Flame structure of HMX/GAP propellant at high pressure

The chemical and thermal structure of a HMX/GAP propellant flame was investigated at a pressure of 0.5 MPa using molecular beam mass spectrometry and a microthermocouple technique. The pressure dependence of the burning rate was measured in the pressure range of 0.5–2 MPa. The mass spectrometric probing technique developed for flames of energetic materials was updated to study the chemical structure of HMX/GAP flames at high pressures. Eleven species, including HMX vapor, were identified, and their concentrations were measured in a zone adjacent to the burning surface at pressures of 0.5 and 1 MPa. Temperature profiles in the propellant combustion wave were measured at pressures of 0.5 and 1 MPa. Species concentration profiles were measured at 0.5 MPa. Two main zones of chemical reactions in the flame were found. The data obtained can be used to develop and validate combustion models for HMX/GAP propellants.     

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.     

Nitrogen release during reaction of coal char with O2, CO2, and H2O

The chemistry of char-N release and conversion to nitrogen-containing products has been probed by studying its release and reactions with O₂, CO₂, and H₂O. The experiments were performed in a fixed bed flow reactor at pressures of up to 1.0 MPa. The results show that the major nitrogen-containing products observed depend on the reactant gas; with O₂, NO, and N₂ being the major species observed. Char-N reaction with CO₂ produces N₂ with very high selectivity over a broad range of pressures and CO₂ concentrations, and reaction with H₂O gives rise to HCN, NH₃, and N₂. Observed distributions of nitrogen-containing products are little affected by pressure when O₂ and CO₂ are the reactant gases, but increasing pressures in the reaction with H₂O results in the formation of increasing proportions of NH₃. Formation of NH₃ is also promoted by increasing concentrations of H₂O in the feed gas. The results suggest that NO and HCN are primary products when O₂ and H₂O, respectively, are used as the reactant gases, and that the other observed products arise from interactions of these primary products with the char surface.     

On the mechanism of inhibition of a hydrogen flame by propane

Numerical simulations demonstrated that small additives of propane to rich hydrogen-air mixtures suppress the formation of HO₂ and OH in the low-temperature region of the flame zone, thereby causing a substantial decrease in the laminar flame speed. In the low-and high-temperature regions, propane interacts predominantly with OH and H, respectively. In the flame zone, propane is completely converted to CO, CO₂, CH₄, C₂H₂, H₂, and H₂O, being oxidized concurrently with hydrogen at that.     

Microscopic insight into catalytic HCN removal over the CuO surface in chemical looping combustion

Hydrogen cyanide (HCN) is well-accepted as a main nitrogen-containing precursor from fuel nitrogen to nitrogen oxides. When using coal as fuel with a CuO-based oxygen carrier in chemical looping combustion (CLC), complex heterogeneous reactions exist among the system of HCN, O₂, NO, H₂O, and CuO particles. This work performs density functional theory (DFT) calculations to systematically probe the microscopic HCN heterogeneous reactions over the CuO particle surface. The results indicate that HCN is chemisorbed on the CuO surface, and the third dissociation step within the consecutive three-step HCN dissociations (HCN*→CN*→NCO*→N*) is the rate-determining step. Namely, the CN*/NCO* radicals can be deemed as an indicator of the performance of HCN removal due to their quite higher dissociation energies. With the existence of O₂, H₂O, and NO, the reaction mechanism of HCN conversion becomes extremely complex. Both DFT calculations and kinetic analyses determine that O₂, NO, and H₂O all significantly accelerate the consumption of CN*/NCO* radicals to produce various N-containing species (NOx or NH₃) to different extents. Finally, a skeletal reaction network in a system of O₂/NO/H₂O/HCN is concluded, which clearly elucidates that CuO exhibits excellent catalytic activity toward HCN removal.     

Dilution effects analysis of opposed-jet H2/CO syngas diffusion flames

This paper reported the analysis of dilution effects on the opposed-jet H₂/CO syngas diffusion flames. A computational model, OPPDIF coupled with narrowband radiation calculation, was used to study one-dimensional counterflow syngas diffusion flames with fuel side dilution from CO₂, H₂O and N₂. To distinguish the contributing effects from inert, thermal/diffusion, chemical, and radiation effects, five artificial and chemically inert species XH₂, XCO, XCO₂, XH₂O and XN₂ with the same physical properties as their counterparts were assumed. By comparing the realistic and hypothetical flames, the individual dilution effects on the syngas flames were revealed. Results show, for equal-molar syngas (H₂/CO = 1) at strain rate of 10 s^?1, the maximum flame temperature decreases the most by CO₂ dilution, followed by H₂O and N₂. The inert effect, which reduces the chemical reaction rates by behaving as the inert part of mixtures, drops flame temperature the most. The thermal/diffusion effect of N₂ and the chemical effect of H₂O actually contribute the increase of flame temperature. However, the chemical effect of CO₂ and the radiation effect always decreases flame temperature. For flame extinction by adding diluents, CO₂ dilution favours flame extinction from all contributing effects, while thermal/diffusion effects of H₂O and N₂ extend the flammability. Therefore, extinction dilution percentage is the least for CO₂. The dilution effects on chemical kinetics are also examined. Due to the inert effect, the reaction rate of R84 (OH+H₂ = H+H₂O) is decreasing greatly with increasing dilution percentage while R99 (CO+OH→CO₂+H) is less affected. When the diluents participate chemically, reaction R99 is promoted and R84 is inhibited with H₂O addition, but the trend reverses with CO₂ dilution. Besides, the main chain-branching reaction of R38 (H+O₂→O+OH) is enhanced by the chemical effect of H₂O dilution, but suppressed by CO₂ dilution. Relatively, the influences of thermal/diffusion and radiation effects on the reaction kinetics are then small.     

Raman spectroscopic study of a laminar hydrogen diffusion flame in air

Spontaneous Raman spectroscopy has been employed for time-averaged, spatially-resolved measurements of temperature and species concentration in an axisymmetric, laminar hydrogen diffusion flame in quiescent air. Temperatures were obtained from vibrational Q-branch raman spectra of N₂, O₂, and H₂ and the rotational Raman spectra of N₂ and H₂, and concentrations of H₂, and N₂ were determined. The results are compared to existing numerical nonequilibrium calculations for the conditions of this experiment. Significant differences between experimental and predicted temperature and concentration profiles are observed. In particular, the flame is larger in both diameter and length and the flame zone is thicker than predicted. Some possible sources of the discrepancies are discussed.     

Interactions of hydrogen and nitric oxide in outwardly propagating spherical flame: Insight into non-hydrocarbon NOX reduction mechanism

Co-firing ammonia (NH₃) and hydrogen (H₂) or H₂-rich fuel and partially cracking NH₃ are promising non-carbon combustion techniques for gas turbines and marine engines, raising a growing need to understand the interactions of H₂ and nitric oxide (NO) as well as the non-hydrocarbon nitrogen oxides (NO_X) reduction mechanism under flame conditions. In this work, the outwardly propagating spherical flame method was used to investigate the laminar flame propagation of H₂/NO and H₂/NO/nitrogen (N₂) mixtures at initial pressure (P_u) of 2 atm, initial temperature (T_u) of 298 K and equivalence ratios of 0.2-1.4. The laminar burning velocities (LBVs) of H₂/NO mixtures are generally 5-10 times lower than those of H₂/air mixtures, while the dilution of N₂ can dramatically inhibit the laminar flame propagation. A kinetic model of H₂/NO combustion was constructed and validated against the new data in this work and other types of experimental data in literature. The modeling analyses reveal that NO+H=N+OH becomes the most important chain-branching reaction in H₂/NO reaction system, while the LBV data of H₂/NO mixtures in this work can provide highly sensitive validation targets for the kinetics in H₂ and NO interactions. Furthermore, the NO reduction to N₂ mainly proceeds through NO+N=N₂+O under various H₂/NO ratios, and NO+O=N+O₂ is found to have a significant contribution to NO reduction under NO-rich conditions.     

Oscillatory cool flame combustion behavior of submillimeter sized n-alkane droplet under near limit conditions

This paper reports simulation results of oscillatory cool flame burning of an isolated, submillimeter sized n-heptane (n-C₇H₁₆) droplet in a selectively ozone (O₃) seeded nitrogen-oxygen (N₂-O₂) environments at atmospheric pressure. An evolutionary one-dimensional droplet combustion code encompassing relevant physics and detailed chemistry was employed to explore the roles of low-temperature chemistry, O₃ seeding, and dynamic flame structure on burning behaviors. For X_O2= 21% and a range of selective ozone seeding, near-quasi-steady cool flame burning is achieved directly (without requiring hot flame initiation and radiative extinction). Under low oxygen index conditions, but with significant O₃ seeding (X_O3 = 5%), a nearly quasi-steady cool flame is initially established that then transitions to a dynamically oscillating cool flame burning mode which continues until the droplet is completely consumed. It is found that the oscillation occurs as result of a initial depletion of fuel vapor-oxidizer layer evolving near the droplet surface and its dynamic re-establishment through liquid vaporization and vapor/oxidizer transport. A kinetic analysis indicates that the dynamic competition between the reaction classes- (a) degenerate chain branching and (b) chain termination/propagation - along with continuous fuel and oxygen leakage through the flame location contributes to an oscillatory burning phenomena of ever-increasing amplitude. Analysis based on single full-cycle of oscillatory burning shows that the reaction progression matrices (evolution of heat and species) for QOOH➔chain propagation/termination reactions (here, Q = C₇H₁₄-) directly scales with the gas phase temperature field. On the contrary, the QOOH➔degenerate branching reactions undergoes three distinct stages within the same oscillatory cycle. The coupled flame dynamics and kinetics suggest that in the oscillatory burning mode, kinetic processes dynamically cross through conditions characterizing the negative temperature coefficient (NTC) turnover temperature, separating low temperature and NTC kinetic regimes. In addition, a parametric study is conducted to determine the role of O₃ seeding level on the observed oscillation phenomena.     

An experimental and kinetic modeling study of a premixed nitromethane flame at low pressure

A premixed nitromethane/oxygen/argon flame at low pressure (4.67 kPa) has been investigated using tunable vacuum ultraviolet (VUV) photoionization and molecular-beam mass spectrometry. About 30 flame species including hydrocarbons, oxygenated and nitrogenous intermediates have been identified by measurements of photoionization efficiency spectra. Mole fraction profiles of the flame species have been determined by scanning burner position at some selected photon energies. The results indicate that N₂ and NO are the major nitrogenous products in the nitromethane flame. Compared with previous studies on nitromethane combustion, a number of unreported intermediates, including C₃H₄, C₄H₆, C₄H₈, C₂H₂O, C₂H₄O, CH₃CN, H₂CNHO, C₃H₃N and C₃H₇N, are observed in this work. Based on our experimental results and previous modeling studies, a detailed oxidation mechanism including 69 species and 314 reactions has been developed to simulate the flame structure. Despite some small discrepancies, the predictions by the modeling study are in reasonable agreement with the experimental results.     

Application of the overtone CO laser to atmosphere gas analysis

In this paper, we consider the applicability of the overtone CO laser to atmosphere gas analysis. The atmosphere transmittance was calculated for lasing lines at the overtone frequencies of the CO laser. The results of the search for informative wavelengths for sensing the minor gas components of the atmosphere N₂O, NO₂, H₂CO, CH₄, C₂H₂, HCl, HBr, and HCN are presented.     

Influence of wall heat loss on the emission characteristics of premixed ammonia-air swirling flames interacting with the combustor wall

The influence of wall heat loss on the emission characteristics of ammonia-air swirling flames has been investigated employing Planar Laser-Induced Fluorescence imaging of OH radicals and Fourier Transform Infrared spectrometry of the exhaust gases in combustors with insulated and uninsulated walls over a range of equivalence ratios, ?, and pressures up to 0.5 MPa. Strong influence of wall heat loss on the flames led to quenching of the flame front near the combustor wall at 0.1 MPa, resulting in large unburned NH₃ emissions, and inhibited the stabilization of flames in the outer recirculating zone (ORZ). A decrease in heat loss effects with an increase in pressure promoted extension of the fuel-rich stabilization limit owing to increased recirculation of H₂ from NH₃ decomposition in the ORZ. The influence of wall heat loss resulted in emission trends that contradict already reported trends in literature. NO emissions were found to be substantially low while unburned NH₃ and N₂O emissions were high at fuel-lean conditions during single-stage combustion, with values such as 55 ppmv of NO, 580 ppmv of N₂O and 4457 ppmv of NH₃ at ? = 0.8. In addition, the response of the flame to wall heat loss as pressure increased was more important than the effects of pressure on fuel-NO emission, thereby leading to an increase in NO emission with pressure. It was found that a reduction in wall heat loss or a sufficiently long fluid residence time in the primary combustion zone is necessary for efficient control of NH₃ and N₂O emissions in two-stage rich-lean ammonia combustors, the latter being more effective for N₂O in addition to NO control. This study demonstrates that the influence of wall heat loss should not be ignored in emissions measurements in NH₃-air combustion, and also advances the understanding of previous studies on ammonia micro gas turbines.     

Characterizing methane and nitric oxide interaction in oxygen-free outwardly propagating spherical flame

Co-firing methane (CH₄) and ammonia (NH₃) has attracted growing concerns as a feasible greenhouse gas reduction strategy in gas turbine-based power generation, which raises the need to better understand the interaction of methane and nitric oxide (NO) under flame conditions. In this work, laminar flame propagation of CH₄/NO mixtures at initial pressure (P_u) of 1 atm, initial temperature (T_u) of 298 K and equivalence ratios of 0.4–1.8 was experimentally investigated using a constant-volume combustion vessel. Laminar burning velocities (LBVs) and Markstein lengths were experimentally determined. A kinetic model of CH₄/NO combustion was developed with rate constants of several important reactions updated, presenting reasonable predictions on the measured LBVs of CH₄/NO mixtures. The modeling analyses reveal that the reduction of NO can proceed through two mechanisms, i.e. the hydrocarbon NO reduction mechanism and non-hydrocarbon NO reduction mechanism. Among the two mechanisms, the non-hydrocarbon NO reduction mechanism which includes reactions NO+H = N+OH, NO+O = N + O₂ and NO+N = N₂+O has a higher contribution to NO reduction at the equivalence ratio of 0.6, while the hydrocarbon NO reduction mechanism with hydrocyanic acid (HCN) as the key intermediate plays a more important role at the equivalence ratio of 1.8. NO+H = N+OH and CH₃+NOHCN+H₂O are found to be the two most sensitive reactions to promote the flame propagation, while the LBVs measured in this work are demonstrated to provide strong constraint for these reactions. Furthermore, previous CH₄/O₂/NO oxidation data measured in flow reactor and rapid compression machine were also simulated, which provides extended validation of the present model over wider conditions.     

Ignition and volatile combustion behaviors of a single lignite particle in a fluidized bed under O2/H2O condition

O₂/H₂O combustion, as a new evolution of oxy-fuel combustion, has gradually gained more attention recently for carbon capture in a coal-fired power plant. The physical and chemical properties of steam e.g. reactivity, thermal capacity, diffusivity, can affect the coal combustion process. In this work, the ignition and volatile combustion characteristics of a single lignite particle were first investigated in a fluidized bed combustor under O₂/H₂O atmosphere. The flame and particle temperatures were measured by a calibrated two-color pyrometry and pre-buried thermocouple, respectively. Results indicated that the volatile flame became smaller and brighter as the oxygen concentration increased. The ignition delay time of particle in dense phase was shorter than that in dilute phase due to its higher heat transfer coefficient. Also, the volatile flame was completely separated from particles (defined as off-flame) in dense phase while the flame lay on the particle surface (defined as on-flame) in dilute phase. The self-heating of fuel particles by on-flame in dilute phase was more obvious than that in dense phase, leading to earlier char combustion. At low oxygen concentration, the flame in the H₂O atmosphere was darker than that in the N₂ atmosphere because the heat capacity of H₂O is higher than that of N₂. With the increase of oxygen concentration, the flame temperature in the O₂/H₂O atmosphere was dramatically enhanced rather than that in the O₂/N₂ atmosphere, where the diffusion rate of oxygen in O₂/N₂ atmosphere became the dominant factor.     

Inhibition of premixed and nonpremixed flames with phosphorus-containing compounds

The inhibition/extinction of various flames—premixed stoichiometric C₃H₈/air, nonpremixed counterflow CH₄/O₂/N₂, and nonpremixed coflow n-heptane/air cup-burner flames doped with a number of phosphorus-containing compounds (PCCs)—has been investigated experimentally. More than 20 PCCs (organic phosphates, phosphonates, phosphates) and their fluorinated derivatives were studied. All PCCs exhibited similar dependencies in burning velocities, extinction strain rates, and extinction volume fractions of CO₂ upon PCC loading in the range of mole fractions of 0–7000 ppm within an experimental deviation of ± 5%. This confirms that the inhibition effectiveness of the PCCs is influenced by the phosphorus content in the PCC molecule rather than by the structure of the molecule. The burning velocity of a stoichiometric C₃H₈/air mixture and the extinction strain rate of a nonpremixed counterflow CH₄/O₂/N₂ flame doped with trimethylphosphate were calculated. Satisfactory agreement between experimental and modeling results confirms the conclusion that the reactions of phosphorus oxyacids with radicals are responsible for flame inhibition.     

Quantitative one-dimensional single-pulse multi-species concentration and temperature measurement in the lift-off region of a turbulent H2/air diffusion flame

In this article, we report on one-dimensional single-pulse measurements of temperature and major-species concentration (O₂, N₂, H₂O and H₂) in a turbulent H₂/air jet diffusion flame using Raman and Rayleigh scattering of KrF* excimer-laser radiation. Spatial resolution of 0.5 mm along a 6mm long line has been obtained, with reasonable error limits for mole fraction ( = 5 % for N₂ detection) and temperature (T = 8 %) determination at flame temperatures. We present various profiles showing the composition and temperature along a line at different heights in the flame with particular emphasis on the lift-off region (i.e. lowx/D). In this zone, temperature and mixture fraction can be determined simultaneously — from a single laser pulse — in a spatial region extending from unburnt gas in the center of the jet across the flame front into the cool air of the surrounding atmosphere. This allows for the first time the systematic study of the shape and width of the high-temperature region and the corresponding concentration and temperature gradients. The comparison of averaged data and scatter plots with previous pointwise measurements shows good agreement.     

Understanding the effect of CaO on HCN conversion and NOx formation during the circulating fluidized combustion process using DFT calculations

Hydrogen cyanide (HCN) is an important intermediate during the conversion of fuel nitrogen to NO_x. The mechanism of HCN oxidation to NO, N₂, and N₂O on the CaO (100) surface model was investigated using density functional theory calculations to elucidate the effect of in-furnace SO_x removal on HCN oxidation in circulating fluidized bed boilers. HCN adsorption on the CaO (100) surface releases as high as 1.396 eV and the HC bond is strongly activated. The CaO (100) surface could catalyze the oxidation of CN radical to NCO with the energy barrier decreasing from 1.560 eV for the homogeneous case to 0.766 eV on the CaO (100) surface. The succeeding oxidation of NCO by O₂ forming NO is catalyzed by the CaO (100) surface with the energy barrier decreasing from 0.349 eV (homogeneous process) to 0.026 eV on the CaO (100) surface, while the reaction between NCO and NO forming either NO or N₂ is prohibited in comparison with corresponding homogeneous routes. The rate constants of these reactions under fluidized bed combustion temperature range are provided, and the calculation results lead to the conclusion that CaO (100) surface catalyzes the HCN conversion and improves the NO selectivity during HCN oxidation in the HCN/O₂/NO atmosphere, which could well explain previous experimental observations. Kinetic parameters of HCN oxidation on the CaO (100) surface are provided in the Arrhenius form for future kinetic model development.     

Enhanced Al-H2O-based fuels combustion characteristics with polyacrylamide at low pressures

The combustion behavior of nano-aluminum-water (n-Al-H₂O) mixture with addition of polyacrylamide (PAM) was investigated in argon at 0.1～1.5 MPa using a constant-pressure strand burner. The burning rates of n-Al-H₂O mixture were measured. The results show that PAM addition can not only help improve the burning rate of n-Al-H₂O mixture, but also decrease the pressure index of burning rate. The mixture of n-Al powder and H₂O cannot be ignited in argon at 0.1 MPa, but the mixture of n-Al powder and H₂O with the 3 wt % PAM can be ignited, and the mixture can support the self-sustaining combustion. The burning rate is 7.64 mm/s. Moreover, the burning rate increases with increasing the pressure. In addition, the combustion process and flame image characteristics were obtained by a high-speed photography technique, and the element composition and surface morphology of the condensed combustion products were evaluated using a scanning electron microscopy combined with energy dispersive X-ray system.     

Influence of nitrogen in aluminum droplet combustion

The influence of nitrogen on the aluminum droplet combustion under forced convection conditions has been studied. An aerodynamic levitation technique of millimetric size liquid droplets heated with a CO₂ laser has been adopted to characterize the combustion of aluminum droplets and, in particular, to observe the surface phenomena. The determination of the burning rate and of the droplet temperature in several atmospheres (H₂O/O₂, H₂O/Ar, H₂O/N₂, and air) has shown that they depend only on the nature and concentration of the oxidizers (O₂ and H₂O); a comparison of experiments in nitrogen and in argon containing mixtures demonstrated that N₂ did not influence the gas phase combustion. However, for nitrogen containing atmospheres we observed the formation of solid aluminum nitride (AlN) at the droplet surface after a latency time depending on the nitrogen pressure. AlN first interacts with the oxide cap producing an aluminum oxynitride, then completely covers the droplet, and finally prevents combustion. The existence of a latency time varying with the nitrogen pressure suggests that the AlN formation is controlled by heterogeneous kinetics. The phenomenon of oxide cap regression during combustion was also observed in all gases, and it is attributed to a chemical decomposition process of alumina by aluminum forming gaseous Al_xO_y species. Therefore, nitrogen effects are significant at the droplet surface rather than in the gas phase, and it is suggested that N₂ is probably one of the main species causing the manifestation of unsteady processes during aluminum droplet burning.     

The effects of water dilution on hydrogen,syngas, and ethylene flames at elevated pressure

This work investigates experimentally and numerically the kinetic effects of water vapor addition on the burning rates of H₂, H₂/CO mixtures, and C₂H₄ from 1 atm to 10 atm at flame temperatures between 1600 K and 1800 K. Burning rates were measured using outwardly propagating spherical flames in a nearly constant pressure chamber. Results show good agreement with newly updated kinetic models for H₂ flames. However, there is considerable disagreement between simulations and measurements for H₂/CO and C₂H₄ flames at high pressure and high water vapor dilution. Both experiments and simulations show that water vapor addition causes a monotonic decrease in mass burning rate and the inhibitory effect increases with pressure. For hydrogen flames, water vapor addition reduces the critical pressure above which a negative pressure dependence of the burning rate is observed. However, for C₂H₄ flames, the burning rate always increases with pressure. The results also show that water vapor addition has the same effect as a pressure increase for H₂ and H₂/CO flames, shifting the reaction zone into a narrower window at higher temperatures. For all fuels, water vapor addition increases OH formation via H₂O + O while reducing the overall active radical pool for hydrogen flames. For C₂H₄, the additional HO₂ production pathway through HCO results in a dramatic difference in pressure dependence of the burning rate from that observed for hydrogen. The present work provides important additions to the experimental database for syngas and C₀–C₂ high pressure kinetic model validations.