电氧化N_2O_4制备N_2O_5工艺研究

以N2O4和HNO3为原料,通过电氧化法制备了新型绿色硝化剂N2O5,并研究了电解氧化法制备N2O5工艺的影响因素,主要讨论了电解反应时间、电流密度和反应温度对该工艺的影响。在反应时间为4～5h,电流密度为0.09～0.10A/cm2,反应温度为5～10℃时,可得到质量分数较高的N2O5阳极液。     

The desorption of O2 during NO and N2O decomposition on Cu- and Fe-zeolites

The decomposition of NO and of N₂O over a CuZSM-5 zeolite and a Fe-mordenite, respectively, has been studied using tracer techniques. The results demonstrate the high mobility of the lattice oxygen ions in self-diffusion. They afford a possible explanation for the problem of how two extralattice oxygens located at positions remote from each other may combine to form the O₂ molecules which are spontaneously desorbed in these redox reactions. They show that a portion of the lattice oxygen mixes into the O₂ released on decomposition. The data also show that N¹⁸O and N₂ ¹⁸O undergo exchange with the catalyst oxygen under reaction conditions.On leave from Central Research Institute for Chemistry, Hungarian Academy of Sciences, H-1525 Budapest, Hungary.     

Low-Temperature Catalytic Decomposition of N2O

Theoretical Foundations of Chemical Engineering - A series of oxide catalysts modified with potassium cations, 1–5% K2О/CoFe2O4, with a spinel structure were obtained via...     

低介电氧氮化硅陶瓷的研制

以氮化硅为主体,外加二氧化硅,研制低密度、高强、低介电的氧氮化硅陶瓷材料。通过分析材料烧结体的XRD物相图、材料的各项性能、材料的显微结构,得出二氧化硅含量对材料性能的影响规律,从而确定了材料最佳配方。     

Recovery of groundwater N2O at the soil surface and its contribution to total N2O emissions

Production and accumulation of the major greenhouse gas nitrous oxide (N₂O) in surface groundwater might contribute to N₂O emissions to the atmosphere. We report on a ¹⁵N tracer study conducted in the Fuhrberger Feld aquifer in northern Germany. A K¹⁵NO₃ tracer solution (60 atom%) was applied to the surface groundwater on an 8 m² measuring plot using 45 injection points in order to stimulate production of ¹⁵N₂O by denitrification and to detect its contribution to emissions at the soil surface. Samples from the surface groundwater, from the unsaturated zone and at the soil surface were collected in regular intervals over a 72-days period. Total N₂O fluxes at the soil surface were low and in a range between ?7.6 and 29.1 μg N₂O-N m^?2 h^?1. ¹⁵N enrichment of N₂O decreased considerably upwards in the profile. In the surface groundwater, we found a ¹⁵N enrichment of N₂O between 13 and 42 atom%. In contrast, ¹⁵N enrichment of N₂O in flux chambers at the soil surface was very low, but a detectable ¹⁵N enrichment was found at all sampling events. Fluxes of groundwater-derived ¹⁵N-N₂O were very low and ranged between 0.0002 and 0.0018 kg N₂O-N ha^?1 year^?1, indicating that indirect N₂O emissions from the surface groundwater of the Fuhrberger Feld aquifer occurring via upward diffusion are hardly significant. Due to these observations we concluded that N₂O dynamics at the soil–atmosphere interface is predominantly governed by topsoil parameters. However, highest ¹⁵N enrichments of N₂O throughout the profile were obtained in the course of a rapid drawdown of the groundwater table. We assume that such fluctuations may enhance diffusive N₂O fluxes from the surface groundwater to the atmosphere for a short time.     

Fertilizers, agronomy and N2O

N₂O is emitted from agricultural soils due to microbial transformation of N from fertilizers, manures and soil N reserves. N₂O also derives from N lost from agriculture to other ecosystems: as NH₃ or through NO ₃ ^- leaching. Increased efficiency in crop N uptake and reduction of N losses should in principle diminish the amount of N₂O from agricultural sources. Precision in crop nutrient management is developing rapidly and should increase this efficiency. It should be possible to design guidelines on good agricultural practices for low N₂O emissions in special situations, e.g. irrigated agriculture, and for special operations, e.g. deep placement of fertilizers and manures. However, current information is insufficient for such guidelines. Slow-release fertilizers and fertilizers with inhibitors of soil enzymatic processes show promise as products which give reduced N₂O emissions, but they are expensive and have had little market penetration. Benefits and possible problems with their use needs further clarification.     

Subsoils: chemo-and biological denitrification, N2O and N2 emissions

Agricultural practices, soil characteristics and meteorological conditions are responsible for eventual nitrate accumulation in the subsoil. There is a lot of evidence that denitrification occurs in the subsoil and rates up to 60–70 kg ha^-1 yr^-1 might be possible. It has also been shown that in the presence of Fe²⁺ (formed through weathering of minerals) and an alkaline pH, nitrate can be chemically reduced. Another possible pathway of disappearance is through the formation of nitrite, which is unstable in acid conditions. With regard to the emission of N₂O and N₂, it can be stated that all conditions whereby the denitrification process becomes marginal are favourable for N₂O formation rather than for N₂. Because of its high solubility, however, an important amount of N₂O might be transported with drainage water.     

Solubility of N2O and CO2 in n-Dodecane

The solubility of CO₂ and N₂O in a physical solvent, n-dodecane [C.A. Registry N° 124–18–5], has been measured at 40, 80 and 120°C at pressures up to 9.6 MPa. The experimental results were correlated by the Peng-Robinson (1976) equation of state, and the interaction parameters, the Henry's constants and the N₂O analogy parameters were obtained.     

Decomposition of N2O on Perovskite-Related Oxides

Mixed metal oxides crystalizing in a perovskite-related structure have long been of interest to solid state chemists and physicists because of their technologically important physical properties. The ready availability of a family of isomorphic solids with controllable physical properties makes these oxides suitable for basic research in catalysis. These mixed metal oxides are more advantageous and are better catalytic materials than simple oxides because: (i) the crystal structure can accomodate various metal ions and can stabilize unusual and mixed valence states of active metal ion; (ii) appropriate formulation of these oxides leads to easy tailoring of many desirable properties such as valence state of transition metal ion, distance between active sites, binding energy, diffusion of oxygen in the lattice, magnetic and conducting properties of the solid; (iii) the catalytic activity can be correlated to solid state properties since many of their solid state properties are thoroughly understood; (iv) the surface of these oxides can be regenerated by suitable activation procedure.     

Decomposition of N2O on Perovskite-Related Oxides

Mixed metal oxides crystalizing in a perovskite-related structure have long been of interest to solid state chemists and physicists because of their technologically important physical properties. The ready availability of a family of isomorphic solids with controllable physical properties makes these oxides suitable for basic research in catalysis. These mixed metal oxides are more advantageous and are better catalytic materials than simple oxides because: (i) the crystal structure can accomodate various metal ions and can stabilize unusual and mixed valence states of active metal ion; (ii) appropriate formulation of these oxides leads to easy tailoring of many desirable properties such as valence state of transition metal ion, distance between active sites, binding energy, diffusion of oxygen in the lattice, magnetic and conducting properties of the solid; (iii) the catalytic activity can be correlated to solid state properties since many of their solid state properties are thoroughly understood; (iv) the surface of these oxides can be regenerated by suitable activation procedure.     

Preparation and Characterization of Copper Catalysts Supported on Mesoporous Al2O3 Nanofibers for N2O Reduction to N2

The gas-phase hydrogenation of benzene to cyclohexane over Ce_{1 - x} Pt _x O_{2 -} (x = 0.01, 0.02) catalyst was investigated in the temperature range 80-200 °C. A 42% conversion of benzene to cyclohexane with 100% specificity was observed at 100 °C over Ce_0.98Pt_0.02O_{2 -} with a catalyst residence time of 1.22 × 10⁴ g s/mol of benzene. The activity of the catalyst was compared with those of Pt metal, combustion-synthesized Pt/-Al₂O₃ and Pt/-Al₂O₃. The turnover frequency value of Ce_0.98Pt_0.02O_{2 -} is 0.292, which is an order of magnitude higher than those of the other Pt catalysts investigated. The kinetics of reaction and the deactivation behavior of the catalyst were studied and a regeneration methodology was suggested. The deactivation kinetics and structural evidence from XRD, XPS, TGA and H₂ uptake studies suggest that the oxidized Pt in Ce_0.98Pt_0.02O_{2 -} is responsible for the high catalytic activity towards benzene hydrogenation.     

Effects of N management on N2O and CH4 fluxes and15N

Forage production in irrigated mountain meadows plays a vital role in the livestock industry in Colorado and Wyoming. Mountain meadows are areas of intensive fertilization and irrigation which may impact regional CH₄ and N₂O fluxes. Nitrogen fertilization typically increases yields, but N-use efficiency is generally low. Neither the amount of fertilizer-N recovered by the forage nor the effect on N₂O and CH₄ emissions were known. These trace gases are long-lived in the atmosphere and contribute to global warming potential and stratospheric ozone depletion. From 1991 through 1993 studies were conducted to determine the effect of N source, and timing of N-fertilization on forage yield, N-uptake, and trace gas fluxes at the CSU Beef Improvement Center near Saratoga, Wyoming. Plots were fertilized with 168 kg N ha^-1. Microplots labeled with¹⁵N-fertilizer were established to trace the fate of the added N. Weekly fluxes of N₂O and CH₄ were measured during the snow-free periods of the year. Although CH₄ was consumed when soils were drying, flood irrigation converted the meadow into a net source of CH₄. Nitrogen fertilization did not affect CH₄ flux but increased N₂O emissions. About 5% of the applied N was lost as N₂O from spring applied NH₄NO₃, far greater than the amount lost as N₂O from urea or fall applied NH₄NO₃. Fertilizer N additions increased forage biomass to a maximum of 14.6 Mg ha^-1 with spring applied NH₄NO₃. Plant uptake of N-fertilizer was greater with spring applications (42%), than with fall applications (22%).     

Catalytic decomposition of propellant N2O Over Ir/Al2O3 catalyst

N₂O, as a green propellant alternative to N₂H₄, shows potential application in satellite propulsion system. The state of Ir species and the reaction behaviors on Ir/Al₂O₃ in the oxidative environment during N₂O decomposition were identified here. Two types of Ir sites existed in this catalyst and affected the process of N₂O decomposition. The strong Ir sites facilitated the dissociative adsorption of N₂O to form N₂ and adsorbed O atoms with adsorption heat of as high as 281 kJ/mol, which promoted the desorption of adsorbed O atoms and favored the self‐sustaining decomposition of N₂O by raising the catalyst bed temperature. The other Ir sites interacted weakly with O atoms but facilitated their combination to form O₂. The Ir/Al₂O₃ catalyst then exhibited an excellent performance in initiating the decomposition of N₂O at low temperature of 200°C and good stability in 0.1 N microthruster for orbit adjustment and attitude control of satellite. © 2016 American Institute of Chemical Engineers AIChE J, 62: 3973–3981, 2016     

N2O emission from cropland in China

Based on the regionalization of uplands and paddy fields in China, the crop intensity in each region and the available field measurements, N₂O emission from cropland in China in 1995 was estimated to be 398 Gg N, in which, 310 Gg N was from uplands, accounting for 78% of the total. 88 Gg N–N₂O was emitted from paddy fields with 35 Gg N emitted during the rice growing season and 53 Gg N emitted during upland crop season. N₂O emission from upland and from paddy field during upland land crop season accounted for 91% of the total emission.     

Eu~(2+)掺杂SrSi_2O_2N_2和Sr_(0.37)Ba_(0.60)Si_2O_2N_2荧光粉的发光性能及应用

采用高温固相法合成Sr_(0.97)Eu_(0.03)Si_2O_2N_2和Sr_(0.37)Ba_(0.60)Eu_(0.03)Si_2O_2N_2荧光粉,通过X射线衍射、激发光谱、发射光谱及转换后LED器件的性能等研究了荧光粉的结构、发光性能和稳定性。结果表明:在稀土Eu2+掺杂的Sr Si2O2N2荧光粉中,当部分Sr2+被Ba2+取代后,形成三斜晶系的Sr_(0.37)Ba_(0.60)Eu_(0.03)Si_2O_2N_2荧光粉,激发和发射光谱红移,在近紫外-蓝光区具有更高的激发效率。将2种荧光粉与Ga(N)In芯片封装,Sr0.37Ba0.60Eu0.03Si2O2N2荧光粉转换的白光LED器件,在光效、显色指数和光效维持特性方面均高于Sr_(0.97)Eu_(0.03)Si_2O_2N_2转换的LED器件。     

Conversions of fuel-N,volatile-N,and char-N to NO and N2O during combustion of a single coal particle in O2/N2 and O2/H2O at low temperature

Oxy-steam combustion is a promising next-generation combustion technology. Conversions of fuel-N, volatile-N, and char-N to NO and N₂O during combustion of a single coal particle in O₂/N₂ and O₂/H₂O were studied in a tube reactor at low temperature. In O₂/N₂, NO reaches the maximum value in the devolatilization stage and N₂O reaches the maximum value in the char combustion stage. In O₂/H₂O, both NO and N₂O reach the maximum values in the char combustion stage. The total conversion ratios of fuel-N to NO and N₂O in O₂/N₂ are obviously higher than those in O₂/H₂O, due to the reduction of H₂O on NO and N₂O. Temperature changes the trade-off between NO and N₂O. In O₂/N₂ and O₂/H₂O, the conversion ratios of fuel-N, volatile-N, and char-N to NO increase with increasing temperature, and those to N₂O show the opposite trends. The conversion ratios of fuel-N, volatile-N, and char-N to NO reach the maximum values at < O₂ > = 30 vol% in O₂/N₂. In O₂/H₂O, the conversion ratios of fuel-N and char-N to NO reach the maximum values at < O₂ > = 30 vol%, and the conversion ratio of volatile-N to NO shows a slightly increasing trend with increasing oxygen concentration. The conversion ratios of fuel-N, volatile-N, and char-N to N₂O decrease with increasing oxygen concentration in both atmospheres. A higher coal rank has higher conversion ratios of fuel-N to NO and N₂O. Anthracite coal exhibits the highest conversion ratios of fuel-N, volatile-N, and char-N to NO and N₂O in both atmospheres. This work is to develop efficient ways to understand and control NO and N₂O emissions for a clean and sustainable atmosphere.     

Kinetics of N2O decomposition on polycrystalline platinum

The kinetics of N₂O decomposition on polycrystalline Pt is studied over a wide range of surface temperatures (400 < T < 1200 °C) and pressures (0.01 < P_N2O < 0.50 Torr) in a steady-state flow system with conversions less than 6% so that differential rates are obtained. It is found that a single Langmuir-Hinshelwood (LH) rate expression correlates all rate data within ± 10% at all temperatures and pressures to give a reaction activation energy of 34.9 kcal/mole and a heat of adsorption of N₂O of 21.3 kcal/mole. A simple reaction mechanism which can give this rate expression is also proposed.     

Influence of electrolytes on the absorption of nitrogen oxide components N2O4 and N2O3 in aqueous absorbents

The influence of electrolytes, which are dissolved in the aqueous absorbent and do not react with nitrogen oxides, on the absorption kinetics of both these components was investigated experimentally. In addition to demineralized water, various salt solutions of different concentrations as well as sodium hydroxide solution were used as absorbents. The term H \documentclass{article}\pagestyle{empty}\begin{document}$ H\sqrt {k_1 D} $\end{document} for N₂O₄ and N₂O₃, which is important for the design of industrial absorbers, was determined as a function of composition and concentration of the absorbents. In the case of N₂O₄, the chosen measuring and evaluation methods permitted a separate determination of the rate constant k of the pseudo first order reaction and of the solubility H. The diffusion coefficient D of the gas in the absorbent can be obtained only by calculation. Experimental results showed that \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document} decreases with increasing ionic strength I, however, without a clear indication of any ion-specific effects. This decrease does not appear to be caused simply by a reduction in solubility (salting out effect), or in diffusion coefficient, but at least, to the same extent, through a decrease of the rate constant k with increasing electrolyte content in the absorbent. The measurements permitted the determination of the gas-based salting out parameter for N₂O₄. The investigations on the absorption of N₂O₃ in water and in an Na₂SO₄ solution showed no experimentally detectable influence of dissolved salts on \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document}. The numerical value of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 3} } $\end{document} is six times that of \documentclass{article}\pagestyle{empty}\begin{document}$(H\sqrt {k_1 D} )\,_{{\rm N}_{\rm 2} {\rm O}_{\rm 4} } $\end{document}.