DC corona discharge influence on chemical composition in mixtures of natural gas with air and its combustion exhaust with air

Experiments in dc supplied corona discharge in natural gas + air mixture and in combustion exhaust of natural gas + air mixture were realized. The influence of discharge on CO, CO₂, NO _x and other minority components was studied using IR absorption spectrometry. Production of NCO radicals in gas and consequent formation of NCO containing surface layers on a plate electrode was detected. In natural gas + air mixture after about 1 min oxygen poor combustion exhaust was produced due to slow combustion by corona discharge. Occurrence of various pulses in discharge current was typical.     

Pulsed cavity ring-down spectroscopy of NO and NO2 in the exhaust of a diesel engine

The application of pulsed cavity ring-down spectroscopy has been demonstrated for the in situ quantitative determination of NO and NO₂ in the exhaust of a diesel engine. NO absorption has been monitored at the transition from the Χ²Π ground state to the A²Σ⁺ state at 226 nm. For NO₂, absorption bands in the spectral region from 438 nm to 450 nm were used. At the selected engine conditions, concentrations of 212±22 ppm and 29±4 ppm have been measured for NO and NO₂, respectively, in good agreement with separate chemical exhaust gas analysis. The method is sensitive enough to meet the European Euro V standard directive on NO_x emissions. This communication discusses the relatively simple setup needed for this type of measurement, the problems encountered, as well as the prospects for single-stroke, simultaneous measurements of both NO and NO₂ at the sub-ppm level. Received: 30 November 2001 / Revised version: 18 February 2002 / Published online: 14 March 2002     

Fundamental investigation of NOx formation during oxy-fuel combustion of pulverized coal

NO_x formation was measured during combustion of pulverized coals and pulverized coal char in N₂ and CO₂ environments under isothermal and nearly constant oxygen conditions (i.e. using dilute coal loading). Three different oxygen concentrations (12% O₂, 24% O₂, and 36% O₂) and two representative US coals were investigated, at a gas temperature of 1050 °C. To investigate the importance of NO reburn reactions, experiments were also performed with an elevated concentration (550 ppm) of NO in the gases into which the coal was introduced. For low levels of background NO, the fractional fuel-nitrogen conversion to NO_x increases dramatically with increasing bath gas oxygen content, for both N₂ and CO₂ environments, though the fuel conversion is generally lower in CO₂ environments. Char N conversion is lower than volatile N conversion, especially for elevated O₂ concentrations. These results highlight the importance of the volatile flame and char combustion temperatures on NO_x formation. For the high background NO_x condition, net NO_x production is only observed in the 36% O₂ environment. Under these dilute loading conditions, NO reburn is found to be between 20% and 40%, depending on the type of coal, the use of N₂ or CO₂ diluent, the bulk O₂ concentration, and whether or not one considers reburn of volatile-NO_x. This dataset provides a unique opportunity to understand and differentiate the different sources and sinks of NO_x under oxy-fuel combustion conditions.     

Incoherent broad-band cavity-enhanced absorption spectroscopy for simultaneous trace measurements of NO2 and NO3 with a LED source

In the past decade, due to a growing awareness of the importance of air quality and air pollution control, many diagnostic tools and techniques have been developed to detect and quantify the concentration of pollutants such as NO _x , SO _x , CO, and CO₂. We present here an Incoherent Broad-Band Cavity-Enhanced Spectroscopy (IBB-CEAS) set-up which uses a LED emitting around 625 nm for the simultaneous detection of NO₂ and NO₃. The LED light transmitted through a high-finesse optical cavity filled with a gas sample is detected by a low resolution spectrometer. After calibration of the spectrometer with a NO₂ reference sample, a linear multicomponent fit analysis of the absorption spectra allows for simultaneous measurements of NO₂ and NO₃ concentrations in a flow of ambient air. The optimal averaging time is found to be on the order of 400 s and appears to be limited by the drift of the spectrometer. At this averaging time the smallest detectable absorption is 2×10⁻¹⁰ cm⁻¹, which corresponds to detection limits of 600 pptv for NO₂ and 2 pptv for NO₃. This compact and low cost instrument is a promising diagnostic tool for air quality control in urban environments.     

Nanoparticle removal and exhaust gas cleaning using gas-liquid interfacial nonthermal plasma

We investigate the removal of air pollutants containing nanoparticles with a wet-type plasma reactor that generates a gas-liquid interfacial nonthermal plasma. To evaluate the performance of this reactor, we prepare a simulated exhaust gas using polystyrene latex particles, as well as gas cylinders of synthesized air and mixed gas of nitric oxide (NO) and sulfur dioxide (SO₂). We achieve a partial collection efficiency of more than 99% for nanoparticles. Moreover, we obtain removal efficiencies exceeding 99% and 81% for SO₂ and NO_x, respectively. We confirm that the proposed reactor is useful for the simultaneous removal of nanoparticles, NO_x, and SO_x.     

In situ sensor for cycle-resolved measurement of temperature and mole fractions in IC engine exhaust gases

We present a multi-species mole fraction and temperature sensor for in situ exhaust gas diagnostic of internal combustion (IC) engines. The sensor is based on Tunable Diode Laser Absorption Spectroscopy (TDLAS) and incorporates four optical channels - two miniature White cells and two double-traversal cells - with base lengths of 6?cm. It has been demonstrated at a hot air test stand and in the exhaust manifold of a single-cylinder research engine, with measured temperatures of up to 1000?K. Stable operation was achieved with absorption lengths of up to 192?cm (test stand) and 97?cm (engine). Employing time-division multiplexed detection, six species were measured simultaneously in the engine exhaust, at wavelengths ranging from 1.4?µm to 5.2 µm: water vapor (H₂O), carbon dioxide (CO₂), carbon monoxide (CO), methane (CH₄), nitrogen dioxide (NO₂) and nitric oxide (NO). The effective measurement rate was as high as 1?kHz, and cycle-to-cycle variations were clearly detected. We show the correlation of the air-fuel equivalence ratio with the spectroscopically measured mole fraction of each species. At a cycle-resolved rate, detection limits for the legally regulated species NO and NO₂ were 1?ppm and 4?ppm, respectively. The sensor is intended to help improve the understanding of IC engine emission behavior during fast transients.     

Application of a difference-frequency-mixing based diode-laser sensor for carbon monoxide detection in the 4.4–4.8 μm spectral region

An all-solid-state continuous-wave (cw) laser system for mid-infrared absorption measurements of the carbon monoxide (CO) molecule has been developed and demonstrated. The single-mode, tunable output of an external-cavity diode laser (ECDL) is difference-frequency mixed with the output of a 550-mW diode-pumped cw Nd:YAG laser in a periodically poled lithium niobate (PPLN) crystal to generate tunable cw radiation in the mid-infrared region. The wavelength of the 860-nm ECDL can be coarse tuned from 860.782 to 872.826 nm, allowing the sensor to be operated in the spectral region 4.4–4.8 μm. CO-concentration measurements were performed in CO/CO₂/N₂ mixtures in a room-temperature gas cell, in the exhaust stream of a well-stirred reactor (WSR) at Wright-Patterson Air Force Base and in a near-adiabatic hydrogen/air CO₂-doped flame. The noise equivalent detection limits were estimated to be 1.1 and 2.5 ppm per meter for the gas cell and flame experiments, respectively. These limits were computed for combustion gas at 1000 K and atmospheric pressure assuming a signal-to-noise ratio of 1. The sensor uncertainty was estimated to be 2% for the gas-cell measurements and 10% for the flame measurements based on the repeatability of the peak absorption. PACS 07.07.Df; 42.62.Fi; 42.65.Ky; 42.72.Ai     

High-temperature NO or NO2 sensor using stabilized zirconia and tungsten oxide electrode

Stabilized zirconia-based electrochemical devices for which the sensing electrode was provided with a single-metal oxide were tested for NO and NO₂ sensing properties at high temperature. Among the many single-metal oxides examined, WO₃ was found to give the best sensing properties to NO and NO₂ at 500–700°C. The EMF response of the WO₃-attached device was linear to the logarithm of NO or NO₂ concentration. The response and recovery kinetics were speedy. The device gave very small cross-sensitivities to H₂, CO, CH₄, CO₂ and water vapor. The sensing mechanism involving mixed-potential was confirmed from the measurements of polarization curves.     

NOx generation in laser-produced plasma in air as a function of dissipated energy

An experimental study on the production of NO_x as a function of dissipated energy in laser-produced plasma in air is presented. A plasma was produced by focusing a (60–180) mJ, 5 ns, 532 nm pulse from a Q-switched Nd:YAG laser. The results show that for laser energy in the range of 13–99 mJ the laser plasma generates 6.7×10¹⁶ NO_x molecules per joule and 4.6×10¹⁶ NO molecules per joule. An order of magnitude estimate of the NO and NO_x production per unit volume of heated gas based on a simple model show that the NO_x and NO production efficiency in air are about 3×10²² and 2×10²² molecules J⁻¹ m⁻³.     

Surface science studies of selective catalytic reduction of NO: Progress in the last ten years

Selective catalytic reduction (SCR) of NO_x is one of the important strategies in regulating NO_x emissions. In the past several decades, the reactions of NO_x (mainly NO) with H₂, CO, NH₃ and hydrocarbons have been extensively investigated under ambient conditions and have been summarized in numerous reviews. Nonetheless, many questions appear to be difficult to answer under ambient conditions, e.g., the pathways through which the reactions proceed. The introduction and development of modern surface science technology has played an indispensable role and is widely employed in the studies of the SCR of NO_x, greatly helping to elucidate the mechanisms of the reactions with CO, H₂, and NH₃. However, so far, there are few review papers systematically summarizing the progress of such studies.Recently, systematic surface science studies have been conducted on the mechanisms of SCR of NO with organic molecules including ethylene, benzene, and ethanol, which are much more complicated than those with H₂, CO and NH₃ and have drawn much less attention before. It is confirmed that these reactions can be reliably and most importantly, reproducibly probed by surface science technology, but a great deal of work remains to be done.Since Delmon et al. have provided a very thorough review of the researches on catalytic removal of NO (reactions with H₂, CO and NH₃) up to 1998, in which the reactions conducted both under ambient and UHV conditions were included, this review mainly concentrates on the progress made since 1998.     

Real-time measurement of nitrogen dioxide in vehicle exhaust gas by mid-infrared cavity ring-down spectroscopy

The application of pulsed cavity ring-down spectroscopy (CRDS) was demonstrated for the measurement of nitrogen dioxide (NO₂) in automotive exhaust gas. The transition of the ν ₃ vibrational band assigned to the antisymmetric stretching mode of NO₂ was probed with a thermoelectrically cooled, pulsed, mid-infrared, distributed feedback, quantum cascade laser (QCL) at 6.13 μm. The measurement of NO₂ in the exhaust gas from two diesel vehicles equipped with different aftertreatment devices was demonstrated using a CRDS-based NO₂ sensor, which employs a HEPA filter and a membrane gas dryer to remove interference from water as well as particulates in the exhaust gas. Stable and sensitive measurement of NO₂ in the exhaust gas was achieved for more than 30 minutes with a time resolution of 1 s.     

Absorption of CO laser radiation by NO

Absorption of CO i.r. laser radiation by NO has been studied over the temperature range 300°–4000°K using a grating-tunable CO laser in conjunction with a room-temperature absorption cell and a shock tube. The CO laser line with strongest absorption at elevated temperatures was determined to be the V = 7 → 6, J = 12 → 13 line at 1935.4817 cm^-1, which is nearly coincident with the ²Π_{$\text{3}\text{2}$}V = 0 → 1, J = 37/2 → 39/2 transition in NO. The absorption cell measurements (300°K) were used to infer the position of the NO absorption line (a Λ-doublet at 1935.492 and 1935.497 cm^-1) as well as collision-broadening parameters in pure NO and NO dilute in foreign gases: 2γ° (collision-broadened full width at half maximum in cm^-1 atm^-1 at 300°K) = 0.110, NO-NO; 0.072, NO in Ar; 0.069, NO in Kr; 0.109, NO in N₂. Calculations of the NO absorption coefficient at 1935.4817 cm^-1 are presented for a range of conditions applicable to current studies in combustion and NO_x kinetics. Shock tube measurements (630°–4000°K) supporting these calculations are also reported.     

Simulation of Pollutant Emissions in a Small-Size GTE Based on the Reactor Network Model

The results of simulation of the NO_x and CO formation in a small-sized gas turbine engine are presented. A comparison of the results of CFD calculations with experimental data showed that calculations in standard three-dimensional formulation in combination with partitioning into a network of reactors can be used to simulate NO_x and CO formation. When using the JetSurf 2.0 chemical reaction mechanism, satisfactory agreement between calculated and experimental data is achieved with a number of elementary reactors above several hundreds.     

Synthesis of nanostructured lean-NO x catalysts by direct laser deposition of monometallic Pt-, Rh- and bimetallic PtRh-nanoparticles on SiO2 support

Monometallic Pt and Rh and bimetallic PtRh catalysts with a highly dispersed noble metal weight loading of ca. 1 wt% were produced via the direct deposition of nanoparticles on different SiO₂ supports by means of pulsed ultra-violet (248 nm) excimer laser ablation of Pt, Rh bulk metal and PtRh alloy targets. Backscattered electron microscopy (BSE), energy dispersive X-ray spectroscopy (EDX), and transmission electron microscopy (TEM) were employed to characterize the deposited nanoparticles, which were found to exhibit narrow size distribution centred around 2.5 nm. The catalytic activities for lean NO _x reduction of the monometallic and bimetallic catalyst samples were investigated in a flow reactor setup in the temperature range 100–400°C using a test gas mixture representative of oxygen rich diesel engine exhaust gas. For comparison a Rh/SiO₂ reference catalyst prepared by a conventional impregnation method was also tested. Further experiments were performed in which PtRh nanoparticles were deposited on a Rh/SiO₂ reference catalyst sample to study the possibility for controlled modification of its activity. The catalytic activity measurements revealed that among the samples solely prepared by laser deposition the PtRh–SiO₂ nanoparticle catalyst showed the highest activity for NO _x reduction at low temperatures 100–300°C. In addition, it could be demonstrated that the initially low NO _x reduction activity and the N₂ selectivity of the Rh/SiO₂ reference catalyst sample for temperatures below 250°C can be enhanced by post laser deposition of PtRh nanoparticles.     

Influence of temperature and humidity on NO x removal by corona discharge

The object of this experimental investigation was the influence of temperature and humidity on the efficiency of removal of NO _x by a pulsed corona discharge from a mixture N₂ : O₂ : CO₂ : H₂O : NO simulating a combustion flue gas. The pulsed corona discharge was generated in a wire-to-cylinder reactor. It was found that removal of NO _x was most efficient when H₂O concentration corresponded with the saturated vapour pressure. In the case of the operating gas containing constant H₂O concentration removal of NO _x decreased with increasing temperature of the operating gas. Dedicated to Prof. Jan Janča on the occasion of his 60^th birthday. This work is devoted to the 60^th birthday of Professor Jan Janca, our good colleague, merited teacher, researcher and famous physicist, discussion with whom stimulated this and other our work during years.     

Spectroscopic detection of aircraft wake gases

Using the technique of limiting information-metric scales, the potential of laser IR absorption spectroscopy for detecting small gas components of aircraft wake was quantitatively analyzed. Formulas for minimum distinguishable and minimum detectable gas concentrations were derived. Calculation was carried out for SO₂, NO, and NO₂ under typical conditions near the Boeing 707 aircraft engine nozzle at altitude H = 12.2 km. Alternative IR laser spectroscopy methods for detecting various gas components in the near wake were considered. Two possibilities to improve the concentration measurement sensitivity were analyzed: (i) a decrease in the background absorption of CO₂ and H₂O and (ii) an increase in the absorption cross section of detected gas.     

Cross-interference correction and simultaneous multi-gas analysis based on infrared absorption

In this paper, we present simultaneous multiple pollutant gases (CO 2 , CO, and NO) measurements by using the non-dispersive infrared (NDIR) technique. A cross-correlation correction method is proposed and used to correct the cross-interferences among the target gases. The calculation of calibration curves is based on least-square fittings with third-order polynomials, and the interference functions are approximated by linear curves. The pure absorbance of each gas is obtained by solving three simultaneous equations using the fitted interference functions. Through the interference correction, the signal created at each filter channel only depends on the absorption of the intended gas. Gas mixture samples with different concentrations of CO 2 , CO, and NO are pumped into the sample cell for analysis. The results show that the measurement error of each gas is less than 4.5%.     

The temperature dependence of the interaction of NO + CO on Pt{1 0 0}

Infrared reflection absorption spectroscopy together with mass spectrometry has been used to investigate the interaction of NO and CO on Pt{1 0 0}, initially prepared in the reconstructed ‘hex’ phase, under ambient pressures of these gases, in the temperature range 300-500 K. The results allow the local and total coverages of adsorbed CO and NO to be related to the rate of reaction to produce gas phase CO₂, and provide insight into the species present on the surface during the so-called low temperature oscillatory reaction regime of this process. At temperatures below that at which NO dissociation occurs (approximately 390-400 K) adsorption is controlled by the non-reactive displacement of NO by CO and results in a CO-poisoned surface. Above 400 K when significant CO₂ production occurs, the NO coverage increases to produce a surface with NO and CO fully intermixed; the increase in NO coverage is attributed to the higher rate of NO arrival from the gas phase (with a partial pressure ratio of P_NO:P_CO>1) at free surface sites created by NO dissociation and subsequent reaction with CO. The competition between these two processes of non-reactive NO displacement by CO and reactive displacement of CO by NO is proposed to determine the parameter space of the low temperature oscillatory regime. Rapid equilibration between bridged and atop CO species leads to them appearing to exhibit identical reaction behaviour. Particularly at the lowest reaction temperatures (around 400 K), islands of pure CO may coexist on the surface but not participate in the reaction. Under conditions corresponding to the high temperature oscillatory regime, small quantities of absorbed CO, but no NO, are seen on the surface.     

Effects of CO2 dilution on partially premixed CH4-air flames in swirl and bluff body stabilized combustor

The effect of CO₂ dilution on the flame characteristics and pollutant emission of a partially premixed CH₄-air flame in a confined bluff body and swirl influenced flowfield is investigated using optical and laser diagnostic methods. The non-premixed burner produced a converging-diverging flowfield at the burner exit and a lifted flame is produced at all test cases, with an upstream movement of the flame with decreasing global equivalence ratios (?_g). Based on variations in ?_g, two flame stabilization modes – bluff body influenced and swirl stabilized – with a transition mode in-between is observed for the cases with (flame FB) and without dilution (flame FM). The characteristics of the heat release zone are influenced by dilution, with the FB flames being longer and also less intense when compared to FM flames. Pollutant measurement at 30 mm downstream from the combustor exit highlighted the ultra-low NO_x capability of the IIST-GS2 burner. CO₂ dilution leads to a reduction in NO_x emission due to both thermal and chemical effects. For ?_g ≥ 0.7 extreme low levels of CO and unburned hydrocarbons (UHC) are observed for both cases. For ?_g ≤ 0.6 the dramatic increase of both CO and UHC maybe due to the lower flame temperatures and shorter flame zone residence times, respectively.     

Adsorption of small molecules on transition metal doped rhodium clusters Rh3X (X = 3d, 4d atom): a first-principles investigation

The adsorption behaviours of seven molecules (CO, CO₂, N₂, NO, O₂, N₂O and NO₂) on Rh₃X (X?=Sc-Zn, Y-Cd) clusters are systematically investigated by density-functional calculations. Rh₃X clusters exhibit physical adsorption when interacting with CO₂, CO, N₂ and NO. The adsorption energies (E_ads) can be ranked as follows: NO?>?CO?>?CO_2?≥?N₂. Compared with pure Rh₄ cluster, the adsorption capacity changes with the doping element. Chemical adsorption can be obtained for Rh₃X when adsorbing O₂, N₂O and NO₂. E_ads shows an order of E_ads(O₂)?>?E_ads(NO₂)?>?E_ads(N₂O). When O₂ is adsorbed, energy barrier with doping Tc or Cr atom is substantially reduced, which indicates that chemical reactivity of O₂ on Rh₄ can be significantly enhanced. The doped rhodium clusters can be viewed as good candidates in the discrimination between different gas molecules.