Oxidation and Reduction Processes During NO x Removal with Corona-Induced Nonthermal Plasma

In this paper, the NO-to-NO ₂ conversion in various gaseous mixtures is experimentally investigated. Streamer coronas are produced with a dc-superimposed high-frequency ac power supply (10–60 kHz). According to NO _x removal experiments in N ₂ +NO _x and N ₂ +O ₂ +NO _x gaseous mixtures, it is supposed that the reverse reaction NO ₂ +ONO+O ₂ may not only limit NO ₂ production in N ₂ +NO _x mixtures, but also increase the energy cost for NO removal. Oxygen could significantly suppress reduction reactions and enhance oxidation processes. The reduction reactions, such as N+NON ₂ +O, induce negligible NO removal provided the O ₂ concentration is larger than 3.6%. With adding H ₂ O into the reactor, the produced NO ₂ per unit removed NO can be significantly reduced due to NO ₂ oxidation. NH ₃ injection could also significantly decrease the produced NO ₂ via NH and NH ₂ - related reduction reactions. Almost 100% of NO ₂ can be removed in gaseous mixtures of N ₂ +O ₂ +H ₂ O+NO ₂ with negligible NO production.     

Studies on Gas Purification by a Pulsed Microwave Discharge at 2.46 GHz in Mixtures of N2/NO/O2 at Atmospheric Pressure

Pulsed microwave discharges operated at atmospheric pressure in gas mixtures containing N₂, O₂, and NO are investigated experimentally and theoretically for various gas mixture constituents and operating conditions with respect to the ability of exhaust gas purification. The rotational gas temperature and the vibrational temperature of N₂ are derived from CARS measurements. The composition of the exhaust gas after treatment is monitored using FTIR spectroscopy. The processes of the chemical, electronic, and vibrational kinetics are described by a model that has been developed to calculate the species densities. The results obtained show that in N₂/NO gas mixtures an overall reduction of NO_x takes place. In the case of N₂/O₂/NO gas mixtures, no net reduction of NO_x is achieved for a pulsed microwave power below 3600 W, a pulse length of 50 s, and a typical repetition frequency of 2 kHz.     

Point and Multipoint to Plane Barrier Discharge Process for Removal of NOx from Engine Exhaust Gases: Understanding of the Reactional Mechanism by Isotopic Labeling

An experimental study on the removal of NO_x in a simulated vehicle exhaust gas has been carried out using point to plane and multipoint to plane DBD corona reactors. Hydrocarbon (C₃H₆) and NO_x by-products were systematically investigated with a Gas Chromatography coupled to a Mass Spectrometry (GC/MS). NO_x (NO and NO₂) and CO output were also monitored with a gas analyzer in order to complete the mass balance. ¹⁸O tracer technique analyzes is applied to investigate the mechanism of propylene decomposition. From the plasma chemical reaction pathway proposed, it is apparent that the oxygen activation is one of the important steps for initiating the oxidation processes and the R-NO_x formation. We present data for the reaction of the (N₂/O₂/C₃H₆/CO₂NO/H₂O system in the corona discharge reactors mentioned above. This system has been shown to generate a significant amount of aldehyde. CH₃NO₂ and CH₃ONO₂ are the main R-NO_x compounds produced. Reactant composition and discharge energy densities (controlled by a numerical oscilloscope) were the operating parameters under study in wet and dry air mixture. Water vapors played an important role in NO_x removal (especially in NO₂ removal) via the reaction forming HNO₃. Therefore, in wet-gas mixture supplied reactors the highest removal rates of NO_x were as high as 30%, while in dry-gas only 15%. Different dielectric materials such as Al₂O₃/SiO₂ and TiO₂ on Al₂O₃/SiO₂ support have been used.     

NOx-Sorbing Metal Oxides, MnOx–CeO2. Oxidative NO Adsorption and NOx–H2 Reaction

(n)MnO_x–(1–n)CeO₂ binary oxides have been studied for the sorptive NO removal and subsequent reduction of NO_x sorbed to N₂ at low temperatures (150 °C). The solid solution with a fluorite-type structure was found to be effective for oxidative NO adsorption, which yielded nitrate (NO^– ₃) and/or nitrite (NO^– ₂) species on the surface depending on temperature, O₂ concentration in the gas feed, and composition of the binary oxide (n). A surface reaction model was derived on the basis of XPS, TPD, and DRIFTS analyses. Redox of Mn accompanied by simultaneous oxygen equilibration between the surface and the gas phase promoted the oxidative NO adsorption. The reactivity of the adsorbed NO_x toward H₂ was examined for MnO_x–CeO₂ impregnated with Pd, which is known as a nonselective catalyst toward NO–H₂ reaction in the presence of excess oxygen. The Pd/MnO_x–CeO₂ catalyst after saturated by the NO uptake could be regenerated by micropulse injections of H₂ at 150 °C. Evidence was presented to show that the role of Pd is to generate reactive hydrogen atoms, which spillover onto the MnO_x–CeO₂ surface and reduce nitrite/nitrate adsorbing thereon. Because of the lower reducibility of nitrate and the competitive H₂–O₂ combustion, H₂–NO reaction was suppressed to a certain extent in the presence of O₂. Nevertheless, Pd/MnO_x–CeO₂ attained 65% NO-conversion in a steady stream of 0.08% NO, 2% H₂, and 6% O₂ in He at as low as 150 °C, compared to ca. 30% conversion for Pd/–Al₂O₃ at the same temperature. The combination of NO_x-sorbing materials and H₂-activation catalysts is expected to pave the way to development of novel NO_x-sorbing catalysts for selective deNO_x at very low temperatures.     

Thermal decomposition of cobalt nitrato compounds: Preparation of anhydrous cobalt(II)nitrate and its characterisation by Infrared and Raman spectra

The thermal decomposition of Co(NO₃)₂·6H₂O (1) as well as that one of NO[Co(NO₃)₃] (Co(NO₃)₂·N₂O₄) (2) was followed by thermogravimetric (TG) measurements, X-ray recording and Raman and IR spectra. The stepwise decomposition reactions of 1 and 2 leading to anhydrous cobalt(II)nitrate (3) were established. In N₂ atmosphere, cobalt oxides are finally formed whereas in H₂/N₂ (10% H₂) cobalt metal is produced. Rapid heating of cobalt(II)nitrate hexahydrate causes melting (formation of a hydrate melt) and therefore side reactions in the hydrate melt by incoupled reactions and evolution/evaporation of different species as, e.g., HNO₃, NO₂, etc. In case of larger amounts in dense packing in the sample container, the formation of oxo(hydoxo)nitrates is possible at higher temperature. For 2, its thermal decomposition to 3 was followed and its decomposition mechanism is proposed.     

Conversion of NO in NO/N2, NO/O2/N2, NO/C2H4/N2 and NO/C2H4/O2/N2 Systems by Dielectric Barrier Discharge Plasmas

An experimental study on the conversion of NO in the NO/N₂, NO/O₂/N₂, NO/C₂H₄/N₂ and NO/C₂H₄/O₂/N₂ systems has been carried out using dielectric barrier discharge (DBD) plasmas at atmospheric pressure. In the NO/N₂ system, NO decomposition to N₂ and O₂ is the dominating reaction; NO conversion to NO₂ is less significant. O₂ produced from NO decomposition was detected by an on-line mass spectrometer. With the increase of NO initial concentration, the concentration of O₂ produced decreases at 298 K, but slightly increases at 523 K. In the NO/O₂/N₂ system, NO is mainly oxidized to NO₂, but NO conversion becomes very low at 523 K and over 1.6% of O₂. In the NO/C₂H₄/N₂ system, NO is reduced to N₂ with about the same NO conversion as that in the NO/N₂ system but without NO₂ formation. In the NO/C₂H₄/O₂/N₂ system, the oxidation of NO to NO₂ is dramatically promoted. At 523 K, with the increase of the energy density, NO conversion increases rapidly first, and then almost stabilizes at 93–91% of NO conversion with 61–55% of NO₂ selectivity in the energy density range of 317–550 J L⁻¹. It finally decreases gradually at high energy density. A negligible amount of N₂O is formed in the above four systems. Of the four systems studied, NO conversion and NO₂ selectivity of the NO/C₂H₄/O₂/N₂ system are the highest, and NO/O₂/C₂H₄/N₂ system has the lowest electrical energy consumption per NO molecule converted.     

The reaction of ammonia with nitrogen dioxide in a flow reactor: Implications for the NH2 + NO2 reaction

The NH₃/NO₂ system has been investigated experimentally in an isothermal flow reactor in the temperature range 850–1350 K. The experimental data were interpreted in terms of a detailed reaction mechanism. The flow reactor results, supported by a theoretical analysis of the NH₂? NO₂ complex, suggest that the NH₂ + NO₂ reaction has two major product channels, both proceeding without activation barriers: Our findings indicate that the N₂O + H₂O channel is dominant at low temperatures while H₂NO + NO dominates at high temperatures. The rate constant for reaction (R21) is estimated to be 3.5 · 10¹² cm³/mol-s in the temperature range studied with an uncertainty of a factor of 3. © 1995 John Wiley & Sons, Inc.     

Methane Decomposition in a Barium Titanate Packed-Bed Nonthermal Plasma Reactor

The behavior of lattice oxygen species of the ferroelectric material during methane oxidation was investigated using a nonthermal plasma reactor packed with BaTiO ₃ pellets. Lattice oxygen species in BaTiO ₃ play an important role in the formation of N ₂ O and the oxidation of CH ₄ . The oxidation products such as CO and CO ₂ were formed from independent reaction pathways. Lattice oxygen species were able to preferentially oxidize the carbon species deposited on the pellet surface into CO. Also, N ₂ O and NO _x were independently formed in the N ₂–O ₂ reaction, suggesting that different oxygen species give N ₂ O and NO _x. N ₂ O was produced by the oxidation of molecular nitrogen with lattice oxygen species.     

Silica-Supported 4-OH-TEMPO/NOx: A Novel and Efficient Catalyst for Aerobic Oxidation of Alcohols

Silica-supported 4-OH-2,2,6,6-tetramethylpiperidyl-1-oxy/NO_x (4-OH-TEMPO was immobilized on the surface of silica using the sol-gel method, and then it adsorbed NO_x), as a heterogeneous catalyst, has exhibited good catalytic performance in alcohol oxidation. A broad range of alcohols were oxidized to their corresponding aldehydes or ketones with more than 99% selectivity and 99% conversion rate by such a catalyst system at room temperature in air. NO_x not only acted as an electron bridge between O₂ and 4-OH-TEMPO but also were conducive to the formation of the aldehydes as active component. A possible mechanism for oxidation of alcohols promoted by silica-supported 4-OH-TEMPO/NO_x was supposed.

[Supplementary materials are available for this article. Go to the publisher's online edition of Synthetic Communications® for the following free supplemental resource(s): Full experimental and spectral details.]     

Effect of the Support in de-NOx HC-SCR Over Transition Metal Catalysts

Several catalysts based on transition metals (Cu, Co, Fe) and different supports (ZSM-5, activated carbon, Al₂O₃) have been tested by Temperature-Programmed Reaction (TPR) experiments for the selective catalytic reduction of NO_x with propene in the presence of excess oxygen, simulating lean-burn conditions. The activity order with respect to the metal was CuFe>Co for all supports used. ZSM-5 catalysts have a superior behavior over Al₂O₃, as observed for noble metal catalysts. Application of activated carbon as a support is not practical due to its consumption at the reaction temperatures. The selectivity to N₂ of the catalysts was also independent of the support, being higher than 95% in all the cases.     

By-Products NOx Control and Performance Improvement of a Packed-Bed Nonthermal Plasma Reactor

NO_x are main toxic by-products in the effluent gas whendecomposing volatile organic compounds in air by a packed-bed plasmareactor. Several types of materials such as 13X zeolite, BaTiO₃and Pd/Pt catalysts have been selected to be packed in the reactor, andmethane decomposition and NOx by-products in discharged gases areinvestigated at different range of reaction temperature and dischargeenergy density at atmospheric pressure. The ratios of methane decompositionpercentage/NO_x concentration are used to assess these packed bedmaterials and reaction conditions. The results show that usingPd/-Al₂O₃ with lower percentage Pd as packedbed, and discharging with lower discharge density at higher reactiontemperature can reduce NO_x output effectively and greatly improveperformance of the reactor.     

Formation of heterometallic compounds in mixed solutions of nickel(II)-Schiff base complexes and lanthanide nitrates: Electrospray ionization mass spectrometry data

Atmospheric-pressure electrospray ionization mass spectrometric data are reported for methanolic Ni(SB) + Ln(NO₃)₃ · nH₂O solutions (H₂SB = N,N′-ethylene-bis(salicylaldiimine), N,N′-ethylene-bis(3-methoxysalicylaldiimine), N,N′-ethylene-bis(acetylacetonediimine); Ln = La, Eu, Lu). Dinuclear and trinuclear heterometallic complexes of composition [(Ni(SB)) _x Ln(NO₃)₃] (x = 1, 2) form in these solutions. The dinuclear-totrinuclear ion intensity ratio depends on the natures of the lanthanide and the Schiff base.     

X-ray photoelectron spectroscopic study of the interaction of supported metal catalysts with NO<Subscript>x</Subscript>

The reactions of the platinum and rhodium model catalysts applied to aluminum oxide with NO_x (10 Torr NO + 10 Torr O₂) were studied by X-ray photoelectron spectroscopy. The reaction conducted at room temperature formed on the surface of the oxide support the NO _3,s ^? nitrate ions characterized by the N1s line at 407.4 eV and O1s line at 533.1 eV and the NO _2,s ^? nitrite ions characterized by the N1s line with a binding energy of 404.7 eV. At the same time, the Pt4f and Rh3d lines of the supported platinum particles are shifted toward higher binding energies by 0.5–1.0 eV and 0.7–1.2 eV, respectively. It is assumed that the binding energies increase due to changes in the chemical state of the platinum metal in which oxygen is dissolved. The reaction of NO_x with Pt/Al₂O₃ at 200°C forms platinum oxide defined by the Pt4f _7/2 line with a binding energy of 72.3 eV.     

Development of PGM-free catalysts for automotive applications

The activity of Ag-based catalysts in soot oxidation using NO₂ and oxygen as oxidants has been characterized in laboratory tests (TGA) and under real conditions on an engine dynamometer. Under low-temperature NO₂-assisted and high-temperature O₂-assisted soot oxidation conditions, the activity of Ag-based catalysts was found to be comparable or higher than that of commercial Pt-catalysts. In addition, Ag-based compositions also revealed noticeable NO _x storage, some passive NO _x reduction ability, and activity in NO oxidation. Ag-catalysts characterized in the present paper may be promising for the retrofit applications and high-temperature periodical regenerations with air for diesel passenger cars.     

Solubility of 13 nonpolar gases in deuterium oxide at 15–45°C and 101.325 kPa. Thermodynamics of transfer of nonpolar gases from H2O to D2O

Using a computer controlled version of the Ben-Naim and Baer apparatus, the solubilities of He, Ne, Ar, Kr, H₂, D₂, N₂, O₂, CH₄, C₂H₆, C₃H₈, CF₄, and SF₆ in D₂O (and the solubility of CF₄ in H₂O) were determined at four temperatures in the range 288 to 318 K and at a partial pressure of gas of 101.325 kPa. The precision of the measurements was 0.3–1.0%. The experimental data were processed using rigorous thermodynamic methods and were fitted to the Clarke-Glew-Weiss equation. Changes in the thermodynamic properties on solution were calculated from the smoothing equations. Scaled-particle theory (SPT) was used to determine the Lennard-Jones (6,12) pair potential parameters for D₂O: =0.275 nm and /k=83.4 K. Experimental mole fraction solubilities and thermodynamic functions at 298.15 K were compared with results calculated using the SPT. The thermodynamic transfer functions of gases from H₂O to D₂O were calculated. The changes induced by the solvation process on the structure of water were estimated from the Gibbs energy of transfer and the difference in the hydrogen bond energies for D₂O and H₂O.     

Elucidation of the Surprising Role of NO in N2O Decomposition over FeZSM-5

The decomposition of N₂O is strongly promoted by NO over steam-activated FeZSM-5. The promoting effect of NO is catalytic, and in addition to NO₂, ₂ is formed much more extensively at lower temperatures than in the absence of NO. The promotion effect only requires low NO concentrations in the feed, with no significant improvements at molar NO/N₂O feed ratios higher than 0.25. No inhibition by NO was identified even at a molar NO/N₂O feed ratio of 10, suggesting different sites for NO adsorption and oxygen deposition by N₂O. The latter sites seem to be remote from each other. Transient experiments using in situ FT-IR/MS and Multitrack over FeZSM-5 further elucidate the mechanism of NO promotion. The release of oxygen from the catalyst surface during direct N₂O decomposition is a rate-determining step due to the slow oxygen recombination, which is favored by high reaction temperatures. NO addition promotes this oxygen desorption, acting as an oxygen transfer agent, probably via NO₂ species. Adsorbed NO may facilitate the migration of atomic oxygen to enhance their recombination. Less than 0.9% of Fe seems to participate in this promotion. A model is proposed to explain the phenomena observed in NO-assisted N₂O decomposition, including NO₂ decomposition.     

Effects of nitric oxide on the thermal decomposition of methyl nitrite: Overall kinetics and rate constants for the HNO + HNO and HNO + 2NO reactions

The effects of NO on the decomposition of CH₃ONO have been investigated in the temperature range 450–520 K at a constant pressure of 710 torr using He as buffer gas. The measured time-dependent concentration profiles of CH₃ONO, NO, N₂O, and CH₂O can be quantitatively accounted for with a general mechanism consisting of various reactions of CH₃O, HNO, and (HNO)₂. The results of kinetic modeling with sensitivity analyses indicate that the disappearance rate of CH₃ONO is weakly affected by NO addition, whereas that of the HNO intermediate strongly altered by the added NO. In the presence of low NO concentrations, the modeling of N₂O yields leads to the rate constant for the bimolecular reaction, HNO + HNO → N₂O + H₂O (25): In the presence of high NO concentrations (P_NO > 50 torr), the modeling of CH₂O yields gives the rate constant for the termolecular radical formation channel, HNO + 2NO → HN₂O + NO₂ (35): Discussion on the mechanisms for reactions (25) and (35), and the alkyl homolog of (35), RNO + 2NO, is presented herein. © John Wiley & Sons, Inc.     

Secondary ion emission of selected transition metals under nitrogen oxides

The emission of various positive secondary ions has been investigated for polycrystalline targets of Ti, V, Cr, Nb, Ta, Co, Ni, Cu, Pd and Pt, which were bombarded by Ar⁺ ions under dynamic SIMS (DSIMS) conditions in the presence of the gaseous nitrogen oxides N₂O, NO and NO₂ at fixed pressure and under residual gas. Besides ions of the Me⁺ type several fragmentary ions (e.g. N⁺, O⁺, NO⁺, MeN⁺ and MeO⁺) and also cluster ions Me _x O _y ⁺ (x 2, 0 y 2) were detected. Signals of a more molecular type with respect to the reactant gas, e.g. MeNO⁺, were only found for Co, Ni, Cu, Pd and Pt. From this, one may infer that for the other targets the nitrogen oxides will exist preferentially in a dissociatively adsorbed state at the metal surface. Several aspects of secondary ion emission can be explained assuming a different degree of oxidation for the metals under the influence of reactant gas.Part of the dissertation     

The 18O signature of biogenic nitrous oxide is determined by O exchange with water

To effectively mitigate emissions of the greenhouse gas nitrous oxide (N₂O) it is essential to understand the biochemical pathways by which it is produced. The ¹⁸O signature of N₂O is increasingly used to characterize these processes. However, assumptions on the origin of the O atom and resultant isotopic composition of N₂O that are based on reaction stoichiometry may be questioned. In particular, our deficient knowledge on O exchange between H₂O and nitrogen oxides during N₂O production complicates the interpretation of the ¹⁸O signature of N₂O. Here we studied O exchange during N₂O formation in soil, using a novel combination of ¹⁸O and ¹⁵N tracing. Twelve soils were studied, covering soil and land‐use variability across Europe. All soils demonstrated the significant presence of O exchange, as incorporation of O from ¹⁸O‐enriched H₂O into N₂O exceeded their maxima achievable through reaction stoichiometry. Based on the retention of the enrichment ratio of ¹⁸O and ¹⁵N of NO into N₂O, we quantified O exchange during denitrification. Up to 97% (median 85%) of the N₂O‐O originated from H₂O instead of from the denitrification substrate NO. We conclude that in soil, the main source of atmospheric N₂O, the ¹⁸O signature of N₂O is mainly determined by H₂O due to O exchange between nitrogen oxides and H₂O. This also challenges the assumption that the O of N₂O originates from O₂ and NO, in ratios reflecting reaction stoichiometry. Copyright © 2008 John Wiley & Sons, Ltd.     

Density of N<Subscript>2</Subscript>O Solutions in Perfluorodecalin As a Function of Concentration

The dependence of density ρ of nitrogen oxide N₂O solutions in perfluorodecalin on the N₂O concentration is measured. At a constant temperature, this dependence has a linear character: ρ = аx + b. Coefficients a and b are tabulated for five temperatures: 293, 298, 303, 313, and 328 K. These data allow us to control the N₂O concentration in perfluorodecalin.