NO emission characteristics in counterflow diffusion flame of blended fuel of H2/CO2/Ar

Flame structure and NO emission characteristics in counterflow diffusion flame of blended fuel of H₂/CO₂/Ar have been numerically simulated with detailed chemistry. The combination of H₂, CO₂ and Ar as fuel is selected to clearly display the contribution of hydrocarbon products to flame structure and NO emission characteristics due to the breakdown of CO₂. A radiative heat loss term is involved to correctly describe the flame dynamics especially at low strain rates. The detailed chemistry adopts the reaction mechanism of GRI 2.11, which consists of 49 species and 279 elementary reactions. All mechanisms including thermal, NO₂, N₂O and Fenimore are taken into account to separately evaluate the effects of CO₂ addition on NO emission characteristics. The increase of added CO₂ quantity causes flame temperature to fall since at high strain rates a diluent effect is prevailing and at low strain rates the breakdown of CO₂ produces relatively populous hydrocarbon products and thus the existence of hydrocarbon products inhibits chain branching. It is also found that the contribution of NO production by N₂O and NO₂ mechanisms are negligible and that thermal mechanism is concentrated on only the reaction zone. As strain rate and CO₂ quantity increase, NO production is remarkably augmented. Copyright © 2002 John Wiley & Sons, Ltd.     

低工作温度的氧化钨气敏材料

本文报道了一种可以在１００℃左右工作的氢化钨气敏材料，它对氢气和一氧化氮有很高的灵敏度和良好的选择性，并可对空气中的一氧化氮进行探测     

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.     

Differences in the structure of copper active sites for decomposition and selective reduction of nitric oxide with hydrocarbons and ammonia

Cu ion co-ordination-location in zeolites of MFI, erionite, mordenite matrices has been determined and the activity of the individual Cu sites compared for NO decomposition and its selective reduction by hydrocarbons or ammonia. It appears that Cu ions in the vicinity of one framework Al (site II), able to form stable Cu⁺-dinitrosyl complexes, and abundant in MFI structure, are responsible for high activity in NO decomposition. The Cu ions neighbouring two framework Al atoms (site I), and forming mostly mononitrosyl complexes, which dominate in erionite structure, provide a high activity in selective reduction of NO.     

Enhancement by SO2 of initial activity for selective catalytic reduction of NO with CH3OH over \gamma-alumina

The effect of SO₂ on catalytic activity for NO reduction to N₂ by methanol in excess oxygen over $\gamma$ -alumina has been investigated. SCR activity increased initially upon exposure of a fresh $\gamma$ -alumina catalyst to SO₂ which is attributed to formation of Brønsted acid sites. Longer exposure to SO₂ leads to a decline in catalytic activity to a lower steady-state NO_x reduction activity which is independent of the SO₂ content in the feed gas.     

Promotion of the NO + O2 Reaction by Ba–Y, FAU Zeolite at 25 °C

A remarkably high inferred initial rate of NO oxidation by O₂ has been observed over Ba–Y, FAU zeolite at 25 °C in simple flow-reactor experiments. The rate of reaction at steady state was found to be lower, but still an order of magnitude greater than over alumina-supported Pt, also at 25 °C.     

Catalytic Conversion of NO and C3H6 in Exhaust Gases Over Silver Catalysts Under Stoichiometric or Excess Oxygen

The role of Ag in simultaneously catalyzing NO reduction and C₃H₆ oxidation was shown to be strongly dependent on the redox properties of its local environment. Under an atmosphere of 1,000 ppm NO, 3,000 ppm C₃H₆, and 1% O₂ and a GHSV of 30,000 h⁻¹, a perovskite La_0.88Ag_0.12FeO₃ prepared by reactive grinding is active giving a complete NO conversion and 92% C₃H₆ conversion at 500 °C. These values are much higher than the NO conversion of 55% and C₃H₆ conversion of 45% obtained over a 3 wt.% Ag/Al₂O₃ catalyst under the same conditions. Under an excess of oxygen (10% O₂) a good SCR performance with a plateau of N₂ yield above 97% over a wide temperature window of 350–500 °C along with C₃H₆ conversion of 90% at 500 °C was observed over Ag/Al₂O₃, while minor N₂ yields (∼10% at 250–350 °C) and high C₃H₆ conversions (reaching ∼100% at 450 °C) were obtained over La_0.88Ag_0.12FeO₃. Abundant molecular oxygen is desorbed from Ag substituted perovskite after 10% O₂ adsorption as verified by O₂- temperature programmed desorption (TPD). This reflects the strongly oxidative properties of La_0.88Ag_0.12FeO₃, which lead to a satisfactory NO reduction at 1% O₂ due to the ease of nitrate formation but to a significant C₃H₆ combustion above that value. The formation of nitrate species over the less oxidizing Ag/Al₂O₃ was accelerated under an excess of oxygen resulting in an excellent lean NO reduction behavior. The redox properties of silver catalysts could be adjusted via mixing perovskite with alumina for an optimal elimination of both NO and C₃H₆ over the whole range of oxygen concentration between 0 to 10%.     

Electrochemical promotion of Rh catalyst in gas-phase reduction of NO by propylene

The concept of non-faradaic electrochemical modification of catalytic activity (NEMCA) has been applied for the in situ control of catalytic activity of a rhodium film deposited on YSZ (yttria stabilized zirconia) solid electrolyte towards reduction of 1000 ppm NO by 1000 ppm C₃H₆ in presence of excess (5000 ppm) O₂ at 300 °C. A temporary heating at this feed composition results in a long-lasting deactivation of the catalyst under open circuit conditions due to partial oxidation of the rhodium surface. Positive current application (5 A) over both the active and the deactivated catalysts gives rise to an enhancement of N₂ and CO₂ production, the latter exceeding several hundred times the faradaic rate. While active rhodium exhibits a reversible behaviour, electrochemical promotion on the deactivated catalyst is composed of a reversible and an irreversible part. The reversible promotion results from the steady-state accumulation of current-generated active species at the gas exposed catalyst surface whereas the irreversible effect is due to the progressive reduction of the catalyst resulting in an increased recovery rate of lost catalytic activity. The results are encouraging with respect to application of rhodium for the catalytic removal of NO from auto-exhaust gases under lean-burn conditions.     

Characterization and Catalytic Properties of Combustion Synthesized Au/CeO2 Catalyst

Ceria-supported Au catalyst has been synthesized by the solution combustion method for the first time and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM) and X-ray photoelectron spectroscopy (XPS). Au is dispersed as Au⁰ as well as Au³⁺ states on CeO₂ surface of 20-30 nm crystallites. On heating the as-prepared 1% Au/CeO₂ in air, the concentration of Au³⁺ ions on CeO₂ increases at the expense of Au⁰. Catalytic activities for CO and hydrocarbon oxidation and NO reduction over the as-prepared and the heat-treated 1% Au/CeO₂ have been carried out using a temperature-programmed reaction technique in a packed bed tubular reactor. The results are compared with nano-sized Au metal particles dispersed on -Al₂O₂ substrate prepared by the same method. All the reactions over heat-treated Au/CeO₂ occur at lower temperature in comparison with the as-prepared Au/CeO₂ and Au/Al₂O₂. The rate of NO + CO reaction over as-prepared and heat-treated 1% Au/CeO₂ are 28.3 and 54.0 mol g^-1 s^-1 at 250 and 300 °C respectively. Activation energy (E _a) values are 106 and 90 kJ mol^-1 for CO + O₂ reaction respectively over as-prepared and heat-treated 1% Au/CeO₂ respectively.     

Low temperature SCR of NO with NH3 over carbon nanotubes supported vanadium oxides

A novel multiwalled carbon nanotube (CNTs) supported vanadium catalyst was prepared. The structure of catalyst prepared was characterized by TEM, BET, FTIR, XRD and temperature-programmed desorption (TPD) methods. The results indicated that vanadium particles were highly dispersed on the wall of carbon nanotubes. The V₂O₅/CNT catalysts showed good activities in the SCR of NO with a temperature range of 373–523 K. The Lewis acid sites on the surface of V₂O₅/CNT are the active sites for the selective catalytic reduction (SCR) of NO with NH₃ at low temperatures. It was suggested that the reaction path might involve the adsorbed NH₃ species reacted with NO from gaseous phase and as well as the adsorbed NO₂ species. The diameter of CNTs showed positive effect on the activities of the catalysts. Under the reaction conditions of 463 K, 0.1 Mpa, NH₃/NO = 1, GHSV = 35,000 h⁻¹, and V₂O₅ loading of 2.35 wt%, the outer diameter of CNTs of 60–100 nm, the NO conversion was 92%.