Kuang C. Lin

Shapes of nonbuoyant round luminous hydrocarbon/air laminar jet diffusion flames

Abstract The shapes (luminous flame boundaries) of round luminous nonbuoyant soot-containing hydrocarbon/air laminar jet diffusion flames at microgravity were found from color video images obtained on orbit in the Space Shuttle Columbia. Test conditions included ethylene- and propane-fueled flames burning in still air at an ambient temperature of 300 K, ambient pressures of 35–130 kPa, initial jet diameters of 1.6 and 2.7 mm, and jet exit Reynolds numbers of 45–170. Present test times were 100–200 s and yielded steady axisymmetric flames that were close to the laminar smoke point (including flames both emitting and not emitting soot) with luminous flame lengths of 15–63 mm. The present soot-containing flames had larger luminous flame lengths than earlier ground-based observations having similar burner configurations: 40% larger than the luminous flame lengths of soot-containing low gravity flames observed using an aircraft (KC-135) facility due to reduced effects of accelerative disturbances and unsteadiness; roughly twice as large as the luminous flame lengths of soot-containing normal gravity flames due to the absence of effects of buoyant mixing and roughly twice as large as the luminous flame lengths of soot-free low gravity flames observed using drop tower facilities due to the presence of soot luminosity and possible reduced effects of unsteadiness. Simplified expressions to estimate the luminous flame boundaries of round nonbuoyant laminar jet diffusion flames were obtained from the classical analysis of Spalding (1979); this approach provided successful correlations of flame shapes for both soot-free and soot-containing flames, except when the soot-containing flames were in the opened-tip configuration that is reached at fuel flow rates near and greater than the laminar smoke point fuel flow rate.

Soot Formation in Laminar Premixed Methane/Oxygen Flames at Atmospheric Pressure

Abstract Flame structure and soot formation were studied within soot-containing laminar premixed methane/oxygen flames at atmospheric pressure. The following measurements were made: soot volume fractions by laser extinction, soot temperatures by multiline emission, gas temperatures (where soot was absent) by corrected fine-wire thermocouples, soot structure by thermophoretic sampling and transmission electron microscope (TEM), major gas species concentrations by sampling and gas chromatography, and gas velocities by laser velocimetry. Present measurements of gas species concentrations were in reasonably good agreement with earlier measurements due to Ramer et al. as well as predictions based on the detailed mechanisms of Frenklach and co-workers and Leung and Lindstedt; the predictions also suggest that H atom concentrations are in local thermodynamic equilibrium throughout the soot formation region. Using this information, it was found that measured soot surface growth rates could be correlated successfully by predictions based on the hydrogen-abstraction/carbon-addition (HACA) mechanisms of both Frenklach and co-workers and Colket and Hall, extending an earlier assessment of these mechanisms for premixed ethylene/air flames to conditions having larger H/C ratios and acetylene concentrations. Measured primary soot particle nucleation rates were somewhat lower than the earlier observations for laminar premixed ethylene/air flames and were significantly lower than corresponding rates in laminar diffusion flames, for reasons that still must be explained.

Structure and Soot Properties of Nonbuoyant Ethylene/Air Laminar Jet Diffusion Flames

The structure and soot properties of round, soot-emitting, nonbuoyant, laminar jet diffusion flames are described, based on long-duration (175-230-s) experiments at microgravity carried out on orbit in the Space Shuttle Columbia. Experimental conditions included ethylene-fueled flames burning in still air at nominal pressures of 50 and 100 kPa and an ambient temperature of 300 K with luminous flame lengths of 49-64 mm. Measurements included luminous flame shapes using color video imaging, soot concentration (volume fraction) distributions using deconvoluted laser extinction imaging, soot temperature distributions using deconvoluted multiline emission imaging, gas temperature distributions at fuel-lean (plume) conditions using thermocouple probes, soot structure distributions using thermophoretic sampling and analysis by transmission electron microscopy, and flame radiation using a radiometer. The present flames were larger, and emitted soot more readily, than comparable flames observed during ground-based microgravity experiments due to closer approach to steady conditions resulting from the longer test times and the reduced gravitational disturbances of the space-based experiments.

Kinetic Modeling of Methyl Butanoate in Shock Tube

An increased necessity for energy independence and heightened concern about the effects of rising carbon dioxide levels have intensified the search for renewable fuels that could reduce our current consumption of petrol and diesel. One such fuel is biodiesel, which consists of the methyl esters of fatty acids. Methyl butanoate (MB) contains the essential chemical structure of the long-chain fatty acids and a shorter, but similar, alkyl chain. This paper reports on a detailed kinetic mechanism for MB that is assembled using theoretical approaches. Thirteen pathways that include fuel decomposition, isomerization, and propagation steps were computed using ab initio calculations [J. Org. Chem. 2008, 73, 94]. Rate constants from first principles for important reactions in CO(2) formation, namely CH(3)OCO=CH(3) + CO(2) (R1) and CH(3)OCO=CH(3)O + CO (R2) reactions, are computed at high levels of theory and implemented in the mechanism. Using the G3B3 potential energy surface together with the B3LYP/6-31G(d) gradient, Hessian and geometries, the rate constants for reactions R1 and R2 are calculated using the Rice-Ramsperger-Kassel-Marcus theory with corrections from treatments for tunneling, hindered rotation, and variational effects. The calculated rate constants of reaction R1 differ from the data present in the literature by at most 20%, while those of reaction R2 are about a factor of 4 lower than the available values. The new kinetic model derived from ab initio simulations is combined with the kinetic mechanism presented by Fisher et al. [Proc. Combust. Inst. 2000, 28, 1579] together with the addition of the newly found six-centered unimolecular elimination reaction that yields ethylene and methyl acetate, MB = C(2)H(4) + CH(3)COOCH(3). This latter pathway requires the inclusion of the CH(3)COOCH(3) decomposition model suggested by Westbrook et al. [Proc. Combust. Inst. 2008, accepted]. The newly composed kinetic mechanism for MB is used to study the CO(2) formation during the pyrolysis of MB as well as to investigate the autoignition of MB in a shock tube reactor at different temperatures and pressures. The computed results agree very well with experimental data present in the literature. Sensitivity and flux (rate-of-production) analyses are carried out for the CO(2) formation with the new MB mechanism, together with available reaction mechanisms, to assess the importance of various kinetic pathways for each regime. With the new mechanism, the flux analyses for the formation of C(2)H species, one of the most important species for ignition delay time, are also presented at different conditions. In addition to giving a better chemical insight of the pyrolysis/oxidation of MB, the results suggest ways to improve the mechanisms capability to predict CO(2) formation and ignition delay times in pyrolysis and oxidation conditions.

Hydrodynamic Suppression of Soot Emissions in Laminar Diffusion Flames

Effects of flow (hydrodynamic) properties on soot formation and oxidation in nonpremixed hydrocarbon/air flames were studied, emphasizing conditions where effects of buoyancy are small in coflowing laminar jet diffusion flames. Effects of air/fuel-stream velocity ratios were of particular interest; therefore, the experiments were carried out at reduced pressures (0.19-0.50 atm) in order to minimize effects of flow acceleration due to buoyancy. Test conditions included acetylene, propylene, and 1,3-butadiene flames burning in air with air/fuel-stream velocity ratios in the range 0.4-6.7. Measurements included laminar smoke-point properties, as well as the following flame structure properties: soot volume fractions, temperatures, soot structure, concentrations of major gas species, and velocities. The measurements showed that laminar smoke-point flame lengths can be increased, and soot emissions possibly suppressed entirely, by increasing air/fuel-stream velocity ratios. The flame structure measurements suggest that the mechanism of this effect involves the magnitude and direction of flow velocities relative to the flame sheet. In particular, large air/fuel-stream velocity ratios cause soot to form in cool and fuel-rich gases, inhibiting soot nucleation, and then to be drawn directly toward the flame sheet with a limited residence time, inhibiting soot growth, so that capabilities to complete the oxidation of soot are enhanced and the tendencies to emit soot are reduced.

Effects of Hydrodynamics on Soot Formation in Laminar Opposed-Jet Diffusion Flames

Effects of flow (hydrodynamic) properties on the presence of soot in hydrocarbon-fueled laminar opposed-jet diffusion flames were studied experimentally at atmospheric pressure, emphasizing effects of velocities normal to the flame sheet. These velocities were varied for conditions corresponding to combustion in air by transferring nitrogen from the oxidizer stream to the fuel stream, which increases the stoichiometric mixture fraction of the flame and causes the stagnation plane of the flow to shift toward the fuel-rich side of the flame sheet. Fuels considered included acetylene, ethylene, ethane, propylene, propane, and 1-3 butadiene. Present measurements consisted of the critical strain rates for the flames to contain soot (the soot extinction limit) and for the flames to extinguish (the flame extinction limit). It was found that increasing the stoichiometric mixture fraction causes a progressive reduction of the critical strain rates for both flame and soot extinction; however, their ratio increases, and even becomes unbounded in most instances to yield a permanently-blue-flame regime. The results suggest that soot formation in nonpremixed flames can be controlled by varying velocities normal to the flame sheet. Nevertheless, definitive conclusions along these lines require evaluation of effects of corresponding variations of fuel and oxygen concentrations on soot formation when velocities normal to the flame sheet are changed by varying stoichiometric mixture fractions for laminar opposed-jet diffusion flames.

Structure of Laminar Permanently Blue, Opposed-Jet Ethylene-Fueled Diffusion Flames

Abstract The structure and state relationships of laminar soot-free (permanently blue) ethylene-fueled diffusion flames at various strain rates were studied both experimentally and computationally using an opposed-jet configuration. Measurements of gas velocities, temperatures, and compositions were carried out along the stagnation stream line. Corresponding predictions of flame structure were obtained, based on numerical simulations using several contemporary reaction mechanisms for methane oxidation. Flame conditions studied included ethylene-fueled opposed-jet diffusion flames having stoichiometric mixture fractions of 0.7 with measurements involving strain rates of 60–240 s −1 and predictions involving strain rates of 0–1140 s −1 at normal temperature and pressure. It was found that measured major gas species concentrations and temperature distributions were in reasonably good agreement with predictions using mechanisms due to GRI-Mech (Version 1.2, 1995) and Peters (1993) and that effects of preferential diffusion significantly influence flame structure even when reactant mass diffusivities are similar. Oxygen leakage to fuel-rich conditions and carbon monoxide leakage to fuel-lean conditions both increased as strain rates increased. Furthermore, increased strain rates caused increased fuel concentrations near the flame sheet, decreased peak gas temperatures, and decreased concentrations of carbon dioxide and water vapor throughout the flames. State relationships for major gas species and gas temperatures were found to exist over a broad range of strain rates, providing potential for significant computational simplifications for modeling purposes in some instances.

Kinetics of Thermal Unimolecular Decomposition of Acetic Anhydride: An Integrated Deterministic and Stochastic Model

An integrated deterministic and stochastic model within the master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) framework was first used to characterize temperature- and pressure-dependent behaviors of thermal decomposition of acetic anhydride in a wide range of conditions (i.e., 300-1500 K and 0.001-100 atm). Particularly, using potential energy surface and molecular properties obtained from high-level electronic structure calculations at CCSD(T)/CBS, macroscopic thermodynamic properties and rate coefficients of the title reaction were derived with corrections for hindered internal rotation and tunneling treatments. Being in excellent agreement with the scattered experimental data, the results from deterministic and stochastic frameworks confirmed and complemented each other to reveal that the main decomposition pathway proceeds via a 6-membered-ring transition state with the 0 K barrier of 35.2 kcal·mol-1. This observation was further understood and confirmed by the sensitivity analysis on the time-resolved species profiles and the derived rate coefficients with respect to the ab initio barriers. Such an agreement suggests the integrated model can be confidently used for a wide range of conditions as a powerful postfacto and predictive tool in detailed chemical kinetic modeling and simulation for the title reaction and thus can be extended to complex chemical reactions.