Effect of stoichiometric mixture fraction on soot fraction and emission spectra with application to oxy-combustion

Many proposed oxy-combustion concepts for carbon capture incorporate the recycling of flue gas which is used as a dilution gas to aid in the control of temperature and heat flux. Improvements in efficiency may be realized by significantly reducing the recycle flue gas (RFG), however, in application, care must be taken to avoid excessive radiant heat flux and gas temperature. One of the features oxy-combustion, unlike air-fired combustion, is that the oxygen and dilution gases are initially separated. RFG can, for example, be strategically blended with either the fuel stream, or oxidizer stream, or both, which affects the stoichiometric mixture fraction, Z_st. In this work, the effects of the amount of dilution, or RFG, and Z_st on soot fraction are experimentally investigated in a laminar coflow flame. Carbon dioxide is employed as the dilution gas to simulate the recycling of dry flue gas. Soot fraction and temperature are quantitatively determined by a flame image processing technique. In addition, the visible and near-IR emission spectra are given. When dilution, or RFG, is reduced, while holding Z_st constant, soot formation and thermal radiation increase due to higher temperature. However, high temperature flames with reduced or zero soot are achieved by increasing Z_st via the combination of fuel dilution and oxygen enrichment. This study highlights the inherent flexibility of oxy-fuel combustion, which offers the opportunity to control flame temperature and gas volume while independently controlling soot formation and radiant heat transfer.     

Numerical study of the effects of gravity on soot formation in laminar coflow methane/air diffusion flames under different air stream velocities

Numerical simulations of laminar coflow methane/air diffusion flames at atmospheric pressure and different gravity levels were conducted to gain a better understanding of the effects of gravity on soot formation by using relatively detailed gas-phase chemistry and complex thermal and transport properties coupled with a semi-empirical two-equation soot model. Thermal radiation was calculated using the discrete-ordinates method coupled with a non-grey model for the radiative properties of CO, CO₂, H₂O, and soot. Calculations were conducted for three coflow air velocities of 77.6, 30, and 5 cm/s to investigate how the coflowing air velocity affects the flame structure and soot formation at different levels of gravity. The coflow air velocity has a rather significant effect on the streamwise velocity and the fluid parcel residence time, especially at reduced gravity levels. The flame height and the visible flame height in general increase with decreasing the gravity level. The peak flame temperature decreases with decreasing either the coflow air stream velocity or the gravity level. The peak soot volume fraction of the flame at microgravity can either be greater or less than that of its normal gravity counterpart, depending on the coflow air velocity. At sufficiently high coflow air velocity, the peak soot volume fraction increases with decreasing the gravity level. When the coflow air velocity is low enough, soot formation is greatly suppressed at microgravity and extinguishment occurs in the upper portion of the flame with soot emission from the tip of the flame owing to incomplete oxidation. The numerical results provide further insights into the intimate coupling between flame size, residence time, thermal radiation, and soot formation at reduced gravity level. The importance of thermal radiation heat transfer and coflow air velocity to the flame structure and soot formation at microgravity is demonstrated for the first time.     

Addition of NO2 to a laminar premixed ethylene-air flame: Effect on soot formation

Experiments were conducted on a laminar premixed ethylene-air flame at equivalence ratios of 2.34 and 2.64. Comparisons were made between flames with 5% NO₂ added by volume. Soot volume fraction was measured using light extinction and light scattering and fluorescence measurements were also obtained to provide added insight into the soot formation process. The flame temperature profiles in these flames were measured using a spectral line reversal technique in the non-sooting region, while two-color pyrometry was used in the sooting region. Chemical kinetics modeling using the PREMIX 1-D laminar flame code was used to understand the chemical role of the NO₂ in the soot formation process. The modeling used kinetic mechanisms available in the literature. Experimental results indicated a reduction in the soot volume fraction in the flame with NO₂ added and a delay in the onset of soot as a function of height above the burner. In addition, fluorescence signals—often argued to be an indicator of PAH—were observed to be lower near the burner surface for the flames with NO₂ added as compared to the baseline flames. These trends were captured using a chemical kinetics model that was used to simulate the flame prior to soot inception. The reduction in soot is attributed to a decrease in the H-atom concentration induced by the reaction with NO₂ and a subsequent reduction in acetylene in the pre-soot inception region.     

Influence of pressure on near nozzle flow field and soot formation in laminar co-flow diffusion flames

Soot formation from combustion devices, which tend to operate at high pressure, is a health and environmental concern, thus investigating the effect of pressure on soot formation is important. While most fundamental studies have utilised the co-flow laminar diffusion flame configuration to study the effect of pressure on soot, there is a lack of investigations into the effect of pressure on the flow field of diffusion flames and the resultant influence on soot formation. A recent work has displayed that recirculation zones can form along the centreline of atmospheric pressure diffusion flames. This present work seeks to investigate whether these zones can form due to higher pressure as well, which has never been explored experimentally or numerically. The CoFlame code, which models co-flow laminar, sooting, diffusion flames, is validated for the prediction of recirculation zones using experimental flow field data for a set of atmospheric pressure flames. The code is subsequently utilised to model ethane-air diffusion flames from 2 to 33 atm. Above 10 atm, recirculation zones are predicted to form. The reason for the formation of the zones is determined to be due to increasing shear between the air and fuel steams, with the air stream having higher velocities in the vicinity of the fuel tube tip than the fuel stream. This increase in shear is shown to be the cause of the recirculation zones formed in previously investigated atmospheric flames as well. Finally, the recirculation zone is determined as a probable cause of the experimentally observed formation of a large mass of soot covering the entire fuel tube exit for an ethane diffusion flame at 36.5 atm. Previously, no adequate explanation for the formation of the large mass of soot existed.     

Soot studies of laminar diffusion flames with recirculation zones

This paper describes the unusual sooting structure of three flames established by the laminar recirculation zones of a centerbody burner. The vertically mounted burner consists of an annular air jet and a central fuel jet separated by a bluff-body. The three ethylene fueled flames are identified as: fully sooting, donut-shape, and ring-shape sooting flames. Different shapes of the soot structures are obtained by varying the N₂ dilution in the fuel and air jets while maintaining a constant air and fuel velocity of 1.2 m/s. All three flames have the unusual characteristic that the soot, entrained into the recirculation zone, follows discrete spiral trajectories that terminate at the center of the vortex. The questions are what cause: (1) the unusual sooting structures and (2) the spiral trajectories of the soot? Flame photographs, laser sheet visualizations, and calculations with a 2D CFD-based code (UNICORN) are used to answer these questions. The different sooting structures are related to the spiral transport of the soot, the spatial location of the stoichiometric flame surface with respect to the vortex center, and the burnout of the soot particles. Computations indicate that the spiral trajectories of the soot particles are due to thermophoresis.     

Laser-induced incandescence technique to identify soot nucleation and very small particles in low-pressure methane flames

This paper presents the study we carried out on the formation of soot particles in low-pressure premixed CH₄/O₂/N₂ flames by using Laser-Induced Incandescence (LII). Flames were stabilised at 26.6 kPa (200 torr). Four different equivalence ratios were tested (Φ = 1.95, 205, 2.15 and 2.32), Φ = 1.95 corresponding to the equivalence ratio for which LII signals begin to be measurable along the flame. The evolution of the LII signals with laser fluence (fluence curve), time (temporal decay) and emission wavelength is reported at different heights above the burner. We specifically took advantage of the low-pressure conditions to probe with a good spatial resolution the soot inception zone of the flames. Significant different behaviours of the fluence curves are observed according to the probed region of the flames and Φ. In addition, while the surface growth process is accompanied by an increase in the LII decay-times (indicator of the primary particle diameter) at higher Φ, decay-times become increasingly short at lower Φ reaching a constant value along the flame at Φ = 1.95. These behaviours are consistent with the detection of the smallest incandescent particles in the investigated flames, these particles having experienced very weak surface growth. Flame modelling including soot formation has been implemented in flames Φ = 2.05 and 2.32. Experimental quantitative soot volume fraction profiles were satisfactorily reproduced by adjusting the fraction of reactive soot surface available for reactions. The qualitative variation of the computed soot particle diameter and the relative weight of surface growth versus nucleation were consistent with the experimental observations.     

Effect of H-atom concentration on soot formation in premixed ethylene/air flames

Soot formation is a major challenge in the development of clean and efficient combustion systems based on hydrocarbon fuels. Fundamental understanding of the reaction mechanism leading to soot formation can be obtained by investigating the role of key reactive species such as atomic hydrogen taking part in soot formation pathways. In this study, two-dimensional laser induced incandescence (LII) measurements using λ?=?1064?nm laser have been used to measure soot volume fraction (f_V) in a series of rich ethylene (C₂H₄)/air flames, stabilized over a McKenna burner fitted with a flame stabilizing metal disc. Moreover, a comparison of UV (λ?=?283?nm), visible (λ?=?532?nm) and IR (λ?=?1064?nm) laser excited LII measurements of soot is discussed. Recently developed, femtosecond two-photon laser-induced fluorescence (fs-TPLIF) technique has been applied for obtaining spatially resolved H-atom concentration ([H]) profiles under the same flame conditions. The structure of the flames has also been determined using hydroxyl radical (OH) planar laser induced fluorescence (PLIF) imaging. The results indicate an inverse dependence of f_V on [H] for a range of C₂H₄/air rich flames up to an equivalence ratio, Φ?=?3.0. Although an absolute relationship between [H] and f_V cannot be easily derived owing to the multiple steps involving H and other intermediate species in soot formation pathways, the present study demonstrates the feasibility to couple [H] and f_V obtained using advanced optical techniques for soot formation studies.     

Effects of pressure and fuel dilution on coflow laminar methane–air diffusion flames: A computational and experimental study

In this study, the influence of pressure and fuel dilution on the structure and geometry of coflow laminar methane–air diffusion flames is examined. A series of methane-fuelled, nitrogen-diluted flames has been investigated both computationally and experimentally, with pressure ranging from 1.0 to 2.7 atm and CH₄ mole fraction ranging from 0.50 to 0.65. Computationally, the MC-Smooth vorticity–velocity formulation was employed to describe the reactive gaseous mixture, and soot evolution was modelled by sectional aerosol equations. The governing equations and boundary conditions were discretised on a two-dimensional computational domain by finite differences, and the resulting set of fully coupled, strongly nonlinear equations was solved simultaneously at all points using a damped, modified Newton's method. Experimentally, chemiluminescence measurements of CH* were taken to determine its relative concentration profile and the structure of the flame front. A thin-filament ratio pyrometry method using a colour digital camera was employed to determine the temperature profiles of the non-sooty, atmospheric pressure flames, while soot volume fraction was quantified, after evaluation of soot temperature, through an absolute light calibration using a thermocouple. For a broad spectrum of flames in atmospheric and elevated pressures, the computed and measured flame quantities were examined to characterise the influence of pressure and fuel dilution, and the major conclusions were as follows: (1) maximum temperature increases with increasing pressure or CH₄ concentration; (2) lift-off height decreases significantly with increasing pressure, modified flame length is roughly independent of pressure, and flame radius decreases with pressure approximately as P^?1/2; and (3) pressure and fuel stream dilution significantly affect the spatial distribution and the peak value of the soot volume fraction.     

The importance of thermal radiation transfer in laminar diffusion flames at normal and microgravity

The importance of radiation heat loss in laminar and turbulent diffusion flames at normal gravity has been relatively well recognized in recent years. There is currently lack of quantitative understanding on the importance of radiation heat loss in relatively small scale laminar diffusion flames at microgravity. The effects of radiation heat transfer and radiation absorption on the structure and soot formation characteristics of a coflow laminar ethylene/air diffusion flame at normal- and microgravity were numerically investigated. Numerical calculations were conducted using GRI-Mech 3.0 combustion chemistry without the NO_x mechanism and complex thermal and transport properties, an acetylene based soot formation model, and a statistical narrow-band correlated-k non-grey gas radiation model. Radiation heat transfer and radiation absorption in the microgravity flame were found to be much more important than their counterparts at normal gravity. It is important to calculate thermal radiation transfer accurately in diffusion flame modelling under microgravity conditions.     

Nonane droplet combustion with and without buoyant convection: Flame structure, burning rate and extinction in air and helium

The burning and extinction characteristics of isolated small nonane droplets are examined in a buoyant convective environment and in an environment with no external axial convection (as created by doing experiments at low gravity) to promote spherical droplet flames. The ambience is air and a mixture of 30%O₂/70%He to assess the influence of soot formation. The initial droplet diameter (D_o) ranges from 0.4 to 0.95 mm. Measurements are reported of the extinction diameter and time to extinction, and of the evolution of droplet diameter, flame diameter, soot shell diameter, burning rate, and broadband radiative emissions.In a buoyancy-free environment for air larger droplets burn slower than smaller droplets for the range of D_o examined, which is attributed to the influence of soot. In the presence of a buoyant flow in air, no influence of D_o is observed on the burning rate while the buoyant flames are still heavily sooting. The effect of D_o is believed to be due to a combination of dominance of the nonluminous, nonsooting, portion of the buoyant flame around the forward half of the droplet on heat transport and the secondary role of the luminous wake portion of the flame. In a non-sooting helium inert at low gravity, no effect of D_o is found on the evolution of droplet diameter.Flame extinction is observed only in the 30%O₂/70%He ambience. For all of the observations, extinction appears to occur before the disappearance of the droplet which is then followed by a period of evaporation. The extinction diameter and time to extinction increases with D_o and an empirical correlation is presented for these two variables.     

Transported JPDF modelling and measurements of soot at elevated pressures

Accurate measurements and modelling of soot formation in turbulent flames at elevated pressures form a crucial step towards design methods that can support the development of practical combustion devices. A mass and number density preserving sectional model is here combined with a transported joint-scalar probability density function (JDPF) method that enables a fully coupled scalar space of soot, gas-phase species and enthalpy. The approach is extended to the KAUST turbulent non-premixed ethylene-nitrogen flames at pressures from 1 to 5 bar via an updated global bimolecular (second order) nucleation step from acetylene to pyrene. The latter accounts for pressure-induced density effects with the rate fitted using comparisons with full detailed chemistry up to 20 bar pressure and with experimental data from a WSR/PFR configuration and laminar premixed flames. Soot surface growth is treated via a PAH analogy and soot oxidation is considered via O, OH and O₂ using a Hertz-Knudsen approach. The impact of differential diffusion between soot and gas-phase particles is included by a gradual decline of diffusivity among soot sections. Comparisons with normalised experimental OH-PLIF and PAH-PLIF signals suggest good predictions of the evolution of the flame structure. Good agreement was also found for predicted soot volume statistics at all pressures. The importance of differential diffusion between soot and gas-phase species intensifies with pressure with the impact on PSDs more evident for larger particles which tend to be transported towards the fuel rich centreline leading to reduced soot oxidation.     

A computational study of soot formation and flame structure of coflow laminar methane/air diffusion flames under microgravity and normal gravity

A numerical study is conducted of methane–air coflow diffusion flames at microgravity (μg) and normal gravity (1g), and comparisons are made with experimental data in the literature. The model employed uses a detailed gas phase chemical kinetic mechanism that includes PAH formation and growth, and is coupled to a sectional soot particle dynamics model. The model is able to accurately predict the trends observed experimentally with reduction of gravity without any tuning of the model for different flames. The microgravity sooting flames were found to have lower temperatures and higher volume fraction than their normal gravity counterparts. In the absence of gravity, the flame radii increase due to elimination of buoyance forces and reduction of flow velocity, which is consistent with experimental observations. Soot formation along the wings is seen to be surface growth dominated, while PAH condensation plays a more major role on centreline soot formation. Surface growth and PAH growth increase in microgravity primarily due to increases in the residence time inside the flame. The rate of increase of surface growth is more significant compared to PAH growth, which causes soot distribution to shift from the centreline of the flame to the wings in microgravity.     

Modelling nongrey gas-phase and soot radiation in luminous turbulent nonpremixed jet flames

Much progress has been made in radiative heat transfer modelling with respect to the treatment of nongrey radiation from both gas-phase species and soot particles, while radiation modelling in turbulent flame simulations is still in its infancy. Aiming at reducing this gap, this paper introduces state-of-the-art models of gas-phase and soot radiation to turbulent flame simulations. The full-spectrum k-distribution method (M.F. Modest, 2003, Journal of Quantitative Spectroscopy & Radiative Transfer, 76, 69–83) is implemented into a three-dimensional unstructured computational fluid dynamics (CFD) code for nongrey radiation modelling. The mixture full-spectrum k-distributions including nongrey absorbing soot particles are constructed from a narrow-band k-distribution database created for individual gas-phase species, and an efficient scheme is employed for their construction in CFD simulations. A detailed reaction mechanism including NO _x and soot kinetics is used to predict flame structure, and a detailed soot model using a method of moments is employed to determine soot particle size distributions. A spherical harmonic P₁ approximation is invoked to solve the radiative transfer equation. An oxygen-enriched, turbulent, nonpremixed jet flame is simulated, which features large concentrations of gas-phase radiating species and soot particles. Nongrey soot modelling is shown to be of greater importance than nongrey gas modelling in sooty flame simulations, with grey soot models producing large errors. The nongrey treatment of soot strongly influences flame temperatures in the upstream and the flame-tip region and is essential for accurate predictions of NO. The nongrey treatment of gases, however, weakly influences upstream flame temperatures and, therefore, has only a small effect on NO predictions. The effect of nongrey soot radiation on flame temperature is also substantial in downstream regions where the soot concentration is small. Limitations of the P₁ approximation are discussed for the jet flame configuration; the P₁ approximation yields large errors in the spatial distribution of the computed radiative heat flux for highly anisotropic radiation fields such as those in flames with localized, near-opaque soot regions.     

Modeling nongray gas-phase and soot radiation in luminous turbulent nonpremixed jet flames

Much progress has been made in radiative heat transfer modeling with respect to treatment of nongray radiation from both gas-phase species and soot particles, while radiation modeling in turbulent flame simulations is still in its infancy. Aiming at reducing this gap, this paper introduces state-of-the-art models of gas-phase and soot radiation to turbulent flame simulations. The full-spectrum k-distribution method (Modest, M.F., 2003, Journal of Quantitative Spectroscopy & Radiative Transfer, 76, 69–83) is implemented into a three-dimensional unstructured CFD code for nongray radiation modeling. The mixture full-spectrum k-distributions including nongray absorbing soot particles are constructed from a narrow-band k-distribution database created for individual gas-phase species, and an efficient scheme is employed for their construction in CFD simulations. A detailed reaction mechanism including NO _x and soot kinetics is used to predict flame structure, and a detailed soot model using a method of moments is employed to determine soot particle size distributions. A spherical-harmonic P₁ approximation is invoked to solve the radiative transfer equation. An oxygen-enriched, turbulent, nonpremixed jet flame is simulated, which features large concentrations of gas-phase radiating species and soot particles. Nongray soot modeling is shown to be of greater importance than nongray gas modeling in sooty flame simulations, with gray soot models producing large errors. The nongray treatment of soot strongly influences flame temperatures in the upstream and the flame-tip region and is essential for accurate predictions of NO. The nongray treatment of gases, however, weakly influences upstream flame temperatures and, therefore, has only a small effect on NO predictions. The effect of nongray soot radiation on flame temperature is also substantial in downstream regions where the soot concentration is small. Limitations of the P₁ approximation are discussed for the jet flame configuration; the P₁ approximation yields large errors in the spatial distribution of the computed radiative heat flux for highly anisotropic radiation fields such as those in flames with localized, near-opaque soot regions.     

Effects of benzene,cyclo-hexane and n-hexane addition to methane on soot yields in high-pressure laminar diffusion flames

Effects of doping high pressure methane diffusion flames with benzene, cyclo-hexane and n-hexane were investigated to assess the sooting propensity of three hydrocarbons with six carbons at elevated pressures. Amount of liquid hydrocarbons added to methane constituted 7.5% of the total carbon content of the fuel stream. The pressure range investigated extended up to 10 bar and the experiments were carried out in a high pressure combustion chamber capable of establishing stable laminar diffusion flames with various fuels at elevated pressures and was used in similar experiments previously. Temperatures and soot volume fractions were measured using the spectral soot emission technique capturing spectrally-resolved line-of-sight intensities which were subsequently inverted using an Abel type algorithm to obtain radial distributions assuming that the flames are axisymmetric. The total mass carbon flow of the fuel stream was kept constant at 0.524 mg/s in neat methane, benzene-doped methane, cyclo-hexane-doped methane, and n-hexane-doped methane flames to have tractable measurements at all pressures. Measured maximum soot volume fractions and evaluated maximum soot yields showed that benzene-doped methane flame had the higher values than cyclo-hexane doped methane flames which in turn had higher values than n-hexane doped methane flames at all pressures. Sooting propensity dependence of the three hydrocarbons on pressure can be ranked as, in descending order, n-hexane, cyclo-hexane, and benzene; however, the difference between pressure dependencies of n-hexane and cyclo-hexane was within the measurement error margins. Ratio of soot yields of benzene to n-hexane doped flames changed from about 2 at 2 bar to 1.2 at 10 bar; the ratio of benzene to cyclo-hexane doped flames showed similar trends.     

Modelling of aromatics and soot formation from large fuel molecules

There is a need for prediction models of soot particles and polycyclic aromatic hydrocarbons (PAHs) formation in parametric conditions prevailing in automotive engines: large fuel molecules and high pressure. A detailed kinetic mechanism able to predict the formation of benzene and PAHs up to four rings from C₂ fuels, recently complemented by consumption reactions of decane, was extended in this work to heptane and iso-octane oxidation. Species concentrations measured in rich, premixed flat flames and in a jet stirred reactor (JSR) were used to check the ability of the mechanism to accurately predict the formation of C₂ and C₃ intermediates and benzene at pressures ranging from 0.1 to 2.0 MPa. Pathways analyses show that propargyl recombination is the only significant route to benzene in rich heptane and iso-octane flames. When included as the first step of a soot particle formation model, the gas-phase kinetic mechanism predicts very accurately the final soot volume fraction measured in a rich decane flame at 0.1 MPa and in rich ethylene flames at 1.0 and 2.0 MPa.     

An experimental and numerical investigation of the catalytic-rich/gaseous-lean combustion of H2/CO/air mixtures at 8 bar

The catalytic-rich/gaseous-lean (R/L) combustion concept was investigated experimentally and numerically for syngas fuels with H₂:CO volumetric ratios 1:0, 4:1 and 1:2, catalytic-rich stoichiometries φ_rich = 2–10 (including operation without air), pressure of 8 bar and air preheat of 673 K. Experiments were performed in a subscale R/L burner with optical access to both catalytic-rich and gaseous-lean stages. OH-PLIF monitored the turbulent combustion in the gaseous-lean stage, OH*-chemiluminescence assessed the propensity for homogeneous ignition in the catalytic-rich stage, and exhaust gas analysis provided the NOx and CO emissions. Two-dimensional simulations were carried out for both stages, while a 1-D opposed-jet code modeled the NOx emissions. The exothermicity of the heterogeneous reactions promoted homogeneous ignition and flame anchoring in the upstream parts of the catalytic-rich stage and allowed for complete consumption of the deficient O₂ reactant, a process that could not be achieved by the catalytic pathway alone due to transport limitations. Homogeneous combustion in the catalytic-rich stage was beneficial for attaining the highest possible fuel pre-conversion. The catalyst not only initiated gaseous combustion but also mitigated potential NOx emissions from the catalytic-rich stage at the highest pre-conversions (lowest φ_rich) and highest CO-content mixtures. Two-sided diffusion flames were established in the gaseous-lean stage due to the recirculation of O₂-rich combustion products, which was advantageous for the burner compactness. It was shown that cardinal to the R/L concept was the fact that a decreasing φ_rich led to an increased heat transfer from the catalytic-rich stage to the bypass air, which reduced the enthalpy in the fuel stream of the gaseous-lean stage and thus lowered the peak flame temperatures (by 400 K for H₂:CO = 1:0). The reduction in flame temperatures with decreasing φ_rich led to a six-fold drop in NOx emissions, while CO emissions were less than 5 ppmv.     

Quantitative measurement of naphthalene in low-pressure flames by jet-cooled laser-induced fluorescence

We have recently developed a new laser based set-up (Jet-Cooled Laser-Induced Fluorescence) for the analysis of aromatic compounds generated in flames. This method relies on the extraction of the species from the flame via a thin microprobe and their direct analysis inside a supersonic free jet by Laser-Induced Fluorescence (LIF). Under the supersonic conditions of the jet, the vibronic spectra of the molecules become structured as the possibility of electronic transitions is reduced, allowing their selective detection by LIF. In addition, due to the very low quenching efficiency inside the jet, LIF signals can be directly related to the population of the probed species and easily calibrated into absolute concentrations. All of the work presented here has been carried out for naphthalene, which is an important PAH involved in soot formation mechanisms. The calibration procedure is described in detail. We also report a detailed study of the quantitative features of the technique, in particular cooling efficiencies and collision rates as well as some additional potential factors that could bias the quantitative aspect of the method. Finally, the possibilities of the technique for the measurement of PAH within flames in the presence of soot particles along with its accuracy and reproducibility are demonstrated by recording naphthalene mole fractions profiles in several rich CH₄/O₂/N₂ flames. A detection limit of the order of a ppb is demonstrated under flame conditions with and without the presence of soot particles.     

Spatially resolved measurements of soot and gaseous precursors in ethylene counterflow diffusion flames up to 32 atm

We investigate the effect of pressure on both flame structure and soot formation in nitrogen diluted counterflow diffusion flames of ethylene in the 8–32atm pressure range. Capillary-probe gas sampling is performed to resolve spatially the profiles of gaseous species up to three-ring aromatics by GC/MS analysis and multi-color pyrometry is used to quantify the soot volume fraction and dispersion exponent. Self-similarity of flames is preserved by keeping constant mixture fraction and strain rate, so that profiles of concentrations and temperature, normalized with respect to their peak values, are unaffected by changes in pressure, once the axial coordinate is nondimensionalized with respect to the pressure-dependent diffusion length scale. When conditions are chosen so that the overall soot loading is approximately constant and compatible with the diagnostics, it is found that both the soot volume fraction and the profiles of key aromatics in the high-temperature nucleation region are virtually invariant. For it to happen, a twofold increase in pressure must be compensated by a ～100 K decrease in peak flame temperature and, therefore, in the temperature across the soot forming region. The implication is that from the perspective of the chemical kinetics of soot formation these two actions counterbalance each other. As pressure increases (and temperature decreases) the peak production rate of the high-temperature soot mechanism decreases and, further downstream, towards the particle stagnation plane, a low-temperature soot mechanism sets in, yielding an increase in soot H/C content. This mechanism is enhanced as the pressure is raised, causing a higher overall soot volume production rate in the 16atm flame and, especially, in the 32atm one. The role of C4/C2 species in the formation of C₆H₆ increases with increasing pressure and dominates over the recombination of propargyl radical at sufficiently high pressures. A comprehensive database is established for soot models at high pressures of relevance to applications.     

Effects of OH concentration and temperature on NO emission characteristics of turbulent non-premixed CH4/NH3/air flames in a two-stage gas turbine like combustor at high pressure

This study examined the effects of OH concentration and temperature on the NO emission characteristics of turbulent, non-premixed methane (CH₄)/ammonia (NH₃)/air swirl flames in two-stage combustors at high pressure. Emission data were obtained using large-eddy simulations with a finite-rate chemistry method from model flames based on the energy fraction of NH₃ (E_NH3) in CH₄/NH₃ mixtures. Although NO emissions at the combustor exit were found to be significantly higher than those generated by CH₄/air and NH₃/air flames under both lean and stoichiometric primary zone conditions, these emissions could be lowered to approximately 300 ppm by employing far-rich equivalence ratios (?) of 1.3 to 1.4 in the primary zone. This effect was possibly due to the lower OH concentrations under far-rich conditions. An analysis of local flame characteristics using a newly developed mixture fraction equation for CH₄/NH₃/air flames indicated that the local temperature and NO and OH concentration distributions with local ? were qualitatively similar to those in NH₃/air flames. That is, the maximum local NO and OH concentrations appeared at local ? of 0.9, although the maximum temperature was observed at local ? of 1.0. Both the temperature and OH concentration were found to gradually decrease with the partial replacement of CH₄ with NH₃. Consequently, NO emissions from CH₄/NH₃ flames were maximized at E_NH3 in the range of 20% to 30%, after which the emissions decreased. Above 2100 K, the NO emissions from CH₄/NH₃ flames increased exponentially with temperature, which was not observed in NH₃/air flames because of the lower flame temperatures in the latter. But, the maximum NO concentration in CH₄/NH₃ flames was occurred at a temperature slightly below the maximum temperature, just as in NH₃/air flames. The apparent exponential increase in NO emissions from CH₄/NH₃ flames is attributed to a similar trend in the OH concentration at high temperatures.