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     

Raman and fluorescence lidar measurements of aircraft engine emissions

Laser induced Raman and fluorescent measurements were made in the exhaust of a gas turbine engine with a new field portable instrument devised specifically for gas turbine exhaust measurements. The gas turbine exhaust was analyzed by conventional instruments for CO, CO₂, NO, NO_x, total hydrocarbons, smoke and temperature, and these data were used as a ‘calibration’ standard for the evaluation of the laser Raman instrument. Results thus far indicate good correlations for CO₂, O₂, smoke, hydrocarbons and temperature. The instrument was not sensitive enough for NO detection but the data analysis indicates that 100 ppm may be detectable with instrument improvements. CO analysis was not attempted, but it is expected that CO could be detected with further research. NO₂ (or NO_x) was not attempted because theoretical and experimental laboratory analysis indicated severe interference with CO₂. The conclusion was that laser Raman shows a good potential for aircraft gas turbine emission analysis.     

NO<Subscript>2</Subscript>-sensing properties of La<Subscript>0.65</Subscript>Sr<Subscript>0.35</Subscript>MnO<Subscript>3</Subscript> synthesized by self-propagating combustion

Ultrafine-structure La_0.65Sr_0.35MnO₃ (LSM) powders synthesized by self-propagating combustion method have been used to fabricate sensing electrodes (SEs) for NO₂ mixed-potential sensors based on yttria-stabilized zirconia (YSZ). This type of sensor was found to provide better NO₂ sensitivity at 500 °C than sensors with LSM powders synthesized by traditional solid-state methods. The response values of the sensor have good linear relationship (sensitivity 36.6 mV/decade and linear fit 0.99) with the logarithm of NO₂ concentration varying from 30 to 500 ppm. The influence of sintering temperature (1000, 1100, 1200, and 1300 °C) on sensor response was also examined and was found to have a significant effect on the morphology of LSM-SEs. Moreover, in the presence of NO, CO₂, CO, and NO₂, the sensor exhibited good NO₂ selectivity.     

Promotion effect of Pt on a SnO2–WO3 material for NOx sensing

Metal-oxide nanocomposites were prepared over screen-printed gold electrodes to be used as room-temperature NO_x (nitric-oxide (NO) and nitrogen dioxide (NO₂)) sensors. Various weight ratios of SnO₂–WO₃ and Pt loadings were used for NO sensing. The sensing materials were characterized using X-ray diffraction (XRD), transmission electron microscopy (TEM) and BET surface analysis. The NO-sensing results indicated that SnO₂–WO₃ (1:2) was more effective than other materials were. The sensor response (S=resistance of N₂/resistance of NO=R_N2/R_NO) for detecting 1000 ppm of NO at room temperature was 2.6. The response time (T₉₀) and recovery time (TR₉₀) was 40 s and 86 s, respectively. By further loading with 0.5% Pt, the sensor response increased to 3.3. The response and recovery times of 0.5% Pt/SnO₂–WO₃ (1:2) were 40 s and 206 s, respectively. The linearity of the sensor response for a NO concentration range of 10–1000 ppm was 0.9729. A mechanism involving Pt promotion of the SnO₂–WO₃ heterojunction was proposed for NO adsorption, surface reaction, and adsorbed NO₂ desorption.     

Mixed-potential-type NOx sensor based on YSZ and zinc oxide sensing electrode

Electrochemical sensors using tubular yttria-stabilized zirconia (YSZ) and oxide sensing electrode (SE) were fabricated and examined for NO_x detection at high temperatures. The mixed-potential-type NO_x sensor using ZnO-SE gave the highest sensitivity to NO_x among other single-type oxides tested as SEs in the temperature range of 600–700 °C. The response of the ZnO-attached device was a linear for the logarithm of NO₂ (NO) concentrations from 40 to 450 ppm. The sensing mechanism of the sensor was discussed on the basis of the gas adsorption-desorption behavior, the catalytic activity data, and electrochemical behavior for oxides examined.     

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.     

Modified INOvent for delivery of inhaled nitric oxide during cardiac MRI

Background

The aim of this study was to assess the feasibility of delivering NO through a modified system to allow clearance of the magnetic field and thus compatibility with cardiac magnetic resonance (CMR). Nitric oxide (NO) is an inhalational, selective pulmonary vasodilator with a wide range of applications in a variety of disease states, including diseases that affect the right ventricle. Accurate assessment of dynamic changes in right ventricular function necessitates CMR; however, delivery of NO is only possible using equipment that is not magnetic resonance imaging (MRI) compatible (INOvent delivery system, Ohmeda, Inc., Madison, WI, USA).

Methods

The INOvent delivery system was modified by using 35 ft. of standard oxygen tubing to allow NO delivery through an electrical conduit and into the MRI suite. The concentrations of oxygen (O₂), nitrogen dioxide (a harmful byproduct, NO₂) and NO were measured in triplicate using the built-in electrochemical analyzer on the INOvent. After confirmation of safety, the system was used to administer drug to a patient x, and dynamic MRI measurements were performed.

Results

When the standard INOvent was set to administer 40 ppm of NO, the mean/standard deviation of gas delivered was as follows: NO: 42/0 ppm; NO₂: 0.3/0.1 ppm; and O₂: 93/0 ppm. In comparison, the gas delivery of the modified INOvent was follows: NO: 41/0 ppm; NO₂: 0.5/0 ppm; and O₂: 93.7/0.6 ppm. During administration to an index patient with severe pulmonic insufficiency (PI), a measurable reduction in PI was observed by CMR.

Conclusions

Nitric oxide can be administered through 35 ft. of standard oxygen tubing without significantly affecting dose delivery. This technique has potential application in patients with right-sided structural heart disease for determination of dynamic physiological changes.     

Temperature dependence of NO2 sensitivity of YSZ-based mixed potential type sensor attached with NiO sensing electrode

A mixed potential type yttria-stabilized zirconia-based sensor using NiO sensing electrode and Pt reference electrode was fabricated, and its NO₂ sensing characteristics were examined at various operating temperatures in the range of 700–950 °C. It was observed that the sensitivity to NO₂ strongly depends on the operating temperature of the sensor; the sensitivity decreases with increasing operating temperature, while the response/recovery rates increase. To rationalize this temperature dependence of NO₂ response, polarization curves and complex impedances of the sensor were measured in the base gas and in the sample gas (400 ppm NO₂?+?base gas) at various operating temperatures. It turned out that the operating temperature had a strong influence on the rate of anodic reaction of oxygen; the increased rate of anodic reaction leads to lower NO₂ sensitivity and quicker response/recovery at higher operating temperature.     

Fiber-Optic Chemical Sensor for Detection of NO2 Using Poly (3-Octylthiophene)

Abstract

A fiber-optic chemical sensor (FOCS) for detection of nitrogen dioxide (NO ₂ ) molecules is reported. The FOCS presents an optropode structure because of the transmission properties of the sensitive material. The NO ₂ FOCS is activated by using the semiconductor polymer: regioregular head-to-tail poly(3-octylthiophene-2,5-diyl). The operation wavelength of the sensor is 543.5 nm such that a simple LED and detector can be used for the design of this device. The sensor response decreases after each exposure, demonstrating the reduction in sensitivity as well as irreversibility lower than 5%. However, its properties such as rapid response, high selectivity, high sensitivity (0.43 ± 0.01 muW/ppm), hygroscopic properties, and its operation at room temperature make this kind of FOCS a good alternative for NO ₂ toxic gas detection.     

Experimental study of a confined premixed metal combustor: Metal flame stabilization dynamics and nitrogen oxides production

This work presents a study of a magnesium/air combustion process in the context of innovative zero carbon dioxide (CO₂) energy carriers for reducing global warming effects. In order to analyze more deeply the confined combustion of magnesium under fluctuating overpressure conditions (0 to 24 hPa) and the generated gaseous by-products, magnesium/air flames have been realized in a combustion chamber with a conical bluff-body as flame holder and different contraction ratios diaphragms at the exit duct. Sieved magnesium samples with two size-fractions were tested: 20–50?µm and 50–70?µm. The gaseous emissions of nitrogen oxides (NO_x) and dioxygen (O₂) were analyzed with on-line infrared, ultraviolet and paramagnetic analyzers. A flame pulsating behavior was clearly observed from light emission intensity (monitored by a photodiode) and pressure fluctuations (monitored by a pressure sensor); the frequencies obtained ranged between 3 and 10?Hz. The frequency of the pulsation exhibited strong dependence on the geometric configuration of the chamber: a contraction diaphragm divided by two the frequency level of the fluctuations in the studied range of maximum overpressure. Such fluctuations may probably be the consequence of periodic perturbations of the recirculation zone behind the bluff-body. These periodic perturbations are themselves caused by strong periodic overpressure variations due to stiff contraction downstream responding to gas velocity fluctuations. This feed-back-loop mechanism was considered in this study. NO_x emissions produced through the thermal pathway were analyzed for equivalence ratios ranging from 0.29 to 1. The representation of NO_x versus equivalence ratio exhibited a parabolic shape with a maximum for an equivalence ratio of 0.4. Moreover, NO_x emissions of this metal combustor have shown a similar order of magnitude than current internal combustion engines.     

Chemical kinetic interactions of NO with a multi-component gasoline surrogate: Experiments and modeling

This work reports an experimental and modeling study on the chemical kinetic interactions of NO with a multi-component gasoline surrogate, namely PACE-20, using a twin-piston rapid compression machine at a stochiometric fuel loading with 20% EGR (exhaust gas recirculation) by mass, pressures of 20 and 40 bar, and temperatures from 700 to 930 K. Five NO concentrations are investigated, namely 0, 20, 50, 70 and 150 ppm, where NO addition effects are characterized through changes in PACE-20 ignition reactivity and heat release characteristics. Experiments indicate that within the low-temperature regime, NO promotes low-temperature heat release rate and main ignition reactivity at low addition levels, with saturation or even inhibiting effects observed at >50 ppm NO addition, while within the NTC/intermediate-temperature regime, adding NO only promotes reactivity. A recently updated, detailed chemical kinetic model with chemistry specific to NOx/hydrocarbons interaction incorporated is used to simulate the experiments, and reasonable agreement is obtained. In-depth sensitivity and rate of production analyses are further performed. The results indicate that NO interacts with PACE-20 via two types of interaction: (a) direct interactions between NO and PACE-20 derivatives, primarily through NO+HO₂↔NO₂+OH and RO₂+NO↔RO+NO₂, and (b) indirect interactions between PACE-20 derivatives and NO₂ produced from the direct interactions, primarily through R+NO₂↔RO+NO. The observed NO inhibiting effect at low temperatures and 150 ppm NO addition is attributed to the lack of HO₂ radicals to sustain NO consumption via NO+HO₂↔NO₂+OH, and the take-up of inhibiting pathways via RO₂+NO↔RO+NO₂. The results also indicate that even with the presence of multiple fuel components, NOx/hydrocarbons interactions are highly selective, and are mainly initiated by the interactions between NO and RO₂ radicals from cyclopentane and ethanol, as well as between NO₂ and R radicals from toluene, 1,2,4-trimethylbenzene and 1-hexene. Further studies on these interactive reactions are therefore highly recommended.     

An optical system for measuring nitric oxide using spectral separation techniques

An optical sensor based on differential absorption spectroscopy for real-time monitoring of industrial nitric oxide (NO) gas emission is described. The influence of gas absorption interference from sulfur dioxide (SO₂) in the environment was considered and a spectral separation technique was developed in order to eliminate this interference effect. The absorption spectrum of SO₂ around 226 nm was evaluated by the SO₂ concentration obtained using the experimentally recorded absorption spectrum around 300 nm. The absorption spectrum of NO around 226 nm was obtained by subtracting the absorption of SO₂ from the integral absorption spectrum of SO₂ and NO. The concentration measurements were performed at atmospheric pressure. The technique was found to have a lower detection limit of 0.8 ppm for NO per meter path length (SNR=2) and be immune from the influence from SO₂ on the NO measurement. The sensor based on this technique was successfully employed for in situ measurement of SO₂ and NO concentrations in the flue gas emitted from an industrial coal-fired boiler.     

The reactions of nitric oxide with nickel films as studied by x-ray photoelectron spectroscopy

X-ray photoelectron spectroscopy has been employed to study the reactions between nitric oxide and freshly deposited nickel films. When the nickel surface is treated with NO at pressures of less than 1 · 10^?4 torr for 60 s (6000L), the NO is dissociatively adsorbed with no oxidation of the nickel surface. When treated with 0.40 torr of NO that has been exposed to varying degrees of oxidation, the nickel surface is oxidized and species such as NO₃^?, NO₂^?, NO and N₂ may be found on the surface. The species found are determined by the extent of oxidation of NO.     

Polypyrrole–NiO hybrid nanocomposite films: highly selective,sensitive, and reproducible NO2 sensors

Polypyrrole–nickel oxide (PPy–NiO) hybrid nanocomposite thin-film sensor was prepared by spin-coating method on glass substrate. The PPy–NiO hybrid nanocomposite thin film sensors were used to study room temperature gas-sensing properties for oxidizing (NO₂, Cl₂) as well as reducing (NO₂, H₂S, C₂H₅OH, NH₃, and Cl₂) gases. It was revealed that PPy–NiO (50 %) hybrid nanocomposite thin-film sensor could detect NO₂ at low concentration (100 ppm) with very high selectivity (47 % compared with Cl₂) and high sensitivity (47 %), with better stability (90 %) and reproducibility. The response and recovery times were changed significantly with NO₂ concentration.     

Engines and exhaust after treatment systems for future automotive applications

Engine concepts for future automotive applicationsSafe, clean and efficient engines will become more important in modern societies where we will see higher levels of mobility on one hand and limited resources on the other hand. Gasoline engines for passenger cars have been developed to generate more power and reduce emissions at the same time. Therefore the engine systems have become complex with a number of subsystems.Because of its reliability and efficiency the diesel engine is classically operated in heavy duty vehicles, however in recent years because of its high torque when used with a turbocharger it has become more popular for passenger cars and even sport vehicles as well. The development of the diesel engine especially the direct injection as well as the common rail high pressure injection brought further improvement regarding power, efficiency and emissions. In the future exhaust after treatment systems will be developed in order to comply with emission standards similar to those of gasoline engines.Emission control systems with chemical and physical sensorsIn order to meet the more and more stringent emission regulations gasoline as well as diesel engines will need continuously improved exhaust after treatment systems. The options for the various applications are highlighted in the following.Today exhaust gas of gasoline engines is typically treated with “Three Way Catalysts” (TWC). The catalyst converts the pollutants CO, NO_X and Hydrocarbons into harmless compounds like CO₂, H₂O and N₂ by chemical reactions. Lambda-Sensors control the air fuel ratio of the engine and catalyst performance in order to get the best possible conversion of the pollutants.Modern lean burn engines have other options. Here the pollutants in the exhaust gases are only partially converted by a TWC function i.e. CO and Hydrocarbons. For the remaining NO_X a so called NO_X Storage Catalyst (NSC) is employed, which chemically stores NO and NO₂ during lean burn phase. For the conversion of stored NO_X the engine is periodically shifted to fuel rich operation. This more complex system is controlled with the help of mathematical catalyst models and by Lambda-, Temperature- and optionally NO_X-Sensors as well.Diesel engine exhaust of heavy duty vehicles will be treated with ammonia by Selective Catalytic Reduction (SCR) to reduce NO_X additionally to the catalytic oxidation of CO and Hydrocarbons. The ammonia is generated on board of the vehicle using harmless precursors like for example urea. For the control of this system Lambda-, Temperature- NO_X- and optionally NH₃-Sensors are employed.In addition to gaseous pollutants the particulate emissions from diesel engines will be removed by Diesel Particulate Filters (DPF). The system of oxidation catalyst and DPF is controlled by Temperature-, Pressure- and Particulate-Sensors.The mentioned highlights show that all three goals safe, clean and efficient can be met in the future by both gasoline and diesel engines combined with modern exhaust after treatment systems.     

Quantum cascade laser-based sensor for detection of exhaled and biogenic nitric oxide

A real-time, in situ CO sensor using 2.3 μm DFB diode laser absorption, with calibration-free wavelength-modulation-spectroscopy, was demonstrated for continuous monitoring in the boiler exhaust of a pulverized-coal-fired power plant up to temperatures of 700 K. The sensor was similar to a design demonstrated earlier in laboratory conditions, now refined to accommodate the harsh conditions of utility boilers. Measurements were performed across a 3 m path in the particulate-laden economizer exhaust of the coal-fired boiler. A 0.6 ppm detection limit with 1 s averaging was estimated from the results of a continuous 7-h-long measurement with varied excess air levels. The measured CO concentration exhibited expected inverse trends with the excess O₂ concentration, which was varied between 1 and 3 %. Measured CO concentrations ranged between 6 and 200 ppm; evaluation of the data suggested a dynamic range from 6 to 10,000 ppm based on a minimum signal-to-noise ratio of ten and maximum absorbance of one. This field demonstration of a 2.3 μm laser absorption sensor for CO showed great potential for real-time combustion exhaust monitoring and control of practical combustion systems.     

Modelling and speciation of nitrogen oxides in engines

The present study extends the Nitrogen Oxide Relaxation Approach (NORA [Vervisch et al., Combust. Flame 158 (2011) 1480–1490]) for NO_x modelling in engines by introducing alternative chemical routes to the thermal pathway as well as a speciation of nitrogen oxides into nitrogen monoxide (NO), nitrogen dioxide (NO₂) and nitrous oxide (N₂O). Perturbations of equilibrium state are considered to identify nitrogen oxide reactivity in various mixture and thermodynamic conditions. A common Intrinsic Low-Dimensional Manifold (ILDM) is identified for NO and NO₂, while nitrous oxides appear to stay in near-equilibrium state for any in-cylinder conditions. The relaxations back towards the equilibrium state after the perturbations are analysed to extract the characteristic times of relaxation, an image of the species reactivity. Tabulation of equilibrium mass fractions and characteristic relaxation times as a function of mixture and thermodynamic conditions allows nitrogen oxide modelling to be performed for internal combustion engines at very low computational cost through idealised ILDMs that are independent of the combustion ones. Results show the accuracy of the modelling approach for nitrogen oxide emissions of a Diesel engine at part and full load.     

Sensors for the nitrogen oxides, NO2, NO and N2O, based on In2O3 and WO3 nanowires

Sensing characteristics of ZnO, In₂O₃ and WO₃ nanowires have been investigated for the three nitrogen oxides, NO₂, NO and N₂O. In₂O₃ nanowires of ∼20 nm diameter prepared by using porous alumina membranes are found to have a sensitivity (defined as the ratio of the sensor resistance in the gas concerned to that in air) of about 60 for 10 ppm of all the three gases at a relatively low temperature of 150 °C. The response and recovery times are around 20 s. The sensitivity of these In₂O₃ nanowires is around 40 for 0.1 ppm of NO₂ and N₂O at 150 °C. WO₃ nanowires of 5–15 nm diameter, prepared by the solvothermal process show a sensitivity of 20–25 for 10 ppm of the three nitrogen oxides at 250 °C. The response and recovery times are 10 s and 60 s, respectively. The sensitivity is around 10 for 0.1 ppm of NO₂ at 250 °C. The sensitivity of In₂O₃ and WO₃ nanowires is not affected by humidity even up to 90% relative humidity. The study also reveals that the sensing mechanism for the three nitrogen oxides have a commonality in that the desorption of oxygen is a crucial step in all the cases. PACS 07.07.Df; 85.35.-p; 82.35.Np     

Impact of nitric oxide on n-heptane and n-dodecane autoignition in a new high-pressure and high-temperature chamber

A New One Shot Engine (NOSE) was designed to simulate the thermodynamic conditions at High Pressure-High Temperature like an actual common-rail diesel engine in order to study the compression ignition of spray. The volume of the combustion chamber provided with large optical windows simplified the implementation of various optical diagnostics. The advantage of this kind of set-up in comparison to pre-burn or flue chambers is that the initial gas mixture can be well controlled in terms of species and mole fraction. The purpose of this work was to investigate the impact of nitric oxide (NO) on ignition delay (ID) for two fuels with different cetane numbers: n-heptane, and n-dodecane. In the thermodynamic conditions chosen (60?bar and over 800–900?K), NO had a strong effect on ID, with increases in NO tending to reduce the ignition delay. Results showed that ID and Lift-Off Length (LOL) presented the same trend as a function of temperature and NO concentration. Experimentally, at 900?K the ignition of n-dodecane was promoted by NO up to 100?ppm, whilst higher NO levels did not further promote ignition and a stabilization of the value has been noticed. For n-heptane, stronger promoting effects were observed in the same temperature conditions: the ignition delays were monotonically reduced with up to 200?ppm NO addition. At a lower temperature (800?K) the inhibiting effect was observed for n-dodecane for [NO] greater than 40?ppm, whereas only a promoting effect was observed for n-heptane. The experimental results of LOL showed that NO shortened LOL in almost all cases, and this varied with both the NO concentration and the mixture temperature. Thus, fuels with shorter ignition delays produce shorter lift-off lengths.     

NO and OH* emission characteristics of very-lean to stoichiometric ammonia–hydrogen–air swirl flames

One of the main concerns regarding ammonia combustion is its tendency to yield high nitric oxide (NO) emissions. Burning ammonia under slightly rich conditions reduces the NO mole fraction to a low level, but the penalties are poor combustion efficiency and unburnt ammonia. As an alternative solution, this paper reports the experimental investigation of premixed swirl flames fueled with ammonia-hydrogen mixtures under very-lean to stoichiometric conditions. A gas analyzer was used to measure the NO mole fraction in the flame and post flame regions, and it was found that low NO emissions (as low as 100 ppm) in the exhaust were achieved under very lean conditions (? ≈ 0.40). Low NO emission was also possible at higher equivalence ratios, e.g. ? = 0.65, for very large ammonia fuel fractions (X_NH3 > 0.90). 1-D flame simulations were performed to elaborate on experimental findings and clarify the observations of the chemical kinetics. In addition, images of OH* chemiluminescence intensity were captured to identify the flame structure. It was found that, for some conditions, the OH* chemiluminescence intensity can be used as a proxy for the NO mole fraction. A monotonic relationship was discovered between OH* chemiluminescence intensities and NO mole fraction for a wide range of ammonia-hydrogen blends (0.40 < ? < 0.90 and 0.25 < X_NH3 < 0.90), making it possible to use the low-cost OH* chemiluminescence technique to qualify NO emission of flames fueled with hydrogen-enriched ammonia blends.