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.     

Reduction of nitrogen oxides by ozonization-catalysis hybrid process

Treatment of nitrogen oxides (NO_x) by using a hybrid process consisting of ozonization and catalysis was investigated. The ozonization method may be an alternative for the oxidation of NO to NO₂. It was found that nitric oxide (NO) was easily oxidized to nitrogen dioxide (NO₂) in the ozonization chamber without using any hydrocarbon additive. In a temperature range of 443 to 503 K, the decomposition of ozone into molecular oxygen was not significant, and one mole of ozone approximately reacted with one mole of NO. A kinetic study revealed that the oxidation of NO to NO₂ by ozone was very fast, almost completed in a few tens of milliseconds. When the amount of ozone added was less than stoichiometric ratio with respect to the initial concentration of NO, negligible NO₃ and N₂O₅ were formed. The oxidation of a part of NO to NO₂ in the ozonization chamber enhanced the selective reduction of NO_x to N₂ by a catalyst (V₂O₅/TiO₂), indicating that the mixture of NO and NO₂ reacts faster than NO.     

Nitrogen Oxides Ozonation as a Method for NOx Emission Abatement

Attempts to develop new technologies of reduction of NO_x emission are still carried out all around the world. However, most of them as literature survey suggests is focused on NO_x emission control from power plants and mobile vehicles. Fewer investigations are conducted on the NO_x emission abatement from the chemical industry. One of the relatively new approaches is the application of ozone injection into exhaust gas stream followed by an absorption process. Ozone is used to transform NO_x to higher nitrogen oxides that are more soluble in water, and therefore the higher yield of nitric acid is expected. The main objective of this article is to present results of our studies in which the effectiveness of the ozonation process, as well as the dependence of the conversion rate and the selectivities of NO ozonation into NO₂, N₂O₅ and HNO₃ on the residence time of reagents in the reactor space were studied. Results of laboratory investigations were confirmed during ozonation experiments with real exhaust gases from a nitric acid pilot plant in Fertilizers Research Institute in Pulawy, Poland.     

Simultaneous oxidation of nitrogen oxides and sulfur dioxide with ozone and hydrogen peroxide

The use of ozone and hydrogen peroxide for the simultaneous oxidation of nitrogen and sulfur oxides was studied in experiments carried out in a stirred cell. It was found that in a gas mixture, containing both nitrogen and sulfur oxides, only the nitrogen oxides are oxidized by ozone. Contrary to earlier results, sulfur dioxide does not disturb the oxidation of nitrogen oxides under dry conditions. The consumption of ozone in the oxidation of nitric oxide was slightly below the stoichiometric level because the ozone was introduced into the reactor in the oxygen flow. When the molar ratio between ozone and nitric oxide was more than 0.4, some of the nitric oxide was oxidized to higher oxides of nitrogen, the final product being a solid mixture of N₂O₅ and (NO)₂S₂O₇. Some nitrosyl sulfuric acid was formed in the aqueous solution of hydrogen peroxide in addition to sulfuric acid under wet conditions. Some white solid was found on the walls of the reactor. This solid is said it the literature to consist of H₂SO₄, HNOSO₄ and (NO)₂S₂O₇.     

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.     

Heterogeneous reactions of NO2 and NO-O2 on the surface of carbons

The interactions of nitrogen oxides with carbons differing in the chemical structure of surface functional groups were studied using in situ FTIR combined with the measurements of catalytic activity. Microporous carbon samples with similar pore size distribution were prepared from cellulose. The structure and coverage of adsorbates during reactions at temperatures between 295 and 573 K are determined by FTIR. No significant changes in NO_x reaction with carbon surface were found by oxidation of the carbonized film. During the study of the reaction of NO/O₂ mixture with carbons, the infrared absorption bands for the surface species formed are similar to the IR bands observed after the reaction of carbon samples with NO₂. For both reactions, surface species, including C-NO₂, C-ONO, C-NCO and anhydride structures are formed. Catalytic NO_x reduction by carbons has been investigated in the temperature range 295-623 K in the flow reactor equipped with an FTIR gas analyzer. As the surface of carbon is exposed to NO₂ gaseous NO is formed. The reduction of NO₂ to N₂ without the use of an externally supplied reductant can be achieved with microporous carbons. Significant NO₂ conversion to N₂ occurred at 623 K on both oxidized and non-oxidized carbons.     

Removal of sulfur dioxide and nitrogen oxides by using ozone injection and absorption–reduction technique

A two-step process capable of removing NO_x and SO₂ simultaneously was proposed, which was made up of an ozonizing chamber and an absorber containing a reducing agent solution. Nitrogen oxides (NO plus NO₂) in most practical exhaust gases consist chiefly of NO. The injection of ozone into the exhaust gas gives rise to a rapid oxidation of NO to NO₂. Compared to NO, NO₂ has relatively high solubility in water, and it can readily be reduced to N₂ when the NO₂-rich exhaust gas is brought into contact with the reducing agent solution. Sodium sulfide (Na₂S) used as the reducing agent in this study can also remove SO₂, effectively. As the exhaust gas passed through the ozonizing chamber and the absorber sequentially, NO_x removal efficiency of about 95% and SO₂ removal efficiency of 100% were obtained. The formation of H₂S from sodium sulfide could be suppressed by using a basic reagent, together with the reducing agent. The rate of depletion of the reducing agent during the treatment of the exhaust gas was much faster than expected by reaction stoichiometry, obviously due to the oxygen in the exhaust gas. The amount of sodium sulfide required was found to be about four times the amount of NO_x and SO₂ removed.     

Investigation of flue-gas treatment with O3 injection using NO and NO2 planar laser-induced fluorescence

Direct ozone (O₃) injection is a promising flue-gas treatment technology based on oxidation of NO and Hg into soluble species like NO₂, NO₃, N₂O₅, oxidized mercury, etc. These product gases are then effectively removed from the flue gases with the wet flue gas desulfurization system for SO₂. The kinetics and mixing behaviors of the oxidation process are important phenomena in development of practical applications. In this work, planar laser-induced fluorescence (PLIF) of NO and NO₂ was utilized to investigate the reaction structures between a turbulent O₃ jet (dry air with 2000 ppm O₃) and a laminar co-flow of simulated flue gas (containing 200 ppm NO), prepared in co-axial tubes. The shape of the reaction zone and the NO conversion rate along with the downstream length were determined from the NO-PLIF measurements. About 62% of NO was oxidized at 15d (d, jet orifice diameter) by a 30 m/s O₃ jet with an influence width of about 6d in radius. The NO₂ PLIF results support the conclusions deduced from the NO-PLIF measurements.     

Experimental Study on Ozone Synthesis via Dielectric Barrier Discharges

The characteristics of ozone generation using a dielectric barrier discharge reactor were investigated experimentally. Results indicate that ozone concentration increases with increasing applied voltage and gas residence time. In addition to applied voltage, ozone generation rate varies with reactor configuration as well. Optimum ozone generation rates can be reached at the specific gas residence time for a given applied voltage and gas composition. At the same applied voltage, the reactor with a single dielectric barrier results in a higher ozone generation rate in comparison with the reactor having double dielectric barriers. Given a constant N₂/O₂ ratio in the feed gas, NO_x concentration increases as applied voltage and gas residence time increase. Results indicate that maximum NO_x concentration is reached when the N₂/O₂ ratio of feed gas is 4.     

Kinetic model of NOx ozonation and its experimental verification

The most of new technologies of reduction of NO_x emission, as literature survey (Skalska et al., 2010b) suggests is focused on NO_x emission control from power plants and mobile vehicles. Fewer investigations are conducted on the NO_x emission abatement from chemical industry. Recently, Chacuk et al. (2007) proposed the model for the nitrous acid oxidation with the use of ozone in gas–liquid contactor. It is well known that not all of NO_x can be totally absorbed in water or nitrous/nitric acid solution, as well as ozone is not totally consumed in the acidic liquid. The reaction between ozone and NO_x can take place also in the gas phase. The ozone injection into exhaust gas stream followed by absorption was proposed as the NO_x emission abatement. The objective of these studies was to propose kinetic model of the process and to determine the rate constants of NO_x ozonation in the laboratory scale batch reactor. The process was carried out in the 0.5 dm³ volume batch reactor for different concentrations of NO, and NO₂ and varying molar ratios of O₃/NO at temperature 25 °C. Gaseous reagents were analyzed using a Fourier Transform Infrared Spectrometer Jasco FTIR-4200. The kinetic model of NO_x ozonation process was proposed and rate constants were estimated based on experimental data.     

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.     

Experimental measurements of the NOx and CO concentrations operating in oscillatory and non-oscillatory burning conditions

The effects of combustion driven acoustic oscillations in carbon monoxide and nitrogen oxides emission rates of a combustor operated with liquefied petroleum gas (LPG) were investigated. Because the fuel does not contain nitrogen, tests were also conducted with ammonia injected in the fuel, in order to study the formation of fuel NO_x. The main conclusions were: (a) the pulsating combustion process is more efficient than the non-pulsating one and (b) the pulsating combustion process generates higher rates of NO_x, with and without ammonia injection, as shown by CO and NO concentrations as function of the O₂ concentration. An increase in the LPG flow rate, keeping constant the air to fuel ratio, increased the acoustic pressure amplitude and the frequency of oscillation. The injection of ammonia had no influence on either pressure amplitude or frequency.     

Removal of Tetravalent NOx from Flue Gases Using Solutions Containing Hydrogen Peroxide

The absorption of NO_x(IV) into nitric acid solutions containing a low concentration of hydrogen peroxide was studied in a small packed column. A simple mathematical model developed for this absorption was used for the determination of kinetic parameters relative to NO₂ and N₂O₄in such solutions. Results obtained at 10, 20 and 30 °C lead to the same interpretation: hydrolysis is the main controlling step for tetravalent nitrogen oxides absorption and there is no sensible effect of the acidity on the absorption efficiency. Hydrogen peroxide, however, plays an essential role in solution by preventing the HNO₂ decomposition. Our mechanistic and kinetic findings were validated as the model has worked with fair success in predicting NO_x removal efficiencies in a pilot-scale packed column.     

Absorption of NO in an Aqueous Solution of NaClO2

A packed column has been used to study the absorption of nitrogen oxide in an alkaline solution of sodium chlorite. The reactions taking place during the absorption have been examined and a lumped reaction model has been used to estimate rate constants from experimental data. Several parallel and consecutive reactions were found to take place during the absorption. NO was found to be oxidized to NO₂and/or to NO₂^–, and ClO₂^– was reduced to Cl^– and/or to ClO^–. The pH value of the absorbing liquid was found to have a great impact both on the absorption rate and on the extent of the different redox reactions within the liquid. Experimental results indicate that sodium chlorite mainly works as an agent to oxidize NO to NO₂ and that the major part of the nitrogen oxides are absorbed via the hydrolysis of N₂O₃ and N₂O₄.     

Removal of Nitric Oxide in a Pulsed Corona Discharge Reactor

Conversion of nitric oxide (NO) in a pulsed corona discharge reactor was investigated. Relative importance of each of the active species such as O, OH, HO₂ and O₃ produced by corona discharge was evaluated with respect to the oxidation of NO to NO₂. Of those species, O₃ was found to be the most important one in the oxidation of NO. In order to reduce the energy required to convert NO, olefins (ethylene, propylene) were used as additive, and the scheme for the oxidation of NO promoted by the hydrocarbon was discussed. In the presence of hydrocarbon, ozone also played very important role in the reaction mechanism. The concentration of ozone was measured at the reactor outlet to verify the importance of ozone in the oxidation chemistry. Compared to ethylene, propylene gave much better performance in the conversion of NO at the same specific energy. When propylene was added to the gas stream at identical amount to initial NO_x (300 ppm), 60 % of NO could be converted with a specific energy of only 2.6 Wh m^–3.     

Oxidation of carbon by NOx, with particular reference to NO2 and N2O

The reactions reviewed here concern those between elemental carbon and NO₂, N₂O and NO, sometimes in the presence of oxygen. The section on NO includes only updates to recent reviews. Soots, activated carbons and carbon blacks are more reactive than graphite. The magnitudes of the reaction rates are found to be: NO₂ > N₂O ≈ NO ≈ O₂. The presence of a soluble organic fraction (SOF) in soot is found to influence some reactions, and all three reactions suffer from inhibition by surface products. The mechanisms proposed for the surface adsorbates are summarised. All authors found that two types of active site were present; one forming weak bonds (physisorption), and the other undergoing chemisorption to form groupings such as -C-ONO, -C-ONO₂ or -C-NO₂. The latter decompose to give oxides of carbon, and are sometimes called redox reactions. The adsorbates appear to be the same for all NO_x species. Some elemental nitrogen adsorption takes place, and can involve incorporation into the C skeleton. The attack of NO on carbon proceeds via NO₂, so that catalysts that facilitate this oxidation are effective. Gaseous SO₂ and H₂O assist in the process by forming acids which are good oxidants. The change in activation energy with temperature found experimentally for NO and N₂O may be due to the form of nitrogen on the edge carbon atoms.     

Low Activation Energy Pathway for the Catalyzed Reduction of Nitrogen Oxides to N<Subscript>2</Subscript> by Ammonia

A low activation energy pathway for the catalytic reduction of nitrogen oxides to N₂, with reductants other than ammonia, consists of two sets of reaction steps. In the first set, part of the NO _x is reduced to NH₃; in the second set ammonium nitrite, NH₄NO₂ is formed from this NH₃ and NO + NO₂. The NH₄NO₂ thus formed decomposes at ~100 °C to N₂ + H₂O, even on an inert support, whereas ammonium nitrate, NH₄NO₃, which is also formed from NH₃ and NO₂ + O₂, (or HNO₃), decomposes only at 312 °C yielding mainly N₂O. Upon applying Redhead's equations for a first order desorption to the decomposition of ammonium nitrite, an activation energiy of 22.4 is calculated which is consistent with literature data. For the reaction path via ammonium nitrite a consumption ratio of 1/1 for NO and NO₂ is predicted and confirmed experimentally by injecting NO into a mixture of NH₃ + NO₂ flowing over a BaNa/Y catalyst. This leads to a yield increase of one N₂ molecule per added molecule of NO. Little N₂ is produced from NH₃ + NO in the absence of NO₂.     

NO and N2O emissions from savanna soils following the first simulated rains of the season

Data on the emissions of oxides of nitrogen from the soil during the early part of the wet season are reported for nutrient-rich and nutrient-poor sandy soils at Nylsvley, South Africa. The emissions of NO_x and N₂O following the first wetting event of the season are elevated relative to subsequent events. The observed high emission rates (76 ng N-NO m^-2 s^-1) are partially attributed to the sandiness of the soil, which permits NO to diffuse out of the soil rapidly. The pulse of high emissions following wetting is maintained for approximately 72 hours, thereafter continuing at around 20 ng NO m^-2 s^-1 while the soil remains moist. The initial pulse is suggested to be due to the accumulation of a substrate pool during the dry period, coupled with an inability of plants and microbes to use it effectively during the first few days after wetting. There were no significant differences in the peak or subsequent emission rates for either NO or N₂O between two sites of differing nitrogen mineralisation potentials. N₂O emissions averaged 8% of NO_x emissions. The enhanced emissions of NO_x which follow the first wetting after a prolonged dry period do not make a very large contribution to the annual gaseous N emission budget, but could be a significant contributor to the high tropospheric ozone levels observed over southern Africa in springtime.     

Absorption of NO x in packed column (I)

A mathematical model for an absorption of nitrogen oxides into water in packed column was developed based on the mass-transfer coefficient in packed column and the chemical reaction accompanying NO _x absorption produces HNO₃ and HNO₂ in the liquid phase. The subsequent dissociation of HNO₂ in the liquid-phase results in the formation of HNO₃ and NO gas, and then this NO gas follows to be oxidized by O₂ in air. The important factors influenced on the absorption of NO _x are the oxidation state of NO gas and the partial pressure of nitrogen oxides in the gas. The efficiency of NO _x absorption increases with the increase of the partial pressure of NO _x . The most critical value for using the model is the constant of .The selection of 11×10⁻⁴kg·mol/atm·m²·sec for resonable for this model.