Insight into fuel isomeric effects on laminar flame propagation of pentanones

Laminar flame propagation was investigated for pentanone isomers/air mixtures (3-pentanone, 2-pentanone and 3-methyl-2-butanone) in a high-pressure constant-volume cylindrical combustion vessel at 393–423 K, 1–10 atm and equivalence ratios of 0.6–1.5, and in a heat flux burner at 393 K, 1 atm and equivalence ratios of 0.6–1.5. Two kinds of methods generally show good agreement, both of which indicate that the laminar burning velocity increases in the order of 3-methyl-2-butanone, 2-pentanone and 3-pentanone. A kinetic model of pentanone isomers was developed and validated against experimental data in this work and in literature. Modeling analysis was performed to provide insight into the flame chemistry of the three pentanone isomers. H-abstraction reactions are concluded to dominate fuel consumption, and further decomposition of fuel radicals eventually produces fuel-specific small radicals. The differences in radical pools are concluded to be responsible for the observed fuel isomeric effects on laminar burning velocity. Among the three pentanone isomers, 3-pentanone tends to produce ethyl and does not prefer to produce methyl and allyl in flames, thus it has the highest reactivity and fastest laminar flame propagation. On the contrary, 3-methyl-2-butanone tends to produce allyl and methyl instead of ethyl, and consequently has the lowest reactivity and slowest laminar flame propagation.     

Laminar flame propagation of acetone and 2-butanone at normal to high pressures: Insight into fuel molecular structure effects of ketones

This work reports an experimental and kinetic modeling investigation on the laminar flame propagation of acetone and 2-butanone at normal to high pressures. The experiments were performed in a high-pressure constant-volume cylindrical combustion vessel at 1–10 atm, 423 K and equivalence ratios of 0.7–1.5. A kinetic model of acetone and 2-butanone combustion was developed from our recent pentanone model [Li et al., Proc. Combust. Inst. 38 (2021) 2135–2142] and validated against experimental data in this work and in literature. Together with our recently reported data of 3-pentanone, remarkable fuel molecular structure effects were observed in the laminar flame propagation of the three C₃C₅ ketones. The laminar burning velocity increases in the order of acetone, 2-butanone and 3-pentanone, while the pressure effects in laminar burning velocity reduces in the same order. Modeling analysis was performed to provide insight into the key pathways in flames of acetone and 2-butanone. The differences in radical pools are concluded to be responsible for the observed fuel molecular structure effects on laminar burning velocity. The favored formation of methyl in acetone flames inhibits its reactivity and leads to the slowest laminar flame propagation, while the easiest formation of ethyl in 3-pentanone flames results in the highest reactivity and fastest laminar flame propagation. Furthermore, the LBVs of acetone and 3-pentanone exhibit the strongest and weakest pressure effects respectively, which can be attributed to the influence of fuel molecular structures through two crucial pressure-dependent reactions CH₃ + H (+M) = CH₄ (+M) and C₂H₄ + H (+M) = C₂H₅ (+M).     

Influence of water mist on propagation and suppression of laminar premixed flame

The combustion of premixed gas mixtures containing micro droplets of water was studied using one-dimensional approximation. The dependencies of the burning velocity and flammability limits on the initial conditions and on the properties of liquid droplets were analyzed. Effects of droplet size and concentration of added liquid were studied. It was demonstrated that the droplets with smaller diameters are more effective in reducing the flame velocity. For droplets vaporizing in the reaction zone, the burning velocity is independent of droplet size, and it depends only on the concentration of added liquid. With further increase of the droplet diameter the droplets are passing through the reaction zone with completion of vaporization in the combustion products. It was demonstrated that for droplets above a certain size there are two stable stationary modes of flame propagation with transition of hysteresis type. The critical conditions of the transition are due to the appearance of the temperature maximum at the flame front and the temperature gradient with heat losses from the reaction zone to the products, as a result of droplet vaporization passing through the reaction zone. The critical conditions are similar to the critical conditions of the classical flammability limits of flame with the thermal mechanism of flame propagation. The maximum decrease in the burning velocity and decrease in the combustion temperature at the critical turning point corresponds to predictions of the classical theories of flammability limits of Zel'dovich and Spalding. The stability analysis of stationary modes of flame propagation in the presence of water mist showed the lack of oscillatory processes in the frames of the assumed model.     

Dilution effects on laminar jet diffusion flame lengths

Many studies have examined the stoichiometric lengths of laminar gas jet diffusion flames. However, these have emphasized normal flames of undiluted fuel burning in air. Many questions remain about the effects of fuel dilution, oxygen-enhanced combustion, and inverse flames. Thus, the stoichiometric lengths of 287 normal and inverse gas jet flames are measured for a broad range of nitrogen dilution. The fuels are methane and propane and the ambient pressure is atmospheric. Nitrogen addition to the fuel and/or oxidizer is found to increase the stoichiometric lengths of both normal and inverse diffusion flames, but this effect is small at high reactant mole fraction. This counters previous assertions that inert addition to the fuel stream has a negligible effect on the lengths of normal diffusion flames. The analytical model of Roper is extended to these conditions by specifying the characteristic diffusivity to be the mean diffusivity of the fuel and oxidizer into stoichiometric products and a characteristic temperature that scales with the adiabatic flame temperature and the ambient temperature. The extended model correlates the measured lengths of normal and inverse flames with coefficients of determination of 0.87 for methane and 0.97 for propane.     

Analysis of the flame dynamics in methane/hydrogen fuel blends at elevated pressures

We investigate the Flame Transfer Function (FTF) of a lean-premixed, laminar slit flame numerically. Based on the reference case at atmospheric pressure, we investigate four different scenarios: (i) varying the hydrogen content in the fuel at constant equivalence ratio (ER) (resulting in an increase of the laminar flame speed); (ii) varying the hydrogen content in the fuel at varying ER (resulting in a constant laminar flame speed); (iii) varying the operating pressures from 1 to 5 bar (resulting in a decrease of the laminar flame speed); and (iv) combining a hydrogen-enriched flame at an elevated pressure of 3 bar (resulting in the same flame speed as the reference case). We identify in this case that the laminar flame speed and the flame thickness impact the FTF independently. We show that the low-pass behavior of the flame is shifted towards higher frequencies when the operating pressure increases, and demonstrate that wrinkles along the flame front preserve in contrast to the atmospheric operating pressure configurations. These results are in line with past studies, that relate the dampening of flame front wrinkling to a decreasing Markstein length. We therefore conclude that a decreasing flame thickness, due to increasing operating pressure, causes a decreasing Markstein length and therefore less pronounced dampening of flame front wrinkles.     

Exploring the pyrolysis chemistry of 1,3,5-trimethylcyclohexane with insight into fuel isomeric and multiple substitution effects

To reveal insights into the combustion mechanism of multiple alkyl substituent cycloparaffins, this work reports an experimental and modeling study of 1,3,5-trimethylcyclohexane (T135MCH) pyrolysis in an extended flow reactor at low and atmospheric pressures. More than 30 species were detected and quantified employing synchrotron vacuum ultraviolet photoionization molecular beam mass spectrometry, and a detailed kinetic model developed based on reaction classes and update kinetic data was validated against the measured species profiles with a reasonable agreement. The reaction flux analyses were performed to reveal the key pathways of the fuel decomposition, intermediates production and aromatics formation. For the primary decomposition, the branching ratios of reaction types show strong dependence on changes of pressures and temperatures, including unimolecular methyl elimination, unimolecular ring-opening isomerization and H-abstraction. Besides the direct dissociation channels, major intermediate hydrocarbons are formed via stepwise dehydrogenation, recombination with ĊH₃ radical or “formally direct” chemically activated reactions triggered by Ḣ atom addition. Monocyclic aromatic hydrocarbons such as benzene and toluene can be produced by traditional H-abstraction/β-C-H scission sequence, cyclopentadiene-related pathways, or recombination mechanism from small linear products. The formations of indene and naphthalene are controlled by C₅+C₅ and C₅+C₄ mechanism respectively. The comparison work of species profiles combined with theoretical calculations of bond dissociation enthalpies (BDEs) was performed to reveal the multiple CH₃-group substituent and isomeric effects of methylcyclohexane (MCH), 1,2,4-trimethylcyclohexane (T124MCH) and T135MCH on pyrolysis activity and ethylene/benzene formation. Besides the increased reaction active sites, the added CH₃-group and ortho-substitution can both weaken the strength of CC and CH bonds, leading to the promoting decomposition activity. The different formation tendencies of products are caused by different BDEs, length of carbon skeleton, as well as complex fuel-specific pathways.     

FXR discharges at various pressures

The formation period time, current rise time, and photon energy of FXR discharges have been investigated at initial pressures of 5×10^?6 to 1×10^?2Torr. It has been found that the parameters studied are almost constant between 5×10^?6 and 1×10^?3Torr. The results obtained indicate that the upper limit of the interelectrode breakdown pressure is about 10^?3 Torr when the initial pressure is 10^?6 Torr.     

Physical and chemical effects of phosphorus-containing compounds on laminar premixed flame

Phosphorus-containing compounds are the promising halon alternatives for flame inhibitions. However, some literatures suggested that the phosphorus-related inhibitors may behave as the unfavorable ones that will increase the burning velocity under lean-burn conditions, and this indeed posed potential threats to the fire prevention and fighting. To seek deeper insights into the reaction process, a numerical investigation was actualized to study the phosphorus-related effects on methane-air flames. By replacing a phosphorus-related inhibitor with the corresponding decomposed molecules, the detailed promoting and inhibiting effects of combustion were separated from the general chemical effect. A comparative study was carried out to identify the interaction between the two effects under different combustion conditions. It is observed that the promoting effect becomes the dominant factor during the reaction process when the equivalence ratio is smaller than 0.60. In this lean-burn condition, the exothermic reactions were faster than the others within the reaction chains due to the reduction of radical recombination in hydrocarbon oxidation. The results are believed to be useful for the further application and improvement of flame inhibitors.     

Heat recirculation effects on flame propagation and flame structure in a mesoscale tube

Heat recirculation effects on flame propagation and flame structure are theoretically and experimentally examined in a mesoscale tube as the simplest model of heat-recirculating burners. Solutions for steady propagation are obtained using a one-dimensional two-temperature approximation. The results show that the low heat diffusivities of common solid materials permit significant heat recirculation through the wall only for a slowly-propagating condition, otherwise the flame behaves almost like a freely-propagating nonadiabatic flame. This limited heat recirculation sharply pinches and stretches two well-known branches of the freely-propagating nonadiabatic flame, resulting in the appearance of two slow-propagation branches. On the upper slow-propagation branch flames can reach superadiabatic temperatures and on the lower one, which is stretched from the classical unstable lower branch, flames can be stable. As the tube inner diameter decreases, another burning regime appears where flames are barely sustained by the heat recirculation. Further reduction of the tube inner diameter makes no flame exist. It is also revealed that a flame in a mesoscale tube has two length scales, i.e. the conventional flame thickness and a convective preheat zone thickness, and that the latter should be much larger than the former for significant heat recirculation. It is theoretically predicted that a heat-recirculating, even superadiabatic, flame with positive propagation velocity against the gas flow can exist in a mesoscale tube. It is also found that a flame transition from one branch to another in a given tube is well described by only one dimensionless parameter. Finally, these theoretical results show good qualitative agreements with experiments, especially for the transition behaviours.     

Effects of pressure on flame propagation in a premixture containing fine fuel droplets

Combustion experiments on fuel droplet–vapor–air mixtures have been performed with a rapid expansion apparatus which generates monodispersed droplet clouds with narrow diameter distribution using the condensation method. The effects of fine fuel droplets on flame propagation were investigated for ethanol droplet–vapor–air mixtures at various pressures from 0.2 to 1.0 MPa. A stagnant fuel droplet–vapor–air mixture, generated in a rapid expansion chamber, was ignited at the center of the chamber using an ignition wire. Spherical flame propagation under constant-pressure conditions was observed with a high-speed video camera and flame speed was measured. Total equivalence ratio, and the ratio of liquid fuel mass to total fuel mass, was varied from 0.6 to 1.4 and from zero to 56%, respectively. The mean droplet diameter of fuel droplet–vapor–air mixtures was set at 8.5 and 11 μm. It was found that the flame speed of droplet–vapor–air mixtures less than 0.9 in the total equivalence ratio exceeds that of premixed gases of the same total equivalence ratio at all pressures. The flame speed of fuel droplet–vapor–air mixtures decreases as the pressure increases in all total equivalence ratios. At large ratios of liquid fuel mass to total fuel mass, the normalized flame speed (the flame speed of droplet–vapor–air mixtures divided by the flame speed of the premixed gas with the same total equivalence ratio), increases with the increase in pressure for fuel-lean mixtures, and it decreases for fuel-rich mixtures. The outcome is reversed at small ratios of liquid fuel mass to total fuel mass; the normalized flame speed decreases with the increase in pressure for fuel-lean mixtures, and increases for fuel-rich mixtures. The results suggest that the increase in pressure promotes droplet evaporation in the preheat zone.     

Combustion of silane-nitrous oxide-argon mixtures: Analysis of laminar flame propagation and condensed products

The laminar burning rate, the explosion peak pressure, and the pressure rise coefficient have been measured for the first time for silane-nitrous oxide-argon mixtures using the spherically expanding flame technique in a constant volume combustion chamber. For these three parameters, the values obtained were higher than for hydrogen-nitrous oxide-argon and typical hydrocarbon-based mixtures. A maximum burning rate of 1800 g/m² s was measured at 101 kPa, whereas under similar conditions, a maximum burning rate around 950 g/m² s has been reported for hydrogen-nitrous oxide-argon mixtures. To better understand the chemical dynamics of flames propagating in SiH₄–N₂O–Ar mixtures, a detailed reaction model from the literature was improved using collision limit violation analysis and updated thermodynamic properties calculated with a high-level ab initio approach. The reaction model predicts the burning rate within 14% on average but demonstrates error close to 50% for the richest mixtures. The chemistry of the H–O–N system is important under all the conditions presently studied. The chemistry of the Si–H–O–N system demonstrates an increasing importance under rich conditions. In particular, the reactions (i) forming SiO_x(s); (ii) describing the interaction of Si-species with N₂O; and (iii) involving silicon hydrides, have an important role for the heat release dynamics. The condensed combustion products formed in the silane-nitrous oxide-argon flames were sampled and characterized using electron micrograph, electronic diffraction, energy-dispersive spectroscopy, and X-ray powder diffraction. For all equivalence ratios, silica spherical particles with a mean diameter in the range 200–300 nm were observed. In addition, for mixtures with Φ ≥ 2.2, silicon nanowires were formed. X-ray diffraction experiments showed that the silicon nanowires are composed of metal silicon characterized by a cubic structure (lattice parameter: a=5.425Å) with the Fm-3m space group.     

Effects of fine fuel droplets on a laminar flame stabilized in a partially prevaporized spray stream

A partially prevaporized spray burner was developed to investigate the interaction between fuel droplets and a flame. Monodispersed partially prevaporized ethanol sprays with narrow diameter distribution were generated by the condensation method using rapid pressure reduction of a saturated ethanol vapor–air mixture. A tilted flat flame was stabilized at the nozzle exit using a hot wire. Particle tracking velocimetry (PTV) was applied to measurements of the droplet velocity; the laminar burning velocity was obtained from gas velocity derived from the droplet velocity. Observations were made of flames in partially prevaporized spray streams with mean droplet diameters of 7 μm and the liquid equivalence ratios of 0.2; the total equivalence ratio was varied. In all cases, a sharp vaporization plane was observed in front of the blue flame. Flame oscillation was observed on the fuel-rich side. At strain rates under 50 s⁻¹, the change in the burning velocity with the strain rate is small in fuel-lean spray streams. In spray streams of 0.7 and 0.8 in the total equivalence ratio, burning velocity increases with strain rates of greater than 50 s⁻¹. However, in spray streams with 0.9 and 1.0 in the total equivalence ratio, burning velocity decreases as the strain rate increases. At strain rates greater than 80 s⁻¹, burning velocity decreases with an increased gas equivalence ratio. The effect of mean droplet diameter, and the entry length of droplets into a flame on the laminar burning velocity, were also investigated to interpret the effect of the strain rate on the laminar burning velocity of partially prevaporized sprays.     

Laminar flame propagation on a horizontal fuel surface: Verification of classical Emmons solution

This work analyses the classical Emmons (1956) solution of flat plate laminar flame combustion on a film of liquid fuel. A two-dimensional (2D) numerical model developed for this purpose has been benchmarked with experimental results available in the literature for methanol. In the parametric study, numerical predictions have been compared with Emmons classical solution. The study shows that the Emmons solution is valid in a range of Reynolds numbers where flame anchors near the leading edge of the methanol pool and the combustion zone is confined around the hydrodynamic and thermal boundary layers. However, in cases of low free stream velocities the combustion zone is beyond the boundary layer zone and the Emmons solution deviates. In cases of very high free stream velocities, the flame moves away from the leading edge and anchors at a location downstream. The Emmons solution is not applicable in this case as well. For the fuel considered in this study (methanol), accounting for thermal radiation, employing an optically thin radiation model, allows better agreement between experimental and numerical temperature profiles but does not affect the mass burning rates.     

One-dimensional modelling of flame propagation in solid composite fuel with different geometrical configurations

In this paper the propagation of combustion waves in solid composite energetic material consisting of fuel and highly thermal conductive inert elements is investigated using a one-dimensional model with a single step reaction mechanism. The analysis is focused on the study of the effect of the geometrical configuration of the composite material on flame speed and dynamics. Spatial averaging over directions transverse to the propagation direction is performed in such a way as to retain the multidimensional nature of the problem. It is shown that the regimes of combustion depend on the geometry of the composite. The largest possible flame speed enhancement is attained in cases when the heat fluxes along the structural elements are not disrupted. For each configuration selected, there exists an optimal choice of the geometric parameters that maximizes the flame velocity.     

Radiation affected ignition and flame propagation for solid fuel in a cylindrical enclosure

Ignition and flame propagation for pyrolysing fuel in a cylindrical enclosure has been examined in this study. The pyrolysing fuel of cylindrical shape was located both eccentrically and concentrically inside an outer cylinder that was sustained at high temperature. Due to gravity, buoyancy motion was inevitably incurred in the enclosure, and this was found to affect the flame initiation and propagation behaviour. Radiative heat transfer also played an important role in the thermo-fluid mechanical behaviour because of the high temperature involved in the problem. Numerical studies have been performed for various parameters such as the Grashof number, overheat ratio, gas absorption coefficient and vertical fuel eccentricity. The flame behaviour and initiation were observed to be totally different depending on the Grashof number. Due to absorbed radiant energy, the radiative gas played a significant role in flame evolution. The location of flame onset was also affected by both the vertical eccentricity of the inner pyrolysing fuel and the thermal conditions applied. The heating process and the flow field development were found to govern flame initiation and propagation.     

Critical conditions at liftoff limit of a laminar n-butane-air jet diffusion flame

The stability mechanism of laminar coflow jet diffusion flames in normal gravity has been studied computationally and experimentally. N-butane, the heaviest alkane in a gaseous state at ambient temperature and pressure, is used as the fuel since the reaction mechanism is similar to that of higher (liquid) hydrocarbons. The critical mean n-butane jet and coflowing air velocities at flame stability limits are measured using a small fuel tube burner (0.8 mm inner diameter). The time-dependent, axisymmetric numerical code with a detailed reaction mechanism (58 species and 540 reactions), molecular diffusive transport, and a radiation model, reveals a flame structure. A fuel-lean peak reactivity spot (i.e., reaction kernel), possessing the hybrid nature of diffusion-premixed flame structure at a constant temperature of ≈1560 K, is formed at the flame base and controls the flame stability. In a near-quiescent environment, the flame base resides below the fuel tube exit plane and thereby premixing is limited. As the coflowing air velocity is increased incrementally under a fixed fuel jet velocity, the flame base moves slightly above (≈1 mm) the burner exit and vigorous premixed combustion becomes prevailing. The local heat-release rate at the reaction kernel nearly doubles due to the increased convective oxygen flux (i.e., a blowing effect). The local Damköhler number, newly defined as a ratio of the square root of the local heat-release rate and the local velocity, decreases gradually first and drops abruptly at a critical threshold value and the flame base lifts off from the burner rim. The calculated coflow air velocity at liftoff is ≈0.38 m/s at the fuel jet velocity of 2 m/s, which is consistent with an extrapolated measured value of 0.41 m/s. This work has determined the critical Damköhler number at the stability limit quantitatively, for the first time, for laminar jet diffusion flames.     

Lewis number effects on laminar and turbulent expanding flames of NH3/H2/air mixtures at elevated pressures

This study clarifies the effects of Lewis number (Le) on laminar and turbulent expanding flames of NH₃/H₂/air mixtures. The laminar burning velocity (S_L) and turbulent burning velocity (S_T) were measured using a medium-scale, fan-stirred combustion chamber with ammonia/hydrogen molar ratio (NH₃/H₂) of 50/50 and 80/20 under the maximum pressures of 5 atm. The lean laminar flame with NH₃/H₂ = 50/50 is significantly accelerated by the diffusional–thermal instability, which dominated the trend of S_T,c=0.1 with the equivalence ratio (ϕ). The lean normalized turbulent burning velocity (S_T/S_L) increases with the decrease of hydrogen content due to the weakening effects of S_L. However, the S_T/S_L reaches peak with hydrogen volumetric content less than 20% due to effects made by diffusional–thermal instability than S_L did. The turbulent flame of NH₃/H₂/air mixtures is characterized by self-similar acceleration propagation, and propagation with Le < 1 is faster. A modified correlation considering the effects of Le was proposed, as (d<r>/dt)/σS_L = 0.118(Re_T,flameLe⁻²)^0.57, which was able to predict not only the self-similar propagation of NH₃/H₂/air but also the previous syngas/air flames. The Kobayashi correlations modified by three kinds of Le power exponents were used to clarify the effects of Le by comparing their fitting parameters and predictive powers on experimental data and literature data. Similar pre-factors, power exponents and the goodness of fit (R²) were obtained with Le ranging from 0.58 to 1.62, which suggested that the determination of Le power exponent had no significant effect on the prediction accuracy of the S_T/S_L trend with data of Le near unity. This might be attributed to the fact that the variation ranges of the dimensionless number that characterizes the experimental conditions is much larger than that of the Le.