The Cool Flames of Hydrocarbons

This review describes the properties of the cool-flame and two-stage ignition processes that characterize the gaseous oxidation of hydrocarbons and discusses the chemical reactions that are responsible for these phenomena. Cool flames result from a chainthermal acceleration of reaction rate. It is probable that the free-radical chain involved is propagated by the reaction of an alkyl radical with oxygen to give an alkyperoxy radical which isomerizes to a hydroperoxyalkyl radical. The decomposition of this radical produces a hydroxyl radical, which attacks the hydrocarbon rapidly and unselectively to regenerate an alkyl radical. Branching probably results from the pyrolysis of mono- and dihydroperoxides, from the oxidation of aldehydes, and from radical-molecule reactions. This reaction scheme explains the existence of a low-temperature ignition peninsula and the relation of the extent and shape of this peninsula to the molecular structure of the hydrocarbon. The chemical relevance of cool flames to abnormal combustion phenomena, such as knock, in gasoline engines is discussed.     

Large eddy simulations of turbulent flames using the filtered density function model

Large eddy simulations (LES) of the Sandia/Sydney swirl burners (SM1 and SMA1) and the Sandia/Darmstadt piloted jet diffusion flame (Flame D) are performed. These flames are part of the database of turbulent reacting flows widely considered as benchmark test cases for validating turbulent-combustion models. In the simulations presented in this paper, the subgrid scale (SGS) closure model adopted for turbulence-chemistry interactions is based on the transport filtered density function (FDF) model. In the FDF model, the transport equation for the joint probability density function (PDF) of scalars is solved. The main advantage of this model is that the filtered reaction rates can be exactly computed. However, the density field, computed directly from the FDF solver and needed in the hydrodynamic equations, is noisy and causes numerical instability. Two numerical approaches that yield a smooth density field are examined. The two methods are based on transport equations for specific sensible enthalpy (h_s) and RT, where R is the gas constant and T is the temperature. Consistency of the two methods is assessed in a bluff-body configuration using Reynolds averaged Navier-Stokes (RANS) methodology in conjunction with the transported PDF method. It is observed that the h_s method is superior to the RT method. Both methods are used in LES of the SM1 burner. In the near-field region, the h_s method produces better predictions of temperature. However, in the far-field region, both methods show deviation from data. Simulations of the SMA1 burner and Flame D are also presented using the h_s method. Some deficiencies are seen in the predictions of the SMA1 burner that may be related to the simple chemical kinetics model and mixing model used in the simulations. Simulations of Flame D show good agreement with data. These results indicate that, while further improvements to the methodology are needed, the LES/FDF method has the potential to accurately predict complex turbulent flames.     

测量层流扩散火焰温度与烟黑浓度分布的实验研究

本文提出了一种通过线性规划中的内点法(仿射变换法)来计算烟黑浓度和温度分布的模型.根据烟黑辐射特性,利用火焰单色辐射强度图像信息采用此模型同时重建轴对称含烟黑火焰的温度与烟黑浓度分布,对层流乙烯扩散火焰的温度与烟黑浓度进行测量,得到了较好的结果.     

The effects of burner stabilization on Fenimore NO formation in low-pressure, fuel-rich premixed CH4/O2/N2 flames

We investigate the effects of varying the degree of burner stabilization on Fenimore NO formation in fuel-rich low-pressure flat CH₄/O₂/N₂ flames. Towards this end, axial profiles of flame temperature and OH, NO and CH mole fractions are measured using laser-induced fluorescence (LIF). The experiments are performed at equivalence ratios between 1.3 and 1.5. The flame temperature is seen to decrease by 200-300 K, with a concomitant decrease in OH mole fraction, upon reducing the total flow rate from 5 to 3 L/min, thus increasing stabilization. At equivalence ratios between 1.3 and 1.5, this decrease in flow rate lowers the maximum CH mole fraction by a factor of 2, and the NO mole fraction by ∼40% in all flames studied. Integrating the reaction rate for CH + N₂ to estimate Fenimore NO formation, using the rate coefficient in GRI-Mech 3.0, and the measured temperatures and CH profiles show very good agreement with the measured NO mole fraction for ? = 1.3 and 1.4, supporting the current choice for this rate. This agreement also shows that the increase in residence time caused by increased stabilization is an important factor in the ultimate impact of the changes in CH mole fraction on NO formation. The results at ? = 1.5 suggest that substantial quantities of fixed nitrogen species, e.g., HCN, are only slowly oxidized in the post-flame zone under these conditions, leading to a significant discrepancy between the measured NO mole fraction and that obtained by integrating over the CH profile. Detailed calculations using GRI-Mech 3.0 predict the experimental results at ? = 1.3 nearly quantitatively, but show increasing differences with the measurements for both CH and NO profiles with increasing equivalence ratio.     

Fuel dependence of benzene pathways

The relative importance of formation pathways for benzene, an important precursor to soot formation, was determined from the simulation of 22 premixed flames for a wide range of equivalence ratios (1.0-3.06), fuels (C₁-C₁₂), and pressures (20-760 torr). The maximum benzene concentrations in 15 out of these flames were well reproduced within 30% of the experimental data. Fuel structural properties were found to be critical for benzene production. Cyclohexanes and C₃ and C₄ fuels were found to be among the most productive in benzene formation; and long-chain normal paraffins produce the least amount of benzene. Other properties, such as equivalence ratio and combustion temperatures, were also found to be important in determining the amount of benzene produced in flames. Reaction pathways for benzene formation were examined critically in four premixed flames of structurally different fuels of acetylene, n-decane, butadiene, and cyclohexane. Reactions involving precursors, such as C₃ and C₄ species, were examined. Combination reactions of C₃ species were identified to be the major benzene formation routes with the exception of the cyclohexane flame, in which benzene is formed exclusively from cascading fuel dehydrogenation via cyclohexene and cyclohexadiene intermediates. Acetylene addition makes a minor contribution to benzene formation, except in the butadiene flame where C₄H₅ radicals are produced directly from the fuel, and in the n-decane flame where C₄H₅ radicals are produced from large alkyl radical decomposition and H atom abstraction from the resulting large olefins.     

Flame dynamics

This lecture describes recent theoretical developments associated with the dynamics of flames, obtained primarily by exploiting the various temporal and length scales involved in the combustion process. In premixed flames the focus is on flame-flow interactions that occur during the nonlinear development of hydrodynamically unstable large-scale flames, or during the propagation of curved flames in two-dimensional channels. The second part of the paper deals with non-premixed and partially premixed flames, where the focus is on understanding the nature of diffusive-thermal instabilities including the effect of thermal expansion, and on stabilization mechanisms of edge flames, which possess characteristics of both premixed and diffusion flames. The results presented in this talk illustrate how simplified models, when analyzed to their extreme, yield predictions of qualitative nature with physical insight that have advanced our understanding of combustion. This insight can be used to guide the experimental efforts, explain observations and validate large-scale numerical simulations.     

Hyperacceleration effects on turbulent combustion in premixed step-stabilized flames

Experimental results are presented from an investigation of the effects of large transverse accelerations on flame propagation and blowout limits in premixed step-stabilized flames. The accelerations, which exceed ±10,000 g in the present study, induce large body forces on the high-density reactants and low-density products. These body forces can substantially alter the flame propagation mechanisms and dramatically increase the flame blowout limits. Sustained centripetal accelerations a_c ≡ U²/R are created by flowing a premixed propane–air reactant stream with equivalence ratios 0.7  Φ  1.9 at various speeds U through a semicircular channel with radius R. A backward-facing step of height h on the radially outer (a_c > 0) or inner (a_c < 0) wall stabilizes the flame. For a_c > 0 the acceleration acts to force high-density reactants into the recirculation zone and low-density products into the reactant stream, while a_c < 0 forces hot products into the recirculation zone and impedes cold reactants from entering this zone. An otherwise identical straight channel provides corresponding baseline (a_c = 0) results for comparison. The flow speed U, equivalence ratio Φ, and step height h are systematically varied for a_c = 0, a_c > 0, and a_c < 0. Shadowgraph and chemiluminescence imaging show that as a_c→ +∞ the propagation of the flame across the channel becomes independent of the flame burning velocity and instead is primarily due to large-scale “centrifugal pumping” driven by the induced body forces. For a_c → −∞ the body forces effectively segregate reactants and products to produce a nearly flat flame. In both cases, for large |a_c| values the resulting blowout limits can be substantially higher than those at a_c = 0.