Transformations and destruction of nitrogen oxides—NO, NO2 and N2O—in a pulsed corona discharge reactor

There has been an increasing recent research interest in the removal of NO_x from combustion gases using electrical discharges, especially pulsed corona discharge reactors. The major issues in development of this technology are (a) the energy consumption required to achieve the desired pollutant reduction; and (b) the formation of undesirable byproducts. In this study, the transformations and destruction of nitrogen oxides—NO, NO₂ and N₂O—were investigated in a pulsed corona discharge reactor. Gas mixtures—NO in N₂, N₂O in N₂, NO₂ in N₂ and NO-N₂O-NO₂ in N₂—were allowed to flow through the reactor with initial concentrations, flow rates and energy input as operating variables. The reactor effluent gas stream was analyzed for N₂O, NO, NO₂, by means of an FTIR spectrometer. In some experiments, oxygen was measured using a gas chromatograph.Reaction mechanisms were proposed for the transformations and destruction of the different nitrogen oxides within a unified model structure. The corresponding reaction rates were integrated into a simple reactor model for the pulsed corona discharge reactor. The reactor model brings forth the coupling between reaction rates, electrical discharge parameters, and fluid flow within the reactor. It was recognized that the electron-impact dissociation of the background gas N₂ leads to both ionic and radical product species. In fact, ionic reactions were found responsible for N₂O destruction. Radical reactions were dominant in the transformation and destruction of NO and NO₂. However, decomposition of N₂⁺ ions also leads to indirect production of N radicals; this appears to be a less-power intensive route for NO destruction though longer residence times may be necessary. In addition, the decomposition of N₂⁺ ions limits the N₂O destruction that can be achieved. Comparison with our experimental data, as well as data in the literature, was very encouraging.     

Development of rate expressions for the catalytic decomposition of nitric oxide with ammonia on iron oxide

The reduction of nitric oxide with ammonia on iron oxide catalysts has been studied in a continuous-flow recycle reactor using simulated flue gas in the temperature range from 573 to 673 K. NO and HN₃ concentrations were varied between 0 and 1000 vpm, O₂ and H₂O concentrations between 0 and 9 vol.-%, the remainder being nitrogen. In the presence of oxygen, the formulated reaction rate equation describes the measured rates of the main reaction NO + 2/3 NH₃ ? 5/6 N₂ + H₂O. Its form corresponds to the Langmuir-Hinshelwood type. The rate equation well fits the data, which cover the whole industrial temperature and concentration range. In the absence of oxygen, the measured reaction rates can be best described by a power law.     

A study of nitrous oxide decomposition over calcium oxide in combustion condition

A study of N₂O decomposition reaction over a bed of CaO particles in a fixed bed reactor has been conducted. Effects of parameters such as concentration of inlet N₂O, reaction temperature and effects of CO, CO₂, O₂, and NO gas presented in the combustion gas environment have been investigated. The experiment showed that the N₂O decomposition reaction was accelerated by the increase of reaction temperature, and the existence of CO, while the reaction was hindered by the existence of CO₂, NO. O₂ also affected the N₂O decomposition. Heterogeneous gas-solid reaction kinetics were proposed for the reaction conditions and compared with homogeneous reaction kinetics.     

The destruction of N2O in a pulsed corona discharge reactor

The removal of N₂O by a pulsed corona reactor (PCR) was investigated. Gas mixtures containing N₂O were allowed to flow in the reactor at various levels of energy input, and for different background gases, flow rates, and initial pollutant concentrations. The reactor effluent gas stream was analyzed for N₂O, NO, NO₂, by means of an FTIR spectrometer. It was found that destruction of N₂O was facilitated with argon as the background gas; the conversion dropped and power requirements increased when nitrogen was used as the background gas.Reaction mechanisms are proposed for the destruction of N₂O in dry argon and nitrogen. Application of the pseudo-steady state hypothesis permits development of expressions for the overall reaction rate in these systems. These reaction rates are integrated into a simple reactor model for the pulsed corona discharge reactor. The reactor model brings forth the coupling between reaction rates, electrical discharge parameters, and fluid flow within the reactor. Comparison with experiment is encouraging, though the needs for additional research are clearly identified.     

The selective non-catalytic reduction of nitric oxide using ammonia at up to 15% oxygen

Selective non-catalytic reduction of nitric oxide (NO) using ammonia was studied with up to 15% (by volume) oxygen at 102 kPa. The experiments were conducted in an electrically heated laminar-flow, quartz reactor using mixtures of N₂, O₂, NO, and CO to simulate exhaust gas. The base case condition included 330 ppmv of NO, 495 ppmv of NH₃, and 15% O₂. At a reactor temperature of 1050 K, 77% of the NO was removed. For a lower oxygen concentration of 1%, the NO removal was as high as 98% at 1100 K. The degraded performance at high oxygen concentrations is attributed to increases in the oxidation reactions. A major result of this work was the quantification of the amount of N₂O in the treated gases. For the base case conditions, 21 ppmv of N₂O was measured for a reactor temperature of 1075 K. Increasing the ratio of NH₃ to NO (by increasing the NH₃ concentration) increased the maximum NO removal and decreased the temperature at which this level of NO removal was achieved. For the higher NH₃ concentrations, however, the N₂O concentration increased to as high as 54 ppmv. The oxidation products of ammonia (in the absence of NO) for these conditions were found to include first N₂O beginning at 900 K and then NO beginning at 1050 K. Comparisons between these experimental results and predictions from the Miller and Bowman (1989) model indicate that further enhancements of the model may be necessary to incorporate the features of high oxygen conditions.     

Influence of soil physical properties, fertiliser type and moisture tension on N2O and NO emissions from nearly saturated Japanese upland soils

In Japan, upland soils are an important source of nitrous oxide (N₂O) and nitric oxide (NO) gas emissions. This paper reports on an investigation of the effect of soil moisture near saturation on N₂O and NO emission rates from four upland soils in Japan of contrasting texture. The aim was to relate these effects to soil physical properties. Intact cores of each soil type were incubated in the laboratory at different moisture tensions after fertilisation with NH₄-N, NO₃-N or zero N. Emissions of N₂O and NO were measured regularly over a 16–20 day period. At the end of the incubation, soil cores were analysed for physical properties. Moisture and N fertiliser significantly affected rates of emissions of both N₂O and NO with large differences between the soil types. Nitrous oxide emissions were greatest in the finer-textured soils, whereas NO emissions were greater in the coarser-textured soils. Emissions of N₂O increased at higher moisture contents in all soils, but the magnitude of increase was much greater in finer-textured soils. Nitric oxide emissions were only significant in soils fertilised with NH₄-N and were negatively correlated with soil moisture. Analysis of soil properties showed that there was a strong relationship between the magnitude of emissions and soil physical properties. The importance of soil wetness to gas emissions was mainly through its influence on soil air-filled porosity, which itself was related to gas diffusivity. From the results of this research, we can now estimate likely effects of soil texture on emissions through the influence of soil type on soil aeration and soil drainage. This is of particular value in modelling N₂O and NO emissions from soil moisture status and land use inputs.     

Numerical Study of NOx Abatement Using Ozone Injection Integrated with Wet Absorption

Nitrogen oxides emitted from power plants and the chemical industry are poisonous to humans and animals, contribute to ozone depletion, and cause acid rain. More than 90% of nitrogen oxides (NO_x) consist of nitric oxide (NO), which is insoluble in water. Among the various available techniques of NO_x abatement, ozone injection is a promising method in which NO is oxidized to higher-order nitrogen oxides (NO₃, N₂O₃, N₂O₄, and N₂O₅), which can easily be absorbed in a wet scrubber. In this article, the ozone injection process integrated with an absorber column is numerically modeled and simulated at various operating conditions. The predicted results of NO_x oxidation with ozone injection and absorption in water agree with the published experimental results. The ozone injection process is modeled using a plug flow reactor, while the wet absorption is based on a rigorous rate-based RateFrac model. Detailed kinetic mechanisms of O₃-NO_x oxidation and absorption of nitrogen oxides in water are incorporated in the model to simultaneously predict the performance efficiency of the ozone reactor and absorber column. Thermodynamic properties of the components are estimated using an Electrolyte NRTL model. The influence of performance parameters (such as feed gas flow rate, inlet gas temperature, reactor configurations, ozone concentration, and NO/NO₂ molar ratio) on the oxidation efficiency of NO_x in the reactor and absorber column is investigated to predict the optimal operating conditions.     

Measurement and modeling of nitrous and nitric oxide emissions from a tea field in subtropical central China

Tea fields represent an important source of nitrous oxide (N₂O) and nitric oxide (NO) emissions due to high nitrogen (N) fertilizer applications and very low soil pH. To investigate the temporal characteristics of N₂O and NO emissions, daily emissions were measured over 2½ years period using static closed-chamber/gas chromatograph and chemiluminescent measurement system in a tea field of subtropical central China. Our results revealed that N₂O and NO fluxes showed similar temporal trends, which were generally driven by temporal variations in soil temperature and soil moisture content and were also affected by fertilization events. The measured average annual N₂O and NO emissions were 10.9 and 3.3 kg N ha^?1 year^?1, respectively, highlighting the high N₂O and NO emissions from tea fields. To improve our understanding of N-cycling processes in tea ecosystems, we developed a new nitrogenous gas emission module for the water and nitrogen management model (WNMM, V2) that simulated daily N₂O and NO fluxes, in which the NO was simulated as being emitted from both nitrification and nitrite chemical decomposition. The results demonstrated that the WNMM captured the general temporal dynamics of N₂O (NSE = 0.40; R² = 0.52, RMSE = 0.03 kg N ha^?1 day^?1, P < 0.001) and NO (NSE = 0.41; R² = 0.44, RMSE = 0.01 kg N ha^?1 day^?1, P < 0.001) emissions. According to the simulation, denitrification was identified as the dominant process contributing 76.5% of the total N₂O emissions, while nitrification and nitrite chemical decomposition accounted for 52.3 and 47.7% of the total NO emissions, respectively.     

A kinetic study of NOx reduction over Pt/SiO2 model catalysts with hydrogen as the reducing agent

Flow reactor experiments and kinetic modeling have been performed in order to study the mechanism and kinetics of NO_x reduction over Pt/SiO₂ catalysts with hydrogen as the reducing agent. The experimental results from NO oxidation and reduction cycles showed that N₂O and NH₃ are formed when NO_x is reduced with H₂. The NH₃ formation depends on the H₂ concentration and the selectivity to NH₃ and N₂O is temperature dependent. A previous model has been used to simulate NO oxidation and a mechanism for NO_x reduction is proposed, which describes the formation/consumption of N₂, H₂O, NO, NO₂, N₂O, NH₃, O₂ and H₂. A good agreement was found between the performed experiments and the model.     

The formation of N2O during the reduction of NO by NH3

The process of selective non-catalytic reduction of NO, SNCR, is important for limiting emissions of nitrogen oxides from coal-fired power plants. Such a process has been studied for many years, both in the laboratory and under practical conditions. This work was an attempt at elucidating some of the problems associated with the method when used under circulating fluidized bed (CFB) conditions and in particular, the formation of the N₂O by-product. The NO + NH₃ reaction has been studied in the laboratory, over quartz sand in a heated fixed bed flow reactor. In comparison with a combustion environment, the composition of the gas phase was drastically simplified and limited to NO and NH₃, in nitrogen as the carrier gas, with O2 added in some experiments. The product gases were analyzed for NO, N₂O and NH₃. The effects the following parameters were studied: temperature inside the reactor between 850 and 1250 K, height of the sand bed, NH₃/NO molar ratio over the range 0.54–2.0 and the addition of 1 or 2% of O₂ in volume. Baseline tests with an empty reactor were also made. With no sand in the reactor, the results were both qualitatively and quantitatively different. The sand helped to increase the efficiency of NO reduction, particularly at lower temperatures, but N₂O formation also appeared to be strongly enhanced, except at the highest temperatures. Higher molar NH₃/NO ratios favored NO reduction and N₂O production, both with and without sand. The reduction of NO did not appear to require the presence of O₂, but the introduction of 1% or 2% of O₂ gave some benefit. The results confirmed that under practical conditions more attention should be paid to the role of the bed solids in the SNCR process.     

The Effect of nitric oxide on the photocatalytic oxidation of small hydrocarbons over titania

The catalytic UV photo-oxidation of NO in the absence and presence of ethane, ethene, propane, propene, and n-butane over TiO₂ in the presence of excess oxygen was studied in the temperature range 21–150 °C. It was confirmed in our system that in the absence of hydrocarbon NO was photocatalytically oxidised by oxygen to NO₂ over TiO₂ and was strongly absorbed. Both NO and hydrocarbon could be simultaneously photo-converted with the conversion varying considerably with both NO and hydrocarbon concentration and the nature of the hydrocarbon. In some instances the presence of NO in the feed gas enhanced hydrocarbon oxidation via reactions involving NO₂ that is a powerful oxidant. The extent of this effect depended on the relative strengths of adsorption on TiO₂ of the reactants and products. To reduce surface coverage of hydrocarbon most reactions were run at 150 °C, and it was shown that at this temperature NOx adsorbed on titania could be reduced by photogenerated hydrocarbon surface species to N₂O and N₂ under these conditions. The formation of N₂ was confirmed using ¹⁵NO with helium as carrier gas. By contrast, at room temperature in the presence of propene NO was converted to NO₂.     

Photo-induced selective gas detection based on reduced graphene oxide/Si Schottky diode

Reduced graphene oxide (RGO)/Si Schottky diode has been fabricated by a simple drop-casting/annealing process. Common combustible and/or toxic gases including CH₄, O₂, CO, NO₂, NO, and SO₂ were employed to evaluate the detection performance of such device. The relationship between current response and gas flow rate, concentration, bias voltage as well as operating time has been systematically studied, and the results indicated that the RGO/Si-based device is selective to gases like NO₂ and NO. In some cases (i.e. flow rate detection), however, the current response for one gas is completely contrary to others, presumably due to the oxygen functional groups (OFGs) presiding on the surface of reduced graphene oxide. Finally, the effects of OFGs on the gas detection performance of RGO/Si-based devices were thoroughly discussed.     

Effects of the depth of NO and N2O productions in soil on their emission rates to the atmosphere: analysis by a simulation model

Many factors are concerned in the changing forms of nitrogen compounds in soil, so it is not easy to make precise models to simulate the concentration profiles of soil nitric oxide (NO) and nitrous oxide (N₂O) and their emission rates under various soil conditions. We prepared a simple mathematical simulation model based on soil concentration profiles of NO and N₂O. The profiles were measured at lysimeters filled with Andosol soil and fertilized with ammonium sulfate at rate of 200 kgNha^-1, incorporating to plow layer (Hirose & Tsuruta, 1996). In this model, diffusion of gases in soil followed Fick's law and the diffusion coefficient was adopted from Sallam et al. (1984). The gas production rate was set up at constant value in the site of gas production, and the gaseous consumption followed Michaelis-Menten kinetics. By changing only the depth of NO and N₂O production in soil in this model, we obtained the following results.(1) When the depth of gas production was set at near the soil surface (NO: 0–10 cm, N₂O: 0-8 cm), the emission rates of both gases corresponded with the results of the lysimeter-measurement.(2) When the depth of gas production was shifted down 10 cm deeper (NO: 10–20 cm, N₂O: 10-18 cm), the gas emission rate of NO decreased to 1.3% of (1), while that of N₂O was almost the same as (1).(3) In the case that the total intensity of produced gases was not changed from (1) or (2), but that the extent of gas productions expanded 3 times wider (NO: 0–30 cm, N₂O: 0–24 cm) than (1) or (2), the emission rates of NO and N₂O became 26% and 95% of (1), respectively.The above results suggest the possibility of mitigating NO emission by setting the site of gaseous production in deeper soil, e.g. by means of deep application of fertilizer.     

Effect of Ozone Injection on the Catalytic Reduction of Nitrogen Oxides

The improvement in the catalytic reduction of nitrogen oxides (NO_x) by means of the ozone injection into the exhaust gas was investigated. Nitric oxide (NO) in the exhaust gas was first oxidized to nitrogen dioxide (NO₂) by ozone, and then the exhaust gas containing the mixture of NO and NO₂ was directed to the catalytic reactor where both NO and NO₂ were reduced to nitrogen. The ozone injection method was very efficient for the oxidation of NO to NO₂ in a wide range of temperatures, and the increase in the content of NO₂ by the ozone injection remarkably improved the performance of the catalytic reactor.     

Mechanism of the Reduction by Ammonia of Nitrates Stored onto a Pt–Ba/Al2O3 LNT Catalyst

The mechanism involved in the formation of N₂ and of N₂O during the reduction of nitrates stored onto a Pt–Ba/Al₂O₃ LNT catalyst is investigated using labeled NO and unlabeled ammonia, in the presence and in the absence of NO in the gas phase. The reduction of the stored NO _x species (labeled nitrates) with NH₃ leads to the selective formation of N₂. Based on the isotopic distribution, it appears that N₂ formation occurs primarily through the statistical coupling of N-atoms formed by dissociation of NO and NH₃ at metal Pt sites. When the reduction of the stored nitrates is carried out in the presence of NO in the gas phase, NO is preferentially reduced. This implies that the rate determining step of the reduction of nitrates by ammonia is likely associated with the release of stored NO _x . Negligible amounts of nitrous oxide have been observed during the NH₃-TPSR with adsorbed nitrates, whereas relevant quantities of N₂O have been detected at low temperatures (below 180 °C) in the runs performed in the presence of NO in the gas phase. The data converge to indicate that N₂O formation involves the presence of gaseous NO and this suggests that the formation of nitrous oxide occurs either through the coupling of two adsorbed NO molecules or the recombination of an adsorbed NO molecule with an adsorbed NH _x species.     

The Effect of Oxygen Concentration on the Reaction of NOx with Soot Over BaAl2O4

The effect of oxygen concentration on the catalytic reaction of NO_x with soot over BaAl₂O₄ has been studied by Diffuse Reflectance Fourier Transform Infrared Spectroscopy (DRIFTS). The introduction of O₂ into the NO flow can result in a reactant mixture of NO/NO₂/O₂. Increasing the O₂ concentration from 2 % to 5 % in the NO‐containing flow promotes the formation of NO₂ from the gas phase oxidation of NO. The reactant mixture with high O₂/NO flow, allows for the formation of greater amounts of nitrate species than that with low O₂/NO flow, which further promotes the reaction of soot with NO_x and leads to a high conversion efficiency of NO_x into N₂ and N₂O. In the absence of O₂, N₂O is not observed since the N₂O produced at high temperatures has reacted with soot before it can be detected.     

Measurements of N2O and NO emissions during tomato cultivation using a flow-through chamber system in a glasshouse

Nitrous oxide (N₂O) and nitric oxide (NO) fluxes resulting from long-term tomato cultivation in a glasshouse were continuously determined using the flow-through chamber method over the course of three cultivation periods. Gas concentrations were measured using an nondispersive infrared (gas filter correlation/infra-red) analyzer and a chemiluminescence-based analyzer, respectively. Following a basal application of fertilizer, daily N₂O and NO emission rates increased, with peaks lasting from 40 to 140 days. Short-term fluctuations in daily N₂O and NO emissions were affected by differences in nitrogen application, soil water, and soil temperature. Diurnal changes in N₂O and NO fluxes during the period of peak emissions depended primarily on soil temperature. Following the application of a top dressing (N as urea or calcium nitrate) in the irrigation water, the N₂O and NO fluxes increased immediately, with a very short period of peak emissions (1–5 h) after urea application. The duration of the peak period in daily accumulated N₂O and NO emissions following application of the top dressing ranged from 3 to 10 days.     

NO-Assisted N2O Decomposition over ex-Framework FeZSM-5: Mechanistic Aspects

The decomposition of N₂O over an ex-framework FeZSM-5 catalyst is strongly promoted by NO. Activity data show that the promoting effect of NO is catalytic, and that besides NO₂, O₂ is formed much more extensively in the presence, than in the absence of NO. Transient in situ FT-IR/MS measurements indicate that NO is strongly adsorbed on the catalyst surface up to at least 650 K, showing absorption frequencies at 1884 and 1876 cm^–1. A change in gas phase composition from NO to N₂O results in the formation of adsorbed NO₂, identified by a sharp IR band at 1635 cm^–1. Switching back to the original NO gas phase induces a rapid desorption of NO₂, restoring the original NO absorption frequencies. During the IR measurements, bands typical of nitro- or nitrate groups were not observed. Multi-Track (a TAP-like technique) experiments show that the presence of NO or NO₂ on the catalyst surface significantly enhances the rate of oxygen desorption at the time of N₂O exposure to the catalyst. The spectral changes and transient experiments are discussed and catalytic cycles are proposed, to explain the formation of NO₂ and the (enhanced) formation of oxygen. The latter can be either explained by an indirect effect (electronic, steric) of NO adsorbed on sites neighboring the active sites, or by a direct effect involving reaction of adsorbed NO₂ groups with neighboring oxidized sites yielding O₂.     

The effect of particle size on nitric oxide decomposition and reaction with carbon monoxide on palladium catalysts

The effect of palladium particle size on its catalytic activity was investigated by the decomposition of chemisorbed nitric oxide and the reaction of nitric oxide with carbon monoxide in flow conditions. Palladium particles (30–500 Å) were prepared on silica thin films (100 Å) which were supported on a Mo(110) surface. The reactivity of the supported palladium varied with the metal particle size. On large palladium particles, nitric oxide (NO) reacts to form nitrous oxide (N₂O), dinitrogen (N₂) and atomic oxygen during temperature-programmed reaction, whereas on small particles (< 50 Å), nitrous oxide is not formed. Similarly, reactions of NO with CO on large particles, in flow conditions produce N₂O, N₂ and CO₂, whereas N₂O is not produced on small particles. In addition, more extensive NO decomposition is observed on the smaller particles.