Smog chamber study of H2O2 formation in ethene?NOx and propene?NOx mixtures

Hydrogen peroxide formation in the photooxidation of CO? NO_x, ethene? NO_x, and propene? NO_x mixtures has been determined in the TVA 31 cubic meter smog chamber under the following conditions: [NO_x] ca. 22–46 ppb; ethene = 0.22–1.1 ppm, [propene] = 0.12–0.97 ppm; [H₂O] ca. 8 × 10^?3 ppm. Ethene, propene, NO, NO_x, PAN, HCHO, and CH₃CHO were also monitored. Computer modeling was performed using the gas phase ethene and propene mechanism of the Regional Acid Deposition Model. There is good agreement between the model predicted and observed H₂O₂ concentrations. However, to successfully model all the propene? NO_x experimental results, organic nitrate formation from the reaction of peroxy radicals with NO must be included in the mechanism.     

Generation of Antimicrobial NO<Subscript>x</Subscript> by Atmospheric Air Transient Spark Discharge

Atmospheric pressure air plasma discharges generate potential antimicrobial agents, such as nitrogen oxides and ozone. Generation of nitrogen oxides was studied in a DC-driven self-pulsing (1–10 kHz) transient spark (TS) discharge. The precursors of NO_x production and the TS characteristics were studied by nanosecond time-resolved optical diagnostics: a photomultiplier module and a spectrometer coupled with fast intensified camera. Thanks to the short (~10–100 ns) high current (>1 A) spark current pulses, highly reactive non-equilibrium plasma is generated. Ozone was not detectable in the TS, probably due to higher gas temperature after the short spark current pulses, but the NO_x production rate of ~7 × 10¹⁶ molecules/J was achieved. The NO₂/NO ratio decreased with increasing TS repetition frequency, which is related to the complex frequency-dependent discharge properties and thus changing NO₂/NO generating mechanisms. Further optimization of NO₂ and NO production to improve the biomedical and antimicrobial effects is possible by modifying the electric circuit generating the TS discharge.     

Plasma Nitrogen Oxides Synthesis in a Milli-Scale Gliding Arc Reactor: Investigating the Electrical and Process Parameters

Nitrogen fixed in the form of nitrogen oxides is essential to produce fertilizers and many other chemical products, which is vital to sustain life. The performance of a milli-scale gliding arc reactor operated under atmospheric pressure has been studied for nitrogen oxides synthesis. In this work, the electrical and process parameters of the gliding arc reactor, such as frequency, pulse width, amplitude and feed ratio were investigated respectively. The experiments were performed at 1 L/min in a gliding arc discharge regime. The highest concentration of NO_x was found to be ~1 % at energy consumption of 10 kWh/kg of NO_x. Increase in frequency, pulse width and amplitude resulted in an increased specific energy input and NO_x concentration. The feed ratio (N₂/O₂) affected the amount of NO and NO₂ produced, which gives possibility to independently obtain the desired ratio of NO/NO₂ by tuning the electrical and process parameters.     

Promotion of Non-thermal Plasma on Catalytic Reduction of NOx by C3H8 Over Co/BEA Catalyst at Low Temperature

The effects of non-thermal plasma on selective catalytic reduction of NO_x by C₃H₈ (C₃H₈-SCR) over Co/BEA catalyst were investigated over a wide range of reaction temperatures (473–773 K). The significant synergistic effect between non-thermal plasma and catalytic reduction by C₃H₈ was exhibited at low temperatures from 473 to 673 K. The synergetic effect diminished with increasing temperature. The NO_x removal efficiency of non-thermal plasma facilitated C₃H₈-SCR hybrid system increased significantly with the increase in NO₂/NO ratio from 0.13 to 1.06 when the specific input energy increased from 0 to 136 J L^?1. The oxidation performance of NO to NO₂ was significantly enhanced by C₃H₈ in the plasma reactor. Results of CO₂/CO ratio and CO₂ selectivity suggested that adding non-thermal plasma improved CO₂ selectivity of C₃H₈-SCR. 200 ppm SO₂ slightly inhibited NO_x conversion of the non-thermal plasma facilitated C₃H₈-SCR hybrid system at below 673 K, whereas it exhibited no obvious effect at over 673 K. Non-thermal plasma was more selective toward NO oxidation than SO₂ oxidation in the presence of C₃H₈. The non-thermal plasma facilitated C₃H₈-SCR hybrid system could be used stably in durability tests with several hundreds ppm of SO₂.     

Production of Reactive Oxygen Species and Application for NOx Control

Current gas ionization discharge techniques used in the removal of NOx from waste gases require large plasma sources, have high energy consumption, and may feature low NOx removal rates. We develop a system to generate reactive oxygen species through a strong ionization discharge, which is injected into a flow of simulated waste gas. The relative proportions and temperatures of input gases were controlled and the rate of consumption by reactive species was monitored. HNO₃ oxidization products of NOx were also collected and measured. The molar ratio of reactive oxygen species to NO was optimized to improve the rate of NOx removal. A input gas temperature of 58–60 °C was also found to be optimal. The O₂ volume fraction has almost no influence on NOx removal, while H₂O volume fractions above 6 %, gave rise to NOx removal rates of 97.2 %. The present study addresses disadvantages of current gas ionization discharge and requires no catalyst, reducing agent or oxidant.     

Influence of NO on the Reduction of NO2 with CO over Pt/SiO2 in the Presence of O2

Reduction of NO2 with CO in the presence of NO and excess oxygen, a model mixture for flue gas, over a 0.1% Pt/SiO2 catalyst was studied. The related reaction mechanisms, such as oxidation of CO and NO, were discussed. It was found that there was a narrow temperature window （180-190 ℃） for the reduction of NO2 by CO. When the temperature was lower than the lower limit of the window, the reduction hardly occurred, while when the temperature was higher than the upper limit of the window, the direct oxidation of CO by O2 occurred and thereby NO2 could not be effectively reduced by CO. The presence of NO shifted the window to higher temperatures owing to the inhibition effect of NO on the activation of O2 on Pt, which made it possible to reduce NO2 by CO in flue gas.     

Catalytic oxidation of NO over Mn–Co–Ce–Ox catalysts: effect of reaction conditions

Manganese–cobalt–cerium oxide (Mn–Co–Ce–Ox) catalysts were synthesized by the co-precipitation method and tested for activity in low-temperature catalytic oxidation of NO in the presence of excess O₂. With the best Mn–Co–Ce mixed-oxide catalyst, approximately 80 % NO conversion was achieved at 150 °C and a space velocity of 35,000 h^?1. The effect of reaction conditions (reaction temperature, volume fractions of NO and O₂, gas hourly space velocity (GHSV), and catalyst stability) was investigated. The optimum reaction temperature was 150 °C. Increasing the O₂ content above 3 % results in almost no improvement of NO oxidation. This catalyst enables highly effective removal of NO within a wide range of GHSV. Furthermore, the stability of the Me–Co–Ce–Ox catalyst was excellent; no noticeable decrease of NO conversion was observed in 40 h.     

Theoretical mechanistic study on the radical-molecule reaction of CH2Br/CHBrCl with NO2

The radical-molecule reaction mechanisms of CH₂Br and CHBrCl with NO₂ have been explored theoretically at the UB3LYP/6-311G(d, p) level. The single-point energies were calculated using UCCSD(T) and UQCISD(T) methods. The results show that the title reactions are more favorable on the singlet potential energy surface than on the triplet one. For the singlet potential energy surface of CH₂Br + NO₂ reaction, the association of CH₂Br with NO₂ is found to be a barrierless carbon-to-oxygen attack forming the adduct IM1 (H₂BrCONO-trans), which can isomerize to IM2 (H₂BrCNO₂), and IM3 (H₂BrCONO-cis), respectively. The most feasible pathway is the 1, 3-Br shift with C–Br and O–N bonds cleavage along with the N–Br bond formation of IM1 lead to the product P1 (CH₂O + BrNO) which can further dissociate to give P4 (CH₂O + Br + NO). The competitive pathway is the 1, 3-H-shift associated with O–N bond rupture of IM1 to form P2 (CHBrO + HNO). For the singlet potential energy surface of CHBrCl + NO₂ reaction, there are three important reaction pathways, all of which may have comparable contribution to the reaction of CHBrCl with NO₂. The theoretically obtained major products CH₂O and CHClO for CH₂Br + NO₂ and CHBrCl + NO₂ reactions, respectively, are in good agreement with the kinetic detection in experiment.     

Removal of Model Pollutants in Aqueous Solution by Gliding Arc Discharge: Determination of Removal Mechanisms. Part I: Experimental Study

The respective roles of short and long-life oxidant species in the degradation of model organic pollutants in water have been investigated in a gas–liquid gliding arc plasma reactor. Three different model pollutants were treated in two configurations: direct discharge mode and spatial post discharge mode. In each case the pollutants were classified according to their ease of removal, from easier to more difficult to remove. The results were as follows: phenol >> 1-heptanol >> pCBA. The removal mechanisms also are different depending on the characteristics of the pollutant treated. Phenol (100 % of phenol was removed for energy density = 1.20 × 10⁵ J/L) was supposed to react strongly with NO₂° radicals produced by the dissociation of N₂O₄ in liquid phase. The degradation of 1-heptanol would proceed by desorption of the liquid phase to the gas phase, where oxidation occurs due to the plasma active short-lived species. In the case of pCBA, oxidation occurs in the liquid solution, but the degradation is low because of its low reactivity with species such as ozone and °NO₂ and insufficient production of OH° radicals in the solution.     

Physicochemical properties of ceramic tape involving Ca<Subscript>0.05</Subscript> Ba<Subscript>0.95</Subscript> Ce<Subscript>0.9</Subscript>Y<Subscript>0.1</Subscript>O<Subscript>3</Subscript> as an electrolyte designed for electrolyte-supported solid oxide fuel cells (IT-SOFCs)

Energetic materials such as a mixture of guanidine nitrate (GN)/basic copper nitrate (BCN) are used as gas generators in automotive airbag systems. However, at the time of the airbag inflation, the gas generators release toxic combustion gases such as CO, NH₃, and NO_x. In this study, we investigated the combustion and thermal decomposition behaviors of GN/BCN mixture, focusing primarily on their exhaust gas composition. As a result, when the exhaust gas of the combustion under constant pressure in an inert gas stream was analyzed using a detection tube, the amount of NO_x (mainly NO) yielded greater decrease with increasing atmospheric pressure as compared to the amounts of CO and NH₃. Thus, provided GN/BCN is ignited in a closed container, a large amount of NO_x is presumed to have been released during the initial stage of combustion, which yielded comparatively low pressure. Results of the thermogravimetry–differential scanning calorimetry–Fourier transform infrared spectroscopy (TG/DSC/FTIR) indicated that the GN/BCN mixture caused endothermic decomposition at 170 °C and exothermic decomposition at 208 °C, which was accompanied by 66% mass loss. The decomposition gases, CO₂, N₂O, and H₂O, were detected via FTIR spectrum. Because N₂O was not detected in the combustion gas, it was suggested that the detected N₂O was generated at a low temperature and decomposed in high-temperature combustion.     

Thermal properties of 1,2,4-triazole-3-one and copper nitrate mixtures

1,2,4-Triazole-3-one (TO) is anticipated to have applications as a high performance alternative gas generating agent, while basic copper nitrate (BCN) is typically used as the oxidizing agent in air bag systems. In order to obtain a better understanding of the thermal properties of TO/BCN mixtures, thermal behavior was investigated using the differential scanning calorimetry. Mixtures of TO with copper, copper oxide, and trihydrated copper nitrate (Cu(NO₃)₂·3H₂O) were also examined for comparison purposes. Samples were prepared at TO/BCN ratios (on a per mass basis) of 10/0, 7/3, 5/5, 3/7, 2/8, 1.6/8.4, 1/9, and 0/10. The endothermic onset temperatures for TO/BCN mixtures were lower than those for either pure TO or pure BCN. TO/BCN mixtures exhibited an initial exothermic peak immediately after an endothermic peak, in the range of 219–234 °C. TO/BCN mixtures with ratios of 3/7, 2/8, 1.6/8.4, and 1/9 displayed a second series of exothermic peaks in the range of 260–300 °C, which appear to result from the oxidation–reduction reaction of previously formed intermediate species with NO₂ and NO generated by unreacted BCN. The TO/CuO mixtures are believed to undergo reaction between molten TO and CuO at approximately 230 °C. In general, the presence of copper was shown to be effective at promoting the decomposition of TO. The reaction between TO and Cu(NO₃)₂·3H₂O seems to be initiated by the melting of Cu(NO₃)₂·3H₂O, following which TO reacts with nitric acid resulting from the dissociation of Cu(NO₃)₂·3H₂O. Overall, the triggering event for the reaction between TO and each of the copper nitrate species is a phase change of one of the two mixture components.     

A DFT study of adsorption and decomposition of nitroamine molecule on Mg(001) surface

The adsorption and dissociation mechanism of NH₂NO₂ on the Mg surface have been investigated by the generalized gradient approximation of density functional theory. Calculations employ a supercell (3 × 3 × 3) slab model and three-dimensional periodic boundary conditions. The strong attractive force between oxygen and Mg atoms induces the N–O bond of the NH₂NO₂ to decompose. The dissociated oxygen atoms and radical fragment of NH₂NO₂ oxidize readily Mg atoms. The largest adsorption energy is ?860.5 kJ/mol. The largest charge transfer is 3.76 e from surface Mg atoms to fragments of NH₂NO₂. The energy barriers of N–O bond dissociation are in a range of 11.6–36.5 kJ/mol. The adsorption energy of NH₂NO₂ on the Mg surface compensates the energy needed for the N–O bond dissociation.     

Modification of zeolites usingin situ generated active species in the gas phase: II. Redox processes over the Mo5+ isolated sites in zeolites ZSM-5 and beta

The redox ability of isolated Mo⁵⁺ cations in model MoH-beta and MoH-ZSM-5 systems is studied byin situ ESR. The oxidation of reduced samples by nitrogen monoxide at 20°C proceeds much faster than oxidation by oxygen. The interaction between Mo⁵⁺ ions and propene at 20°C results in the formation of a complex in which the oxidizability of Mo(V) by NO is substantially enhanced. UV irradiation increases the oxidation rate for Mo⁵⁺ ions in HZSM-5 by nitrogen monoxide at 20°C, indicating the possibility for the photochemical activation of the process. The step of active site reduction during the interaction of the samples with the H₂ + NO + He gas mixtures of various compositions at 500°C is fast, and the dynamic equilibrium of the redox Mo(V) ai Mo(VI) reaction is shifted to the left Deceased.     

Gas-phase reaction of NO3 radicals with isoprene: a kinetic and mechanistic study

The gas-phase reaction of NO₃ radicals with isoprene was investigated under flow conditions at 298 K in the pressure range 6.8<P(mbar)<100 using GC-MS/FID, direct MS, and long-path FT–IR spectroscopy as detection techniques. By means of a relative rate method, the rate constant for the primary attack of NO₃ radicals toward isoprene was determined to be (6.86±2.60)×10⁻¹³ cm³ molecule⁻¹ s⁻¹. The formation of the possible oxiranes, 2-methyl-2-vinyl-oxirane and 2-(1-methyl-vinyl)-oxirane, was observed in dependence on total pressure. In the presence of O₂ in the carrier gas, the product distribution was found to be strongly dependent on the reaction pathways of formed peroxy radicals. If the peroxy radicals mainly reacted in a self-reaction, the formation of organic nitrates was detected and 4-nitroxy-3-methyl-but-2-enal was identified as a main product. On the other hand, when NO was added to the gas mixture and the peroxy radicals were converted via RO₂+NO→RO+NO₂, the formation of methyl vinyl ketone as the main product as well as 3-methylfuran and meth-acrolein was observed. From the ratio of the product yields if NO was added to the gas mixture it was concluded that the attack of NO₃ radicals predominantly takes place in the 1-position. A reaction mechanism is proposed and the application of these results to the troposphere are discussed. © 1997 John Wiley & Sons, Inc.     

Reduction of NO2 in Flue Gas by CO and Propylene over CuO‐CeO2/SiO2 in the Presence of O2

Catalytic reduction of NO₂ with CO and/or propylene in the presence of NO and excess oxygen, a model mixture for flue gas, was studied over a series of CuO‐CeO₂/SiO₂ catalysts between 120–260 °C. The effect of HCl, an impurity in flue gas, on the activity of the catalysts was evaluated. It was found that a binary oxide catalyst, 2% CuO‐8% CeO₂/SiO₂, was active for the reduction of NO₂ by CO and/or propylene. CO was effective for selective reduction of NO₂ in the presence of NO and O₂ in a temperature window between 160–200 °C while propylene was effective at temperature higher than 200 °C. In the presence of HCl, the activity of the catalyst for reduction of NO₂ with CO was irreversibly deactivated. However, the activity for reduction of NO₂ with propylene was not influenced by HCl.     

Effectiveness of nitric oxide ozonation

Attempts to develop new technologies of NO _x (NO + NO₂) emission reduction are still carried out all around the world. One of the relatively new approaches is the application of ozone injection into the exhaust gas stream followed by the absorption process. Ozone is used to transform NO _x to higher nitrogen oxides which yield nitric acid with better effectiveness. The main objective of this paper was to study the influence of mole ratio (MR) O₃/NO used in the ozonation process of NO _x on the effectiveness of NO _x oxidation to higher oxides. The ozonation process was carried out in a flow reactor for concentrations of nitric oxide in the range of 1.5 × 10⁻⁵−7.7 × 10⁻⁵ mol dm⁻³ and varying O₃/NO mole ratios. Measurements were conducted with the use of a FTIR spectrometer. The results obtained prove that for MR higher than 1, the oxidation effectiveness of nitric oxides generally reaches 95 %, whereas for MR higher than 2, oxidation of NO _x to higher nitrogen oxides is completed.     

Oxidation of Elemental Mercury by Active Species Generated From a Surface Dielectric Barrier Discharge Plasma Reactor

A surface dielectric barrier discharge plasma reactor was employed to study Hg⁰ oxidation in coal-fired flue gas. The experimental results showed that 98 % of Hg⁰ oxidation efficiency and 13.7 μg kJ^?1 of energy yield were obtained under a specific energy density (SED) of 7.9 J L^?1. Increasing SED was beneficial for Hg⁰ oxidation due to higher production of active species. Higher initial concentration resulted in lower Hg⁰ oxidation efficiency, but higher amount of Hg⁰ oxidation. Water vapor inhibited Hg⁰ oxidation because the generation of O₃ was suppressed. The presence of NO remarkably restrained Hg⁰ oxidation, while SO₂ showed little effect on Hg⁰ oxidation. Roles of active species in Hg⁰ oxidation were examined under different gas atmospheres (O₂ and air), indicating that O₃ played an important role in Hg⁰ oxidation. Deposits on the internal surface of the reactor were analyzed by energy dispersive spectroscopy and the product was identified as HgO.     

Activated carbon prepared by physical activation of olive stones for the removal of NO2 at ambient temperature

Activated carbon was prepared from olive stones by physical activation using water vapor at 750 °C. Textural, morphology and surface chemistry characterizations were achieved (nitrogen adsorption, SEM, FTIR and TPD–MS). NO₂ adsorption was performed for different inlet gas compositions and temperatures. NO₂ may adsorb directly on the oxygenated surface groups, and can also be reduced to NO. Therefore, a second NO₂ molecule adsorbs on the oxygen left on the carbon surface. TPD performed after NO₂ adsorption showed the presence of various surface groups. The adsorption capacity was about 131 mg/g, which is higher than with several activated carbon prepared from classical lignocellulosic biomass. NO₂ reduction into NO decreased with increasing the inlet oxygen concentration. In contrast, a slight decrease in the NO₂ adsorption capacity was observed with increasing temperature. It seems that the activated carbons prepared from olive stones by steam activation could be used as efficient adsorbents for NO₂ removal.     

高硅 Na-ZSM-5 分子筛表面 NO 的常温吸附-氧化机理

 采用程序升温表面反应 (TPSR) 和原位漫反射红外光谱 (DRIFTS) 等手段研究了常温下 NO 和 O₂ 在高硅 Na-ZSM-5 分子筛上吸附-氧化反应机理. 结果表明, Na-ZSM-5 分子筛上 NO 的催化氧化过程中伴随着显著的 NO₂ 物理吸附, 表现为 NO 氧化和 NO₂ 吸附间的动态平衡. Na-ZSM-5 分子筛表面 NO_x 吸附物种的 TPSR 和原位 DRIFTS 表征表明, 化学吸附的 NO 和气相中的 O₂  在 Na-ZSM-5 表面反应生成吸附态的 NO₃, 并继续与 NO 作用生成弱吸附的 NO₂  和 N₂ O₄, 它们吸附饱和后释放出来; 其中, 强吸附的 NO₃ 在 NO 氧化过程中起到了反应中间体的作用, 同时也促进了 NO 的吸附.     

臭氧氧化结合湿法喷淋对玻璃窑炉烟气同时脱硫脱硝实验研究

采用臭氧氧化结合湿法喷淋对模拟玻璃窑炉烟气开展了同时脱硫脱硝实验研究.采用不同溶液(NaOH、Na₂S)进行了喷淋实验.结果表明,保证溶液pH值在10以上,NaOH浓度对NO_x脱除效率无影响,SO₂的存在促进了NO_x吸收.当O₃/NO物质的量比为1.6、溶液NaOH浓度为0.5%时,NO_x脱除效率可达70%,SO₂脱除效率在99%以上.往喷淋液中添加Na₂S,NO_x脱除效率随Na₂S浓度增加而提高,SO₂的存在对NO_x脱除效率无影响.当O₃/NO物质的量比为1.2、溶液中NaOH浓度为0.5%、添加剂Na₂S浓度为0.6%时,NO_x脱除效率可达70%,SO₂脱除效率在95%以上.60 min长时间运行实验证明,模拟烟气中的NO_x经碱液和添加剂吸收后主要以NO^-₂的形式存在于喷淋液中,且NO_x脱除效率不随溶液pH值的变化而变化.