Ignition in a supersonic flow by a plasma jet of mixed feedstock including CH4

Ignition tests of hydrocarbon fuels in a supersonic airflow by plasma jet (PJ) torches of mixed feedstock, including methane (CH₄), such as N₂/CH₄ and N₂/CH₄/O₂ mixtures, were conducted. The Mach number of the airflow was 2.0, and the total temperature and total pressure of the main flow were those of room conditions. The wall pressure increase due to combustion of hydrocarbon fuels for the N₂/CH₄ PJ exceeded those of pure O₂ and N₂ PJs at high electric power input. Equilibrium calculations showed that the main species in high-temperature PJ, aside from N₂, were H₂, H, and HCN. Considering the slight impact of the HCN species on ignition delay time, the combustion enhancement by the N₂/CH₄ PJ was caused primarily by the existence of a large amount of H and H₂ dissociated from CH₄ molecules in the PJ. Moreover, the addition of O₂ to the N₂/CH₄ feedstock further enhanced the combustion and stability of the N₂/CH₄ PJ. The existence of O₂ increased the temperature and the number of H radicals in the PJ exhaust.     

Optimization of double plasma jet torches in a scramjet combustor

Ignition tests by double plasma jet (PJ) torches in a supersonic flow were conducted. Two PJ torches with different feedstocks were arranged in a straight line in the direction of flow. The Mach number of the airflow was 2.3, and the total temperature and total pressure of the main flow were those of room conditions. A C₂H₄ fuel perpendicularly injected with its sonic speed into the main flow was tested. A combination of O₂–O₂ feedstocks for the two torches was more effective than other combinations such as H₂/N₂–O₂. Moreover, the effectiveness of the double PJs was found to be almost the same as that of a single PJ. These results indicate that combustion reactions of the main fuel injected upstream of the PJ were mostly completed in the vicinity of the upstream PJ. The upstream PJ was considered to be dominant for ignition and the combustion process, indicating that the influence of the downstream PJ was small. On the other hand, the advantage of the double PJs over the single PJ in reducing damage to the torch nozzle was confirmed.     

Characterization of LaMnAl11O19 by FT-IR spectroscopy of adsorbed NO and NO/O2

The nature of the NO_x species produced during the adsorption of NO at room temperature and during its coadsorption with oxygen on LaMnAl₁₁O₁₉ sample with magnetoplumbite structure obtained by a sol-gel process has been investigated by means of in situ FT-IR spectroscopy. The adsorption of NO leads to formation of anionic nitrosyls and/or cis-hyponitrite ions and reveals the presence of coordinatively unsaturated Mn³⁺ ions. Upon NO/O₂ adsorption at room temperature various nitro-nitrato structures are observed. The nitro-nitrato species produced with the participation of electrophilic oxygen species decompose at 350 °C directly to N₂ and O₂. No NO decomposition is observed in absence of molecular oxygen. The adsorbed nitro-nitrato species are inert towards the interaction with methane and block the active sites (Mn³⁺ ions) for its oxidation. Noticeable oxidation of the methane on the NOx⁻-precovered sample is observed at temperatures higher than 350 °C due to the liberation of the active sites as a result of decomposition of the surface nitro-nitrato species. Mechanism explaining the promoting effect of the molecular oxygen in the NO decomposition is proposed.     

AP/(N2 + C2H2 + C2H4) gaseous fuel diffusion flame studies

Counterflow diffusion flame experiments and modeling results are presented for a fuel mixture consisting of N₂, C₂H₂, and C₂H₄ flowing against decomposition products from a solid AP pellet. The flame zone simulates the diffusion flame structure that is expected to exist between reaction products from AP crystals and a hydrocarbon binder. Quantitative species and temperature profiles have been measured for one strain rate, given by a separation of 5 mm, between the fuel exit and the AP surface. Species measured include C₂H₂, C₂H₄, N₂, CN, NH, OH, CH, C₂, NO, NO₂, O₂, CO₂, H₂, CO, HCl, H₂O, and soot volume fraction. Temperature was measured using a combination of a thermocouple at the fuel exit and other selected locations, spontaneous Raman scattering measurements throughout the flame, NO vibrational populations, and OH rotational population distributions. The burning rate of the AP was also measured for this flame’s strain rate. The measured eighteen scalars are compared with predictions from a detailed gas-phase kinetics model consisting of 105 species and 660 reactions. Model predictions are found to be in good agreement with experiment and illustrate the type of kinetic features that may be expected to occur in propellants when AP particles burn with the decomposition products of a polymeric binder.     

Experimental and kinetic investigations of the effect of H2/CH4/C2H4 addition on the burning properties of practical jet fuel

Laminar flame speeds of premixed jet fuel/air with the addition of hydrogen, methane and ethylene are measured in a constant-volume bomb at an initial temperature of 420 K, initial pressure of 3 atm, equivalence ratios of 0.6–1.5 and gas mass fractions of 0–50%. The experimental results show that the addition of hydrogen and ethylene can significantly improve the laminar flame speed of the liquid jet fuel, while the addition of methane shows a weak inhibitory effect, and these effects are relatively remarkable on the fuel-rich conditions. The laminar flame speed of the dual fuels/air is linearly dependent on the additional gas mass fraction. A kinetic analysis indicates that the gas addition causes both thermodynamic and chemical kinetic effects on the laminar flame speed of the dual fuels/air. The adiabatic temperature increases and decreases with the addition of hydrogen/ethylene and methane, respectively. A sensitivity analysis shows that the reactions concerning to the H, CH₃ and C₂H₃ radicals become significant with the addition of hydrogen, methane and ethylene, respectively, and that the different values of the rate of product (ROP) of these species via the critical reactions lead to a different promotional or inhibitory effect on the fuel-rich and fuel-lean conditions.     

Homogeneous ignition of CH4/air and H2O and CO2-diluted CH4/O2 mixtures over Pt; an experimental and numerical investigation at pressures up to 16 bar

The homogeneous ignition of CH₄/air, CH₄/O₂/H₂O/N₂, and CH₄/O₂/CO₂/N₂ mixtures over platinum was investigated experimentally and numerically at pressures 4 bar p 16 bar, temperatures 1120 K T 1420 K, and fuel-to-oxygen equivalence ratios 0.30 0.40. Experiments have been performed in an optically accessible catalytic channel-flow reactor and included planar laser induced fluorescence (LIF) of the OH radical for the determination of homogeneous (gas-phase) ignition and one-dimensional Raman measurements of major species concentrations across the reactor boundary layer for the assessment of the heterogeneous (catalytic) processes preceding homogeneous ignition. Numerical predictions were carried out with a 2D elliptic CFD code that included elementary heterogeneous and homogeneous chemical reaction schemes and detailed transport. The employed heterogeneous reaction scheme accurately captured the catalytic methane conversion upstream of the gaseous combustion zone. Two well-known gas-phase reaction mechanisms were tested for their capacity to reproduce measured homogeneous ignition characteristics. There were substantial differences in the performance of the two schemes, which were ascribed to their ability to correctly capture the p–T– parameter range of the self-inhibited ignition behavior of methane. Comparisons between measured and predicted homogeneous ignition distances have led to the validation of a gaseous reaction scheme at 6 bar p 16 bar, a pressure range of particular interest to gas-turbine catalytically stabilized combustion (CST) applications. The presence of heterogeneously produced water chemically promoted the onset of homogeneous ignition. Experiments and predictions with CH₄/O₂/H₂O/N₂ mixtures containing 57% per volume H₂O have shown that the validated gaseous scheme was able to capture the chemical impact of water in the induction zone. Experiments with CO₂ addition (30% per volume) were in good agreement with the numerical simulations and have indicated that CO₂ had only a minor chemical impact on homogeneous ignition.     

光腔衰荡光谱法测量大气中的NO3和N2O5

本文应用基于二极管激光器的双路光腔衰荡光谱技术,分别对大气中NO₃和N₂O₅浓度进行监测. 通过使用实验室标准样校正有效吸收腔长比R_L和系统的总损耗系数?,并获得了NO₃有效吸收截面. 该装置在时间分辨率为1 s时,对NO₃的测量灵敏度达到1.1 pptv,N₂O₅被在线转换成NO₃,从而被另一路光腔衰荡光谱装置探测. 利用该装置,对合肥市区冬季夜间大气中的NO₃,N₂O₅浓度进行了实时监测. 通过对比一次大气快速清洁过程中氮氧化物、臭氧、PM_2.5等组分的浓度变化,讨论了大气环境下可能影响NO₃及N₂O₅浓度的因素.     

The effect of hydrogen addition on flammability limit and NOx emission in ultra-lean counterflow CH4/air premixed flames

The effect of hydrogen addition to ultra lean counterflow CH₄/air premixed flames on the extinction limits and the characteristics of NO_x emission was investigated by numerical simulation. Detailed chemistry and complex thermal and transport properties were employed. The results show that the addition of hydrogen can significantly enlarge the flammable region and extend the flammability limit to lower equivalence ratios. If the equivalence ratio is kept constant, the addition of hydrogen increases the emission of NO in a flame due to the enhancement in the rate of the NNH or N₂O intermediate NO formation routes. The addition of hydrogen causes a monotonic decrease in the formation of NO₂ and N₂O, except flames near the extinction limits, where the emission of NO₂ and N₂O first increases, and then decreases with the increase in the fraction of hydrogen. Overall, hydrogen enrichment technology allows stable combustion under ultra lean conditions, resulting in significant CO₂ and NO emission reduction.     

NO dissociation and N2 production in the presence of co-adsorbed SO2 and D2 on Pt(3 3 2)

NO dissociation and subsequent N₂ production in the presence of co-adsorbed S¹⁸O₂ and D₂ on the surface of stepped Pt(3 3 2) were studied using Fourier transform infra red reflection–absorption spectroscopy (FTIR-RAS) combined with thermal desorption spectroscopy (TDS). Reduction of NO by D (D₂ is adsorbed dissociatively on Pt surfaces) proceeds to a limited extent, because this reaction is rate-controlled by NO dissociation and the supply of D atoms at the higher surface temperatures at which NO dissociation becomes significant (350 K and higher). NO–D reaction is suppressed in the presence of S¹⁸O₂, depending significantly on the S¹⁸O₂ coverage and the competition between the reactions NO–D and S¹⁸O₂–D. When the supply of D₂ is limited, e.g., 0.1 L in this study, the presence of S¹⁸O₂ suppresses the NO–D reaction. With a sufficient supply of D₂, e.g., 0.4 L and higher, D-atom competing reactions do not play a role any more because the reactions of both NO and S¹⁸O₂ with D proceed only to a very limited extent. As such, generation of O atoms from S¹⁸O₂ dissociation is the main reaction that leads to the suppression in NO dissociation and consequently, N₂ production.It is also concluded that the presence of S¹⁸O₂ does not seriously poison the active sites on the Pt surface, providing that there is a sufficient D supply to remove O atoms from both NO dissociation and S¹⁸O₂ dissociation.     

Coadsorption of NO and other small gases (H2 and CO) on polycrystalline rhodium surface

The coadsorption of NO and other small gases (H₂ and CO) on a polycrystalline Rh filament has been studied by thermal desorption mass spectroscopy, using ¹⁵NO. The sample was exposed to a mixture of nitric oxide and other gases with various concentrations of ¹⁵NO at room temperature. It is indicated that NO, CO and H₂ coadsorbs on the rhodium surface, and NO desorbs as N₂ and O₂. NO is adsorbed mainly in the dissociation at lower coverage and molecular adsorption becomes dominant at higher coverage. But the amount of desorbed O₂ was very small. The chemisorption of CO is affected by the chemisorbed NO. Thermal desorption of hydrogen is detected when the value of P_15NO/P_CO is very small. The hydrogen adsorbed on the rhodium surface is replaced by NO with a longer exposure time.     

Experimental and numerical investigation of hetero-/homogeneous combustion of CO/H2/O2/N2 mixtures over platinum at pressures up to 5 bar

The hetero-/homogeneous combustion of fuel-lean CO/H₂/O₂/N₂ mixtures over platinum is investigated at pressures up to 5 bar, inlet temperatures (T_IN) up to 874 K, and a constant CO:H₂ molar ratio of 2:1. Experiments are performed in an optically accessible channel-flow catalytic reactor and involve planar laser induced fluorescence (LIF) of the OH radical for the assessment of homogeneous (gas-phase) ignition and 1-D Raman measurements of major gas-phase species concentrations over the catalyst boundary layer for the evaluation of the heterogeneous (catalytic) processes. Simulations are carried out with an elliptic 2-D model that includes detailed heterogeneous and homogeneous chemical reaction schemes. The predictions reproduce the Raman-measured catalytic CO and H₂ consumption, and it is further shown that for wall temperatures in the range 975 ? T_w ? 1165 K the heterogeneous pathways of CO and H₂ are largely decoupled. However, for wall temperatures below a limiting value of 710–720 K and for the range of pressures and mixture preheats investigated, CO(s) blockage of the surface inhibits the catalytic conversion of both fuel components. The homogeneous ignition distance is well-reproduced by the model for T_IN > 426 K, but it is modestly overpredicted at lower T_IN. Possible reasons for these modest differences can be the values of third body efficiencies in the gas-phase reaction mechanism. The sensitivity of homogeneous ignition distance on the catalytic reactions is weak, while the H₂/O₂ subset of the CO/H₂/O₂ gaseous reaction mechanism controls the onset of homogeneous ignition. Pure hydrogen hetero-/homogeneous combustion results in flames established very close to the catalytic walls. However, in the presence of CO the gaseous combustion of hydrogen extends well-inside the channel core, thus allowing homogeneous consumption of H₂ at considerably shorter reactor lengths. Finally, implications of the above findings for the design of syngas-based catalytic reactors for power generation systems are discussed.     

Opto-galvanic spectroscopy of some molecules in discharges: NH2, NO2, H2 and N2

The change of the discharge voltage when laser light crossing the discharge is tuned to a molecular transition has been measured. Experiments have been performed in the wavelength region between 570 nm and 620 nm with discharges in NH₃, NO₂, H₂, N₂, O₂ and argon. Transitions from the ground states of NH₂ and NO₂ and transitions from metastable states of N₂ and H₂ have been detected. The spacial dependence of the opto galvanic in a low pressure dc-discharge of H₂ and N₂ has been studied.     

Electron spectroscopy using excited atoms and photons IX. Penning ionization of CO2, CS2, COS,N2O,H2S,SO2, and NO2

The electron spectra resulting from thermal collisions of He* (predominantly 2³S) metastable atoms with the seven triatomic molecules, CO₂, COS, CS², N₂O H₂S, SO₂ and NO₂, are compared with their respective 584-Å photoelectron spectra using a transmission-corrected electron spectrometer. The normalised relative electronic-state transition probabilities for production of ionic states in Penning ionization and photoionization are reported together with energy shifts (ΔE values) for He*(2³S) Penning ionization. The cross-section for Penning ionization to lower states of NO₂⁺ is extremely low as has been observed in other open shell molecules such as NO and O₂.     

Oxidation of H2/CO2 mixtures and effect of hydrogen initial concentration on the combustion of CH4 and CH4/CO2 mixtures: Experiments and modeling

An experimental investigation of the oxidation of hydrogen diluted by nitrogen in presence of CO₂ was performed in a fused silica jet-stirred reactor (JSR) over the temperature range 800-1050 K, from fuel-lean to fuel-rich conditions and at atmospheric pressure. The mean residence time was kept constant in the experiments: 120 ms at 1 atm and 250 ms at 10 atm. The effect of variable initial concentrations of hydrogen on the combustion of methane and methane/carbon dioxide mixtures diluted by nitrogen was also experimentally studied. Concentration profiles for O₂, H₂, H₂O, CO, CO₂, CH₂O, CH₄, C₂H₆, C₂H₄, and C₂H₂ were measured by sonic probe sampling followed by chemical analyses (FT-IR, gas chromatography). A detailed chemical kinetic modeling of the present experiments and of the literature data (flame speed and ignition delays) was performed using a recently proposed kinetic scheme showing good agreement between the data and this modeling, and providing further validation of the kinetic model (128 species and 924 reversible reactions). Sensitivity and reaction paths analyses were used to delineate the important reactions influencing the kinetic of oxidation of the fuels in absence and in presence of additives (CO₂ and H₂). The kinetic reaction scheme proposed helps understanding the inhibiting effect of CO₂ on the oxidation of hydrogen and methane and should be useful for gas turbine modeling.     

Adsorption of pairs of NOx molecules on single-walled carbon nanotubes and formation of NO + NO3 from NO2

The adsorption of NO_x(x = 1, 2, 3) molecules on single-walled carbon nanotubes (SWCNTs) is investigated using first-principle calculations. Single NO, NO₂ and NO₃ molecules are found to physisorb on SWCNTs, but molecules can be chemisorbed in pairs on the top of carbon atoms at close sites of SWCNTs. The adsorption energy for pairs of NO or NO₃ molecules is larger than for pairs of NO₂ molecules. The local curvature is found to have a sizable effect on adsorption energies. The possibility of a surface reaction NO₂ + NO₂ → NO + NO₃ is examined and the relative pathway and barrier is calculated. The results are discussed with reference to available experimental results.     

FEM study of NOW and NO2W adsorption system

Nitric oxide adsorption on tungsten and nitric dioxide adsorption on tungsten have been investigated by the FEM method. When NO or NO₂ adsorbs gradually on W at 300 K and at 80 K, the FEM patterns which appear at first are found to be similar to those which appear in N₂ adsorption on W. In the case of NO adsorption on W at 80 K, with further exposure, no further change of the FEM patterns is observed. However, in the cases of NO adsorption on W at 300 K, NO₂ adsorption on W at 300 K, and NO₂ adsorption on W at 80 K, further changes of the FEM patterns are observed with further exposure, and the FEM pattern which is obtained at the saturated state is found to be similar to the FEM pattern which appears at the saturated state of O₂ adsorption on W. From the above results it is suggested that NO and NO₂ dissociate on W at 300 and at 80 K.     

Heterogeneous fixation of N2: Investigation of a novel mechanism for formation of NO

Formation of NO initiated by heterogeneous fixation of N₂ during pyrolysis is investigated experimentally and theoretically. The experiments were conducted with beech wood as well as with the pure biomass components cellulose, xylan, and lignin. The NO formation during char oxidation was recorded as function of pyrolysis atmosphere (N₂ or Ar), pyrolysis temperature (700–1050 °C), and oxidizing atmosphere (O₂ in N₂ or Ar). The results confirm earlier reports that biomass char may be enriched in N during pyrolysis at 900 °C and above. The N-uptake involves re-capture of N-volatiles as well as uptake of N₂. During char oxidation, the captured N is partly oxidized to NO, resulting in increased NO formation. The NO yield from oxidation of beech wood char made in N₂ increases with pyrolysis temperature, and is about a factor of two higher at 1050 °C than the corresponding yield from chars made in Ar. The experiments with pure materials show that the lignin char has the strongest ability to form NO from uptake of N₂, while xylan char forms only small amounts of NO from N₂. Density Functional Theory (DFT) calculations on model chars have revealed a number of chemisorption sites for N₂, many of which are weakly bound and therefore expected to have a short half-life at the higher pyrolysis temperatures. However, the chemisorption of N₂ across a single ring of the armchair surface was found to have an activation energy of 344 ± 30 kJ mol⁻¹ and form a stable, exothermic product with cyano groups. This demonstrates that at least one channel exists for the high-temperature incorporation of N₂ into a char which could give rise to the observed increase in NO release in subsequent char oxidation.     

An experimental and modeling study on auto-ignition of ammonia in an RCM with N2O and H2 addition

Deep insights into the combustion kinetics of ammonia (NH₃) can facilitate its application as a promising carbon-free fuel. Due to the low reactivity of NH₃, experimental data of NH₃ combustion can only be obtained within a limited range. In this work, nitrous oxide (N₂O) and hydrogen (H₂) were used as additives to investigate NH₃ auto-ignition in a rapid compression machine (RCM). Ignition delay times for NH₃, NH₃/N₂O blends, and NH₃/H₂ blends were measured at 30 bar, temperatures from 950 to 1437 K. The addition of N₂O and H₂ ranged from 0 to 50% and 0 to 25% of NH₃ mole fraction, respectively. Time-resolved species profiles were recorded during the auto-ignition process using a fast sampling system combined with a gas chromatograph (GC). An NH₃ combustion model was developed, in which the rate constants of key reactions were constrained by current experimental data. The addition of N₂O affected the ignition of NH₃ primarily through the decomposition of N₂O (N₂O (+M) = N₂ + O (+M), R1) and direct reaction between N₂O and NH₂ (N₂H₂ + NO = NH₂ + N₂O, R2). The rate constant of R2 was constrained effectively by experimental data of NH₃/N₂O mixtures. Two-stage ignition behaviors were observed for NH₃/H₂ mixtures, and the corresponding first-stage ignition delay times were reported for the first time. Experimental species profiles suggested the first-stage ignition resulted from the consumption of H₂. The oxidation of H₂ provided extra HO₂ radicals, which promoted the production of OH radicals and initiated first-stage ignition. Reactions between HO₂ radicals and NH₃/NH₂ dominated the first-ignition delay times of NH₃/H₂ mixtures. Moreover, the first-stage ignition led to the fast production of NO₂, which acted as a key intermediate and affected the following total ignition. Consequently, the reaction NH₂ + NO₂ = H₂NO + NO (R3) was constrained by total ignition delay times.     

大气等离子体中氮氧化物粒子行为的数值模拟

利用一个空间零维大气等离子体模型对其中的氮氧化物在不同电离度情况下的变化规律进行了数值模拟,得到了放电后不同初始电子密度下的氮氧化物(包括NO,NO⁺,NO₂,NO₂⁺,N₂O,N₂O⁺,NO₃和N₂O₅)及影响其产消的主要反应物N和O₃的密度随时间的演化规律.结果表明,电子初始密度n_e0=10⁹ cm^-3时,NO和NO₂的去除率较高,氮氧化物总密度较小,最适合消除氮氧化物污染.同时,还对N和O₃随电离度变化的行为进行了分析. 关键词： 大气等离子体 氮氧化物 电离度 数值模拟     

Experimental and numerical study of product gas and N2O emission characteristics of ammonia/hydrogen/air premixed laminar flames stabilized in a stagnation flow

In order to achieve carbon neutrality, the use of ammonia as a fuel for power generation is highly anticipated. The utilization of a binary fuel consisting of ammonia and hydrogen can address the weak flame characteristics of ammonia. In this study, the product gas characteristics of ammonia/hydrogen/air premixed laminar flames stabilized in a stagnation flow were experimentally and numerically investigated for various equivalence ratios for the first time. A trade-off relationship between NO and unburnt ammonia was observed at slightly rich conditions. At lean conditions, NO reached a maximum value of 8,700 ppm, which was larger than that of pure ammonia/air flames. The mole fraction of nitrous oxide (N₂O) which has large global warming potential rapidly increased around the equivalence ratio of 0.6, which was attributed to the effect of a decrease in flame temperature downstream of the reaction zone owing to heat loss to the stagnation wall. To understand this effect further, numerical simulations of ammonia/hydrogen/air flames were conducted using the stagnation flame model for various equivalence ratios and stagnation wall temperatures. The results show that the important reactions for N₂O production and reductions are NH +NO = N₂O + H, N₂O + H = N₂ + OH, and N₂O (+M) = N₂ + O (+M). A decrease in flame temperature in the post flame region inhibited N₂O reduction through N₂O (+M) = N₂ + O (+M) because this reaction has a large temperature dependence, and thus N₂O was detected as a product gas. N₂O is reduced through N₂O (+M) = N₂ + O (+M) in the post flame region if the stagnation wall temperature is sufficiently high. On the other hand, it was clarified that an increase in equivalence ratio enhances H radical production and promotes N₂O reduction by H radical through the reaction of N₂O + H = N₂ + OH.