Different chemical effect of hydrogen addition on soot formation in laminar coflow methane and ethylene diffusion flames

Previous studies showed that adding hydrogen (H₂) can have an opposite chemical effect on soot formation: its chemical effect enhances and suppresses soot formation in methane (CH₄) and ethylene (C₂H₄) diffusion flames, respectively. Such opposite chemical effect of H₂ (CE-H₂) remains unresolved. The different CE-H₂ is studied numerically in the two laminar coflow diffusion flames. A detailed chemical mechanism with the addition of a chemically inert virtual species FH₂ is used to model the gas-phase combustion chemistry in this study. Particularly, a reaction pathway analysis was performed based on the numerical results to gain insights into how H₂ addition to fuel affects the pathways leading to the formation of benzene (A₁) in CH₄ and C₂H₄ flames. The numerical results show that the CE-H₂ in CH₄ diffusion flame to prompt soot formation is ascribed that the higher mole fraction of H atom promotes the formation of A₁ and Acetylene (C₂H₂) and leads to higher nucleation rate and eventually higher soot surface growth rate. In contrast, adding H₂ to C₂H₄ diffusion flames decreases soot nucleation and surface growth rate. The lower soot nucleation rate is due to the lower mole fractions of pyrene (A₄), while the lower soot surface growth rate is due to the lower mole fractions of H atom and C₂H₂, higher mole fraction of H₂ and lower soot nucleation rate. Furthermore, the CE-H₂ in C₂H₄ diffusion flames promotes the formation of A₁, but suppresses the formation of A₄.     

Structure of laminar sooting inverse diffusion flames

The flame structure of laminar inverse diffusion flames (IDFs) was studied to gain insight into soot formation and growth in underventilated combustion. Both ethylene-air and methane-air IDFs were examined, fuel flow rates were kept constant for all flames of each fuel type, and airflow rates were varied to observe the effect on flame structure and soot formation. Planar laser-induced fluorescence of hydroxyl radicals (OH PLIF) and polycyclic aromatic hydrocarbons (PAH PLIF), planar laser-induced incandescence of soot (soot PLII), and thermocouple-determined gas temperatures were used to draw conclusions about flame structure and soot formation. Flickering, caused by buoyancy-induced vortices, was evident above and outside the flames. The distances between the OH, PAH, and soot zones were similar in IDFs and normal diffusion flames (NDFs), but the locations of those zones were inverted in IDFs relative to NDFs. Peak OH PLIF coincided with peak temperature and marked the flame front. Soot appeared outside the flame front, corresponding to temperatures around the minimum soot formation temperature of 1300 K. PAHs appeared outside the soot layer, with characteristic temperature depending on the wavelength detection band. PAHs and soot began to appear at a constant axial position for each fuel, independent of the rate of air flow. PAH formation either preceded or coincided with soot formation, indicating that PAHs are important components in soot formation. Soot growth continued for some time downstream of the flame, at temperatures below the inception temperature, probably through reaction with PAHs.     

Soot formation and temperature field structure in laminar propane-air diffusion flames at elevated pressures

The effect of pressure on soot formation and the structure of the temperature field was studied in coflow propane-air laminar diffusion flames over the pressure range of 0.1 to 0.73 MPa in a high-pressure combustion chamber. The fuel flow rate was selected so that the soot was completely oxidized within the visible flame and the flame was stable at all pressures. Spectral soot emission was used to measure radially resolved soot volume fraction and soot temperature as a function of pressure. Additional soot volume fraction measurements were made at selected heights using line-of-sight light attenuation. Soot concentration values from these two techniques agreed to within 30% and both methods exhibited similar trends in the spatial distribution of soot concentration. Maximum line-of-sight soot concentration along the flame centerline scaled with pressure; the pressure exponent was about 1.4 for pressures between 0.2 and 0.73 MPa. Peak carbon conversion to soot, defined as the percentage of fuel carbon content converted to soot, also followed a power-law dependence on pressure, where the pressure exponent was near to unity for pressures between 0.2 and 0.73 MPa. Soot temperature measurements indicated that the overall temperatures decreased with increasing pressure; however, the temperature gradients increased with increasing pressure.     

Soot formation in high pressure laminar diffusion flames

The details of the chemical and physical mechanisms of the soot formation process in combustion remain uncertain due to the highly complex nature of hydrocarbon flames, and only a few principles are firmly established mostly for atmospheric conditions. In spite of the fact that most combustion devices used for transportation operate at very high pressures (e.g., aircraft gas turbines up to 40 atm, diesel engines exceeding 100 atm), our understanding of soot formation at these pressures is not at a desirable level, and there is a fundamental lack of experimental data and complementary predictive models. The focus of this review is to assess the experimental results available from laminar co-flow diffusion flames burning at elevated pressures. First, a brief review of soot formation mechanisms in diffusion flames is presented. This is followed by an assessment of soot diagnostics techniques, both intrusive and non-intrusive, most commonly used in soot experiments including the laser induced incandescence. Then the experimental results of soot measurements done at elevated pressures in diffusion flames are reviewed and critically assessed. Soot studies in shock tubes and in premixed flames are not covered. Smoke point fuel mass flow rate is revisited, and shortcomings in recent measurements are pointed. The basic requirements for tractable and comparable measurements as a function of pressure are summarized. Most recent studies at high pressures with aliphatic gaseous fuels show that the soot yield displays a unified behaviour with reduced pressure. The maximum soot yield seems to reach a plateau asymptotically as the pressure exceeds the critical pressure of the fuel. Lack of experimental data on the sensitivity of soot morphology to pressure is emphasized. A short summary of efforts in the literature on the numerical simulation of soot formation in diffusion flames at high pressures is the last section of the paper.     

Effects of fuel inlet boundary condition on aromatic species formation in coflow diffusion flames

In a number of previous numerical studies, the fuel inlet velocity boundary conditions (BC) of coflow diffusion flames were specified at the exit of the fuel nozzle with a parabolic velocity profile. Such choices were based on the assumption that the flow inside the vertical fuel tube is fully developed and the buoyancy has negligible impact on the fuel flow at the nozzle exit. These assumptions, however, might not hold in practical experiments. This study demonstrates it is necessary to account for the effect of inlet BC location to accurately predict the nozzle exit velocity profile as well as the velocity, temperature profiles downstream, which are prerequisites for meaningful polycyclic aromatic hydrocarbon (PAH) and soot prediction in coflow diffusion flames. In particular, laboratory-scale laminar coflow diffusion flames at atmospheric pressure have been studied computationally with a focus on the effects of the fuel inlet velocity profile on PAH formation. Two sets of simulations were conducted which differ in the location specified for the fuel inlet boundary. In the first case, the fuel inlet boundary was specified at the nozzle exit while in the second case it was specified at a distance of 7 cm upstream of the nozzle exit. Parabolic velocity profiles were specified for both cases. In each set of simulations, flames with three different fuels (methane, ethylene and propane) were tested. Detailed high-temperature reaction mechanisms accounting for the formation of aromatic species were employed. The results showed that the fuel inlet BC location notably influence the predicted flow/temperature field and the resultant PAH concentration. Moreover, the effects become more notable with lower fuel stream velocities. It was also found that for propane with a density larger than air, recirculation zones were formed near the nozzle exit which exerted an additional influence on the flow development and temperature field as well as PAH formation. In addition, the effects of nozzle heating on flow development and PAH formation were also investigated.     

Investigation of the effect of molecular structure on sooting tendency in laminar diffusion flames at elevated pressure

A specially designed High Pressure Vessel and Burner and fueling system (called “doped flame”) are presented in this paper. This setup allows for soot measurements in laminar diffusion flames of liquid fuel blends at elevated pressure. Fuels with two typical molecular structures, namely linear and saturated cyclic hydrocarbons, are examined in both non-oxygenated (n-hexane (C₆H₁₄) and cyclohexane (C₆H₁₂)) and oxygenated form (1-hexanol (C₆H₁₄O) and cyclohexanol (C₆H₁₂O)). All compounds are blended into n-heptane. Focus of the research is on soot volume fraction at elevated pressure in the range of 1.5–2.0 bar. Sooting tendency is evaluated by means of Laser Induced Incandescence (LII) with Line of Sight Attenuation calibration (LOSA), and the data suggests that soot is more prevalent for cyclic structures relative to their linear counterparts.     

On evolution of particle size distribution functions of incipient soot in premixed ethylene-oxygen-argon flames

The evolution of the soot particle size distribution function (PSDF) and particle morphology are studied for premixed ethylene-oxygen-argon flat flames at equivalence ratio ?=2.07 over the maximum flame temperature range of 1600-1900 K. Experiments were carried out using an in-situ probe sampling method in tandem with a scanning mobility particle sizer (SMPS), yielding the PSDF for various distances from the burner surface. The morphology of the particles was examined by transmission electron microscopy (TEM) and atomic force microscopy (AFM). Within the particle size range that can be detected, the PSDF transitions from an apparent unimodal PSDF for high temperature flames (Tf>∼1800 K) to a bimodal PSDF at lower temperatures (Tf<∼1800 K). The bimodal PSDF has a noticeable trough that separates the nucleation tail and log-normal mode. This mode-transition trough had been previously thought to occur at a fixed particle size, but these results show a continuous shift of the trough location towards smaller sizes with increasing flame temperature. TEM images show that the particles are spherical, even when the PSDF is bimodal, suggesting that the bimodality occurs as the primary particles undergoes mass and size growth, and is not a result of particle aggregation. Atomic force microscopy of substrate deposited particles shows that particles spread and form hill like structures upon impact with the substrate surface, indicating that the particles are liquid-like at the time of impact.     

Study of polycyclic aromatic hydrocarbons (PAHs) in hydrogen-enriched methane diffusion flames

Polycyclic aromatic hydrocarbons (PAHs) are the carcinogenic components of soot. Detailed understanding of PAH formation characteristics is required for development of effective strategies to curtail PAH formation and reduce soot in combustion devices. This study presents an experimental methodology to analyse PAH formation characteristics of a non-premixed methane-air flame with and without hydrogen (H₂) addition, using simultaneous planar laser induced fluorescence (PLIF) imaging of PAH and hydroxyl radical (OH). OH PLIF was used to represent peak temperature regions in the flame front. One-dimensional, opposed-jet laminar non-premixed flame simulations were also carried out for the same fuel mixture conditions. This work describes comparison of trends from both sets of studies. PAH fluorescence intensity values were observed to increase with increasing height above burner, however this rate of increase reduced with H₂ addition. This observed rate of change in PAH fluorescence (that is, PAH growth characteristics) is indicative of the sooting potential of the fuel mixture. PAH fluorescence from experiments and PAH concentration from simulation show strong reduction with increase in H₂ addition. The percentage reduction in PAH fluorescence signal with H₂ addition closer to the burner tip was of a similar magnitude to that observed with flame simulations. The reduction in PAH with H₂ addition could be attributed to the reduction in acetylene and propargyl concentrations, and reduced H-abstraction rates, which reduced the availability of active sites for PAH growth. The proposed experimental methodology for PAH measurements can be readily applied to any fuel mixtures.     

Experimental and kinetic studies of soot formation in methanol-gasoline coflow diffusion flames

Methanol has been considered to be a potential alternative fuel to reduce soot emissions from GDI engine. In order to fully understand the effect of methanol addition on soot formation, the 2-D distribution of soot volume fraction in methanol/gasoline laminar diffusion flames was measured quantitatively with two-color laser induced incandescence (TC-LII) technique. In addition, the Methanol-TRF-PAH mechanism is constructed and used to analyze the formation pathways of soot precursors based on the CHEMKIN PRO 0-D constant pressure reactor. In this experiment, the blending ratio of methanol/gasoline was set as M0/20/40/60/80. Considering the carbon content decreasing due to methanol addition, carbon mass flow rate was remained constant. The experimental results showed that methanol is able to decrease the soot significantly, while the effect of methanol on soot reduction is weakened with the increasing methanol ratio. Compared with pure gasoline, the average soot volume fraction in the M20, M40, M60, and M80 flames decrease by 48.2%, 70.4%, 83.8%, and 97.7%, and the peak soot volume fraction decrease by 41.5%, 64.1%, 75.8% and 91.8% respectively. There is little soot formation in the M80 flame, inferring the pure methanol hardly forms soot. The kinetic analysis showed that mole fraction of A1-A4 decrease with the increasing methanol ratio. For the toluene-containing fuel M0-M80, A1 is mainly formed by C₆H₅CH₃ + H = A1 + CH₃ and oxidized by A1 + OH = A1- + H₂O. A4 is mainly produced by C₆H₅CH₂ + C₉H₇ = A4 + 2H₂ and oxidized by H-abstraction reaction with H or OH radical. The major reaction pathways of A1 and A4 formation are consistent under different methanol blending ratios. The soot reduction as methanol added mainly attributes to aromatics dilution effect. In addition, the formation process of soot precursors is largely affected by chemical processes of OH, CH₃, HO₂ radicals.     

Soot concentration and temperature measurements in co-annular, nonpremixed CH4/air laminar flames at pressures up to 4 MPa

Laminar nonpremixed methane-air flames were studied over the pressure range of 0.5 to 4 MPa using a new high-pressure combustion chamber. Flame characterization showed very good flame stability over the range of pressures, with a flame tip rms flicker of less than 1% in flame height. At all pressures, soot was completely oxidized within the visible flame. Spectral soot emission (SSE) and line-of-sight attenuation (LOSA) measurements provided radially resolved measurements of soot volume fraction and soot temperature at pressures from 0.5 to 4.0 MPa. Such measurements provide an improved understanding of the influence of pressure on soot formation and have not been reported previously in laminar nonpremixed flames for pressures above 0.4 MPa. SSE and LOSA soot concentration values typically agree to within 30% and both methods exhibit similar trends in the spatial distribution of soot concentration. Maximum soot concentration depended on pressure according to a power law, where the exponent on pressure is about 2 for the range of pressures between 0.5 and 2.0 MPa, and about 1.2 for 2.0 to 4.0 MPa. Peak carbon conversion to soot also followed a power-law dependence on pressure, where the pressure exponent is unity for pressures between 0.5 and 2.0 MPa and 0.1 for 2.0 to 4.0 MPa. The pressure dependence of sooting propensity diminished at pressures above 2.0 MPa. Soot concentrations measured in this work, when transformed to line-integrated values, are consistent with the measurements of Flower and Bowman for pressures up to 1.0 MPa [Proc. Combust Inst. 21 (1986) 1115-1124] and Lee and Na for pressures up to 0.4 MPa [JSME Int. J. Ser. B 43 (2000) 550-555]. Soot temperature measurements indicate that the overall temperatures decrease with increasing pressure; however, the differences diminish with increasing height in the flame. Low down in the flame, temperatures are about 150 K lower at pressures of 4.0 MPa than those at 0.5 MPa. In the upper half of the flame the differences reduce to 50 K.     

Measurements of sooting tendency in laminar diffusion flames of n-heptane at elevated pressure

This research focuses on the effects of an increasing pressure on the soot formation during combustion of vaporized liquid fuel. Therefore soot formation is measured in a laminar diffusion flame, with n-heptane as fuel, over a range of pressures from 1.0 to 3.0 bar. The soot volume fraction in the diffusion flames has been measured using Laser-Induced Incandescence (LII) calibrated by means of the Line Of Sight Attenuation (LOSA) technique. The values of the calibration factors between LII intensities and soot volume fraction from LOSA are slightly varied for different pressure. The integral soot volume fractions show power law dependence on pressures, being proportional to pⁿ, with n being 3.4 ± 0.3 in the pressure range of 1.0–3.0 bar.     

Synergistic effect on soot formation in counterflow diffusion flames of ethylene-propane mixtures with benzene addition

The characteristics of the formation of polycyclic aromatic hydrocarbon (PAH) and soot in counterflow diffusion flames of ethylene/propane mixtures have been investigated experimentally to identify the effect of fuel structure. The synergistic effect, that is, the enhancement of PAH and soot formation by the fuel mixing of ethylene and propane has been further analyzed to examine the suggested mechanisms based on the competition between PAH and soot growths through the H-abstraction-C₂H₂-addition (HACA) mechanism and the incipient ring formation through the propargyl recombination reaction. To mitigate the effect of incipient ring formation on the synergistic effect, a small amount of benzene was added to the fuel stream. Planar laser-induced incandescence and laser-induced fluorescence techniques were employed to measure relative soot volume fractions and PAH concentrations, respectively. Results showed that the synergistic effect on soot formation remained, even though the synergistic effects for relatively small aromatics mitigated with the benzene addition. Larger size PAHs have shown enhanced synergistic effects compared to smaller size PAHs regardless of benzene addition. These results implied that the role of propane mixing on the synergistic effect cannot be explained solely by the incipient ring formation via a propargyl recombination reaction; thus, it is suggested that the C₃ pathways could also contribute to the growth of PAH species.     

An experimental study on soot distribution characteristics of ethanol-gasoline blends in laminar diffusion flames

In view of the potential of bio-ethanol as an alternative fuel and the particulate matter (PM) issues during gasoline combustion, the soot distribution characteristics of ethanol-gasoline blends in laminar diffusion flames were studied on a Gülder liquid burner using the two-color laser induced incandescence (TC-LII) technique. During the experiments, the ethanol ratio in the blends was varied from 20% to 80% by volume in order to investigate quantitatively the soot reduction potential of ethanol. In order to study the effect of reduction in carbon content due to ethanol addition on soot formation, the experiments were performed under a fixed fuel mass flow rate and a fixed carbon mass flow rate. It was found that both peak and average soot volume fraction in the flame reduced significantly with increasing ethanol content under both fuel supplying modes, however, this effect was progressively less pronounced as ethanol content increased. By comparing the two fueling modes, it was found that the reduction in carbon content due to ethanol addition has little impact on soot reduction. For a given ethanol blending ratio, the soot reduction under the same carbon mass flow rate was only slightly smaller than that under the same fuel mass flow rate. In terms of flame characteristics, the initial height of soot formation increases with increasing ethanol content under both fuel supply modes mainly due to the increased fuel outlet velocity. Radially, the peak soot location moves from the outside towards the center gradually as height increases. However, along the center line of the flame, the initial height of soot formation decreases with increasing ethanol content under the same fuel flow rate, whereas the trend remained similar to that in the whole flame under the same carbon flow rate.     

Laser raman measurements of temperature and species concentration in swirling lifted hydrogen jet diffusion flames

Simultaneous spatially and temporally resolved point measurements of temperature, mixture fraction, major species (H₂, H₂O, O₂, N₂), and minor species (OH) concentrations are performed in unswirled (S_g = 0), low swirl (S_g = 0.12), and high swirl (S_g = 0.5) lifted turbulent hydrogen jet diffusion flames into still air. Ultraviolet (UV) Raman scattering and laser-induced predissociative fluorescence (LIPF) techniques are combined to make the multi-parameter measurements using a single KrF excimer laser. Experimental results are compared to the fast chemistry (equilibrium) limit, to the mixing without reaction limit, and to simulations of steady stretched laminar opposed-flow flames. It is found that in the lifted region where the swirling effects are strong, the measured chemical compositions are inconsistent with those calculated from stretched laminar diffusion flames or stretched partially premixed flames. Sub-equilibrium values of temperature, sub-flamelet values of H₂O, and super-flamelet values of OH are found in an intermittent annular turbulent brush of the swirled flame but not in the unswirled flame. Farther downstream of the nozzle exit (x/D ≥ 50), swirl has little effect on the finite-rate chemistry.     

Effects of hydrogen addition on soot formation and oxidation in laminar premixed C2H2/air flames

In an effort to elucidate the influence of hydrogen addition on soot formation and oxidation, a series of numerical investigations was performed for fuel rich laminar C₂H₂/air premixed flat flames using a modified CHEMKIN-II PREMIX code with a detailed soot chemistry mechanism. To clarify the influence of hydrogen addition, the hydrogen content (in volume %) in the fuel mixture was gradually increased from 10 to 50%. The hydrogen addition was found to slow the oxidation of C₂H₂ near the burner surface. The lowered rate of C₂H₂ oxidation coupled with lower C₂H₂ concentration near the burner surface impedes the formation of benzene. However, the formation of benzene was enhanced with the hydrogen addition as the height above burner (HAB) was increased. This was due to the increased reverse rate of the H abstraction reaction that prevents the radical formation process. Through the identical mechanism, the hydrogen addition slows further growth of benzene to larger polycyclic aromatic hydrocarbons (PAHs), eventually lowering the rate of particle inception. Numerical results also indicated that reductions in the soot emissions were mainly attributed to a significant reduction in the mass growth of soot particles. The abundance of hydrogen in the flames deactivated the surface site of soot particles covered with C-H bonds, lowering the surface growth rate (which leads to reductions in the mass growth of soot particles).     

A numerical study on the effects of pressure and gravity in laminar ethylene diffusion flames

The effects of pressure and gravity on sooting characteristics and flame structure were studied numerically in coflow ethylene–air laminar diffusion flames between 0.5 and 5 atm. Computations were performed by solving the unmodified and fully-coupled equations governing reactive, compressible, gaseous mixtures which include complex chemistry, detailed radiation heat transfer, and soot formation/oxidation. Soot formation/oxidation was modeled using an acetylene-based, semi-empirical model which has been verified with previously published experimental data to correctly capture many of the observed trends at normal-gravity. Calculations for each pressure considered were performed for both normal- and zero-gravity conditions to help separate the effects of pressure and buoyancy on soot formation. Based on the numerical predictions, pressure and gravity were observed to significantly influence the flames through their effects on buoyancy and reaction rates. The zero-gravity flames have higher soot concentrations, lower temperatures and broader soot-containing zones than normal-gravity flames at the same pressure. The zero-gravity flames were also found to be longer and wider. Differences were observed between the two levels of gravity when pressure was increased. The zero-gravity flames displayed a stronger dependence of the maximum soot yield on pressure from 0.5 to 2 atm and a weaker dependence from 2 to 5 atm as compared to the normal-gravity flames. In addition, flame diameter decreased with increasing pressure under normal-gravity while it increased with pressure in the zero-gravity cases. Changing the prescribed wall boundary condition from fixed-temperature to adiabatic significantly altered the numerical predictions at 5 atm. When the walls were assumed to be adiabatic, peak soot volume fractions and temperatures increased in both the zero- and normal-gravity flames, emphasizing the importance of heat conduction to the burner rim on flame structure.     

Experimental investigation and detailed modeling of soot aggregate formation and size distribution in laminar coflow diffusion flames of Jet A-1, a synthetic kerosene,and n-decane

A fully-coupled soot formation model is developed to predict the concentration, size, and aggregate structure of soot particles in the atmospheric pressure laminar coflow diffusion flames of a three-component surrogate for Jet A-1, a three-component surrogate for a Fischer–Tropsch Synthetic Paraffinic Kerosene (SPK), and n-decane. To model the chemical structure of the flames and soot precursor formation, a detailed chemical kinetic mechanism for fuel oxidation, with 2185 species and 8217 reactions, is reduced and combined with a Polycyclic Aromatic Hydrocarbon (PAH) formation and growth scheme. The mechanism is coupled to a highly detailed sectional particle dynamics model that predicts the volume fraction, structure, and size of soot particles by considering PAH-based nucleation, surface growth, PAH surface condensation, aggregation, surface oxidation, fragmentation, thermophoresis, and radiation. The simulation results are validated by comparing against experimental data measured for the flames of pre-vaporized fuels. The objectives of the present effort are to more accurately simulate the physical soot formation processes and to improve the predictions of our previously published jet fuel soot formation models, particularly for the size and aggregate structure of soot particles. To this end, the following improvements are considered: (1) addition of particle coalescence submodels to account for the loss of surface area, reduction of the number of primary particles, and increase of primary particle diameters upon collision, (2) consideration of a larger PAH molecule (benzopyrene instead of pyrene) for nucleation and surface growth to enhance the agreement between the soot model and the measured chemical composition of soot particles, and (3) implementation of a dimerization efficiency in the soot inception submodel to account for the collisions between PAH molecules that do not lead to dimerization. The results of two different particle coalescence submodels show that this process is too slow to account for the growth of primary particles, mainly because of the limited rate of particle collisions. Soot volume fraction predictions on the wings and at lower flame heights are considerably improved by using benzopyrene, due to the different distribution of the soot forming PAH molecule in the flame. The computed number of primary particles per aggregate and the diameters of primary particles agree very well with the experimentally measured values after implementing the dimerization efficiency for PAH collisions, because of the reduced rate of soot inception compared to growth by PAH condensation. Concentrations of major gaseous species and flame temperatures are also well predicted by the model. The underprediction of soot concentration on the flame centerline, observed in previous studies, still exists despite minor improvements.     

An experimental and numerical study of the effects of dimethyl ether addition to fuel on polycyclic aromatic hydrocarbon and soot formation in laminar coflow ethylene/air diffusion flames

The effects of dimethyl ether addition to fuel on the formation of polycyclic aromatic hydrocarbons and soot were investigated experimentally and numerically in a laminar coflow ethylene diffusion flame at atmospheric pressure. The relative concentrations of polycyclic aromatic hydrocarbon species and the relative soot volume fractions were measured using planar laser-induced fluorescence and two-dimensional laser-induced incandescence techniques, respectively. Experiments were conducted over the entire range of dimethyl ether addition from pure ethylene to pure dimethyl ether in the fuel stream. The total carbon mass flow rate was maintained constant when the fraction of DME in the fuel stream was varied. Numerical calculations of nine diffusion flames of different dimethyl ether fractions in the fuel stream were performed using a detailed reaction mechanism consisting of 151 species and 785 reactions and a sectional soot model including soot radiation, inception of nascent soot particle due to collision of two pyrene molecules, heterogeneous surface growth and oxidation following the hydrogen abstraction acetylene addition mechanism, soot particle coagulation, and PAH surface condensation. The addition of a relatively small amount of dimethyl ether to ethylene was found experimentally to increase the concentrations of both polycyclic aromatic hydrocarbons and soot. The synergistic effect on polycyclic aromatic hydrocarbons persists over a wider range of dimethyl ether addition. The numerical results reproduce the synergistic effects of dimethyl ether addition to ethylene on both polycyclic aromatic hydrocarbons and soot, though the magnitude of soot volume fraction overshoot and the range of dimethyl ether addition associated with the synergistic effect of soot are less than those observed in the experiment. The synergistic effects of dimethyl ether addition to ethylene on many hydrocarbon species, including polycyclic aromatic ones, and soot can be fundamentally traced to the enhanced methyl concentration with the addition of dimethyl ether to ethylene. Contrary to previous findings, the pathways responsible for the synergistic effects of benzene, polycyclic aromatic hydrocarbons, and soot in the ethylene/dimethyl ether system are found to be primarily due to the cyclization of l-C₆H₆ and n-C₆H₇ and to a much lesser degree due to the interaction between C2 and C4 species for benzene formation, rather than the propargyl self-combination reaction route, though it is indeed the most important reaction for the formation of benzene.     

Soot graphitic order in laminar diffusion flames and a large-scale JP-8 pool fire

High-resolution transmission electron microscopy (HRTEM) has been performed on soot samples collected from two smoking laminar ethylene diffusion flames (one steady and one unsteady) and from the active-flaming region of a 5-m diameter JP-8 pool fire. The motivation for this study is to improve the understanding of the influence of soot microstructure on its optical properties. The soot sampling positions in the steady ethylene flame correspond to locations of maximum soot mass growth, partial soot oxidation, and quenched oxidation along a common streamline. Visual examination of the HRTEM images suggests that the graphitic crystalline layers of soot undergo increased densification along the sampled streamline in the steady laminar flame. Quantitative image analysis reveals a small decrease in the mean graphitic interlayer spacing (d₀₀₂) with increasing residence time in the high-temperature region. However, the differences in the mean interlayer spacing are far smaller than the spread of interlayer spacings measured for any given soot sample. Post-flame samples from the unsteady ethylene flame show interlayer spacing distributions similar to the lower region of the steady flame. The soot samples from the pool fire show little evidence of oxidized soot and have interlayer spacings similar to the unsteady ethylene flame. Previous research in the carbon black field has demonstrated a direct relation between the graphitic interlayer spacing and the optical absorptivity of the carbon. Consequently, the current HRTEM results offer support to recent measurements of the dimensionless extinction coefficient of soot that suggest that the optical absorptivity of agglomerating soot shows only minor variations for different fuels and flame types.     

Physical and chemical comparison of soot in hydrocarbon and biodiesel fuel diffusion flames: A study of model and commercial fuels

Data are presented to compare soot formation in both surrogate and practical fatty acid methyl ester biodiesel and petroleum fuel diffusion flames. The approach here uses differential mobility analysis to follow the size distributions and electrical charge of soot particles as they evolve in the flame, and laser ablation particle mass spectrometry to elucidate their composition. Qualitatively, these soot properties exhibit a remarkably similar development along the flames. The size distributions begin as a single mode of precursor nanoparticles, evolve through a bimodal phase marking the onset of aggregate formation, and end in a self preserving mode of fractal-like particles. Both biodiesel and hydrocarbon fuels yield a common soot composition dominated by C_x ions, stabilomer PAHs, and fullerenes in the positive ion mass spectrum, and and C_2xH⁻ in the negative ion spectrum. These ion intensities initially grow with height in the diffusion flames, but then decline during later stages, consistent with soot carbonization. There are important quantitative differences between fuels. The surrogate biodiesel fuel methyl butanoate substantially reduces soot levels, but soot formation and evolution in this flame are delayed relative to both soy and petroleum fuels. In contrast, soots from soy and hexadecane flames exhibit nearly quantitative agreement in their size distribution and composition profiles with height, suggesting similar soot precursor chemistry.