chain reaction, but rather by direct reactions with reactive moieties of the dissolved organic matter (DOM). A larger ozone dose increases ozone consumption prior to 350 milliseconds but decreases the rate of ozone decomposition later on; this effect is predicted by a second-order kinetic model. Transferred Ozone Dose (TOD) is poorly correlated with ozone exposure (= ∫[O₃]dt) indicating that TOD is not a suitable parameter for the prediction of disinfection or oxidation in wastewater. HO^? concentrations (> 10^?10 M) and R_ct (=∫[HO^?]dt/∫[O₃]dt > 10^?6) are larger than in most advanced oxidation processes (AOP) in natural waters, but rapidly decrease over time. R_ct also decreases with increasing pre-ozonation doses. An increase in pH accelerates ozone decomposition and HO^? generation; this effect is predicted by a kinetic model taking into account deprotonation of reactive moieties of the DOM. DOC emerges as a crucial water quality parameter that might be of use to normalize ozone doses when comparing ozonation in different wastewaters. A rapid drop of absorbance in the water matrix—with a maximum between 255–285 nm—is noticeable in the first 350 milliseconds and is directly proportional to ozone consumption. The rate of absorbance decrease at 285 nm is first order with respect to ozone concentration. A kinetic model is introduced to explore ozone decomposition induced by distributions of reactive moieties at sub-stoichiometric ozone concentrations. The model helps visualize and comprehend the operationally-defined “instantaneous ozone demand” observed during ozone batch experiments with DOM-containing waters.     

Characterization of the ozone zero phenomenon by infrared spectroscopy

The presence of a small amount of nitrogen in the feed gas is necessary to generate ozone efficiently out of oxygen. Operating an ozone generator with ultra-pure oxygen for extended periods results in highly deteriorated ozone generation efficiency. In extreme cases, when the nitrogen levels in the feed gas are in the lower ppm range, the efficiency of the ozone generation process even drops to zero. In this article, we present our results concerning the correlation between the N₂O₅ concentration in the off-gas and the ozone generation efficiency. After the ozone generator is run for a well-defined amount of time with an oxygen–nitrogen mixture, the N₂ supply is shut off, and the behavior of the system is monitored by near-infrared spectroscopy. Different surface materials lead to different temporal behavior of both the nitrogen oxide levels and the ozone concentration after shutting down the nitrogen supply. The measurements show a good correlation between the evolution of ozone generation efficiency and the changes of the N₂O₅ concentration in the off-gas.     

Optimal Sizing of a DBD Ozone Generator Using Response Surface Modeling

Dielectric barrier discharge (DBD) reactors used as ozone generators are well known today and widely used for water treatment and air disinfection. The purpose of this article is to propose an experimental procedure based on the response surface modeling in order to optimize the geometrical dimensions of the cylindrical shape ozone generator, i.e., the discharge gap and the electrodes length. Because an effective ozone generator is expected to give high ozone concentration with a minimum of power requirements, the applied high voltage was associated with the geometrical parameters to carry out a composite centered faces design. Obtained results indicate that for an efficient ozone generator, length of the electrodes needs to be optimized while the discharge gap should be minimized.     

The Reaction of Ozone with Bisulfide (HS−) in Aqueous Solution – Mechanistic Aspects

The ozone demand to oxidize HS^?/H₂S [pK_a(H₂S) = 6.9, k(HS^? + O₃) = 3 × 10⁹ M^?1 s^?1, k(H₂S + O₃) = 3 × 10⁴ M^?1 s^?1] to SO₄ ^2? is only 2.4 mol ozone per mol SO₄ ^2? formed, much lower than stoichiometric 4.0 mol/mol if a series of O-transfer reactions would occur. As primary step, the formation of an ozone adduct to HS^?, HSOOO^–, is suggested that decomposes into HSO^– and singlet oxygen (16%) or rearranges into peroxysulfinate ion, HS(O)OO^– (84%). Potential reactions of the above intermediates are discussed. Some of these can account for the low ozone demand.     

Ozone Generator with Cylindrical Type of Rotating Electrode

An ozone generator using a rotating electrode to improve ozone generation efficiency is proposed. The ozone generator electrode unit consists of a rotating electrode and fixed electrode. The rotating electrode has the grounded 36 pieces of tungsten wires fixed in parallel to the rotation axis on the rotating cylinder surface. A dielectric electrode is used as a fixed electrode located on the inside of the tube of the electrode unit. The width of the apparent discharge gap is 1mm. Alternating current with a frequency of 50 Hz is applied to the electrode unit. The rotation speed can be adjusted from 0 rpm to 1200 rpm by a variable speed motor. Oxygen gas is used as the material gas. Higher ozone concentration and higher ozone generation efficiency are obtained compared with that when the rotation speed is 0 rpm. The gas temperature is measured at the inlet and outlet of the ozone generator, and the rotation speed for the cooling effect is most effective at about 500 rpm. The maximum generation efficiency is estimated to be 61 g/kWh at 800 rpm, and this value is twice as large as in the case of 0 rpm.     

Investigation of the properties of Ti/[IrO2-Nb2O5] electrodes for simultaneous oxygen evolution and electrochemical ozone production, EOP

A systematic investigation of the influence of Ti/[IrO₂-Nb₂O₅] electrode composition ([IrO₂]=40, 45 and 50 mol%) on electrochemical ozone production (EOP), was conducted in 3.0 mol dm⁻³ H₂SO₄ in the presence and absence of 0.03 mol dm⁻³ KPF₆. “In situ” characterisation revealed all oxide layer presented similar structures, except for the 50 mol% IrO₂ nominal composition which showed a higher porosity/roughness. The introduction of KPF₆ in the electrolyte resulted in an inhibition of the oxygen evolution reaction (OER) at high current densities, improving ozone generation efficiency at i > 0.4 A cm⁻², while reducing overpotential for OER. When normalised for the area, the ozone current efficiency presented a good performance of the system. However, improvement of the electrode service life is necessary in order to support the drastic conditions observed during EOP.     

Ultraviolet-Enhanced Ozonation of Organic Compounds: 1,2-Dichloroethane and Trichloroethylene as Model Substrates

1,2–Dichloroethane (DCE) and trichloroethylene (TCE) were used as model compounds to study the oxidation of organic chemicals by ozone/ultraviolet radiation, ozone, and hydrogen peroxide/ultraviolet radiation. It was found that ozone/ultraviolet radiation oxidized both 1,2–dichloroethane and trichloroethylene in batch systems, at pH = 2 (phosphate buffer). At ozone concentrations in the 1 to 5 mg/L range, the reaction was first order in both ozone and substrate. At pH = 2 and initial ozone concentration 2.2–2.6 mg/L, rate constants (k)Q = 25 and 130 M^-1sec^-1 were observed for the ozone/ultraviolet radiation oxidation of DCE and TCE, respectively. The rat e constants for ozone oxidation of DCE and TCE without ultraviolet radiation were 4.3 and 47 M^-1sec^-1, respectively.

The higher rate of TCE oxidation implies that direct reaction occurs with the double bond. Finite reaction rate of DCE with ozone, and substantial increases in rate at higher pH imply the participatation of hydroxyl radicals in the oxidation of both compounds. For example, at pH = 7, initial ozone concentration of 2.3 mg/L, the k_o for TCE oxidation by ozone/ultraviolet radiation is approximately 500 M^?1 sec^?1 almost too fast to measure in a batch system.The rate also is increased by increased ultraviolet radiation intensity, and by the presence of hydrogen peroxide, which acts as a catalyst.     

Investigations on the Effect of Ozone as a Disinfectant of Egg Surfaces

The feasibility of gaseous ozone to reduce the number of microorganisms on the shell surface, of Salmonella Enteritidis (S.E.) in particular, of avian hatching eggs was investigated. Shell eggs were externally contaminated with S.E. to contain either 10²–10⁴ or 10⁵–10⁶ cfu/shell. Subsequently, the eggs were exposed to several ozone concentrations ranging from 0.5% to 5% wt/wt in combination with two relative humidities (< 30, > 70%) at room temperature. Exposure times varied between 20 minutes and 24 hours. A complete inactivation of 10²–10⁴cfu S.E./egg shell was reached by using an ozone concentration of 1% (wt/wt) for 120 min. Considering higher concentrations of S.E. on the shell ozone treatment caused approximately a 6 log₁₀ reduction. This demonstrates that gaseous ozonation is suitable for applications in hatcheries provided that high-power ozone generators are available. The parameters should be verified in large ozone cabinets.     

Reduction of COD and color of acid and reactive dyestuff wastewater using ozone

Wastewaters obtained from bromamine acid dye and reactive dye manufacturing were treated by ozone bubbling in a cylindrical batch reactor for the purpose of reducing COD to below 150 mg/L, which is the environmental discharge standard of the Republic of Korea. Remarkable COD reduction and decolorization were observed at pH over 11. High inlet gas flowrate and high concentration of ozone gave better results. Little precipitation was observed under the conditions of remarkable COD reduction. At pH of 11, 15 LPM of inlet gas flowrate and 89.3 g/Nm³ of ozone flowrate, the COD of bromamine acid dyestuff wastewater was reduced to 95 mg/L after 90 minutes, and the COD of reactive dyestuff wastewater was reduced to 120 mg/L after 120 minutes. Decolorization was completed after 30 minutes of reaction.