Thesis (M.S.)--Worcester Polytechnic Institute. / Keywords: soot formation; FDS; flame radiation; soot oxidation; field modeling; diffusion flames; soot. Includes bibliographical references (p. 14-15).

A better understanding and control of internal combustion engine pollutants require more insightful investigation of gasoline oxidation chemistry. An oxidation study has been done on n-heptane, iso-octane, their binary mixtures (Primary Reference Fuel, (PRF)), and nine hydrocarbon mixtures which represent the second generation of gasoline surrogates (multi-component surrogates). This study aims to develop a better understanding of the combustion reaction by studying the oxidation reaction of different fuels inside a jet-stirred reactor and numerically simulating the reaction using different models under the following conditions: pressure 1 bar, temperature 500-1050K, residence time 1.0 and 2.0s, and two fuel-to-oxygen ratios (ϕ=0.5 and 1.0). Intermediate and product species mole fractions versus temperature profiles were experimentally measured using a GC (gas chromatograph). The experiment was performed within the high and low-temperature regions, where the high-temperature oxidation showed similar behavior for different compositions but the low-temperature oxidation showed significant dependence on the composition of the surrogates. Additionally, the effect of octane number on oxidation chemistry has been investigated and it was found that the low octane number surrogates were more reactive than high octane number surrogates during the low temperature regime. Furthermore, Kinetic analysis was conducted to provide insightful understanding of different factors of fuel reactivity. In addition, the pyrolysis of two TPRF, (Toluene primary reference fuels) mixtures (TPRF70 and TPRF97.5), representing low octane (research octane number 70) and high octane (research octane number 97.5) gasoline, was also studied in jet-stirred reactor coupled with gas chromatography (GC) analysis to investigate the formation of soot and polycyclic aromatic hydrocarbons (PAH) formation.

Abstract: Soot from combustion emissions has a negative impact on human health and the environment. Understanding and controlling soot formation is desirable to reduce this negative impact, especially as energy demands continue to increase. In this work, a range of fundamental combustion experiments are performed to better understand the soot formation process, and to develop diagnostics for measuring soot properties. First, studies on the effects of doping the flame with different polycyclic aromatic hydrocarbons (PAHs) was performed to investigate soot nucleation mechanisms. Soot formation was found to be most sensitive to phenylacetylene addition and nucleation through physical dimerization appears to be unlikely. Next, the effects of ammonia addition, a possible future fuel, on soot formation in laminar nonpremixed ethylene counterflow flames was performed. A reduction in soot volume fraction was observed and attributed to chemical effects of ammonia addition. Second, the investigation and development of several types of diagnostics was performed. Soot is typically reported to scale with pressure as Pn where P is pressure and n is a scaling factor. A wide range of scaling factors for ethylene coflow flames have been reported using different types of diagnostics. In this work, a comparison between a light extinction technique and PLII was performed and differences between reported values was explored. Next, the time resolved laser induced incandescence (TiRe-LII) diagnostic was advanced by exploring the effects of SVF on local gas heating. Errors introduced into this model by neglecting local gas heating are explored. Finally, a new diagnostic was developed for 3 dimensional measurements of SVF and velocity in turbulent flames using a technique known as diffuse-backlight illumination extinction imaging. Third, the application of gated 2D TiRe-LII was assessed in pressurized environments on laminar coflow flames. Comparisons between TiRe-LII and thermophoretically captured soot imaged by transmission electron microscopy (TEM) was performed. TiRe-LII was found to have reasonable agreement with TEM measurements if the SNR was high, but due to the large disparity in primary particle size in pressurized environments errors in 2D TiRe-LII can be significant.

An experimental study was conducted using axisymmetric co-flow laminar diffusion flames of methane-air, methane-oxygen and ethylene-air to examine the effect of pressure on soot formation and the structure of the temperature field. A liquid fuel burner was designed and built to observe the sooting behavior of methanol-air and n-heptane-air laminar diffusion flames at elevated pressures up to 50 atm. A non-intrusive, line-of-sight spectral soot emission (SSE) diagnostic technique was used to determine the temperature and the soot volume fraction of methane-air flames up to 60 atm, methane-oxygen flames up to 90 atm and ethylene-air flames up to 35 atm. The physical flame structure of the methane-air and methane-oxygen diffusion flames were characterized over the pressure range of 10 to 100 atm and up to 35 atm for ethylene-air flames. The flame height, marked by the visible soot radiation emission, remained relatively constant for methane-air and ethylene-air flames over their respected pressure ranges, while the visible flame height for the methane-oxygen flames was reduced by over 50 % between 10 and 100 atm. During methane-air experiments, observations of anomalous occurrence of liquid material formation at 60 atm and above were recorded. The maximum conversion of the carbon in the fuel to soot exhibited a strong power-law dependence on pressure. At pressures 10 to 30 atm, the pressure exponent is approximately 0.73 for methane-air flames. At higher pressures, between 30 and 60 atm, the pressure exponent is approximately 0.33. The maximum fuel carbon conversion to soot is 12.6 % at 60 atm. For methane-oxygen flames, the pressure exponent is approximately 1.2 for pressures between 10 and 40 atm. At pressures between 50 and 70 atm, the pressure exponent is about -3.8 and approximately -12 for 70 to 90 atm. The maximum fuel carbon conversion to soot is 2 % at 40 atm. For ethylene-air flames, the pressure exponent is approximately 1.4 between 10 and 30 atm. The maximum carbon conversion to soot is approximately 6.5 % at 30 atm and remained constant at higher pressures.

The steady coflow diffusion flame is a widely used configuration for studying combustion kinetics, flame dynamics, and pollutant formation. In the current work, a set of diluted ethylene-air coflow flames are simulated to study the formation, growth, and oxidation of soot, with a focus on the effects of pressure on soot yield. Firstly, we assess the ability of a high performance CFD solver, coupled with detailed transport and kinetic models, to reproduce experimental measurements, like the temperature field, the species’ concentrations and the soot volume fraction. Fully coupled conservation equations for mass, momentum, energy, and species mass fractions are solved using a low Mach number formulation. Detailed finite rate chemistry describing the formation of Polycyclic Aromatic Hydrocarbons up to cyclopenta[cd]pyrene is used. Soot is modeled using a moment method and the resulting moment transport equations are solved with a Lagrangian numerical scheme. Numerical and experimental results are compared for various pressures. Reasonable agreement is observed for the flame height, temperature, and the concentrations of various species. In each case, the peak soot volume fraction is predicted along the centerline as observed in the experiments. The predicted integrated soot mass at pressures ranging from 4-8 atm, scales as P2.1, in satisfactory agreement with the measured integrated soot pressure scaling (P2.27). Significant differences in the mole fractions of benzene and PAHs, and the predicted soot volume fractions are found, using two well-validated chemical kinetic mechanisms. At 4 atm, one mechanism over-predicts the peak soot volume fraction by a factor of 5, while the other under-predicts it by a factor of 5. A detailed analysis shows that the fuel tube wall temperature has an effect on flame stabilization.

An experimental study was conducted using axisymmetric co-flow laminar diffusion flames of methane-air, methane-oxygen and ethylene-air to examine the effect of pressure on soot formation and the structure of the temperature field. A liquid fuel burner was designed and built to observe the sooting behavior of methanol-air and n-heptane-air laminar diffusion flames at elevated pressures up to 50 atm. A non-intrusive, line-of-sight spectral soot emission (SSE) diagnostic technique was used to determine the temperature and the soot volume fraction of methane-air flames up to 60 atm, methane-oxygen flames up to 90 atm and ethylene-air flames up to 35 atm. The physical flame structure of the methane-air and methane-oxygen diffusion flames were characterized over the pressure range of 10 to 100 atm and up to 35 atm for ethylene-air flames. The flame height, marked by the visible soot radiation emission, remained relatively constant for methane-air and ethylene-air flames over their respected pressure ranges, while the visible flame height for the methane-oxygen flames was reduced by over 50 % between 10 and 100 atm. During methane-air experiments, observations of anomalous occurrence of liquid material formation at 60 atm and above were recorded. The maximum conversion of the carbon in the fuel to soot exhibited a strong power-law dependence on pressure. At pressures 10 to 30 atm, the pressure exponent is approximately 0.73 for methane-air flames. At higher pressures, between 30 and 60 atm, the pressure exponent is approximately 0.33. The maximum fuel carbon conversion to soot is 12.6 % at 60 atm. For methane-oxygen flames, the pressure exponent is approximately 1.2 for pressures between 10 and 40 atm. At pressures between 50 and 70 atm, the pressure exponent is about -3.8 and approximately -12 for 70 to 90 atm. The maximum fuel carbon conversion to soot is 2 % at 40 atm. For ethylene-air flames, the pressure exponent is approximately 1.4 between 10 and 30 atm. The maximum carbon conversion to soot is approximately 6.5 % at 30 atm and remained constant at higher pressures.

Soot formation from complex solid fuels, such as coal or biomass, is an under-studied and little understood phenomena which has profound physical effects. Any time a solid fuel is combusted, from coal-burning power plants to wildland fires, soot formation within the flame can have a significant influence on combustion characteristics such as temperature, heat flux, and chemical profiles. If emitted from the flame, soot particles have long-last effects on human health and the environment. The work in this dissertation focuses on creating and implementing computational models to be used for predicting soot mechanisms in a combustion environment. Three models are discussed in this work; the first is a previously developed model designed to predict soot yield in coal systems. This model was implemented into a computational fluid dynamic software and results are presented. The second model is a detailed-physics based model developed here. Validation for this model is presented along with some results of its implementation into the same software. The third model is a simplified version of the detailed model and is presented with some comparison case studies implemented on a variety of platforms and scenarios. While the main focus of this work is the presentation of the three computational models and their implementations, a considerable bulk of this work will discuss some of the technical tools used to accomplish this work. Some of these tools include an introduction to Bayesian statistics used in parameter inference and the method of moments with methods to resolve the 'closure' problem.

Soot formation is one of the most complex phenomena in combustion science and an understanding of the underlying physico-chemical mechanisms is important. This work adopted both experimental and numerical approaches to study soot formation in laminar counterfl ow diffusion flames. As polycyclic aromatic hydrocarbons (PAHs) are the precursors of soot particles, a detailed gas-phase chemical mechanism describing PAH growth upto coronene for fuels with 1 to 4 carbon atoms was validated against laminar premixed and counter- flow diffusion fl ames. Built upon this gas-phase mechanism, a soot model was then developed to describe soot inception and surface growth. This soot model was sub- sequently used to study fuel mixing effect on soot formation in counterfl ow diffusion flames. Simulation results showed that compared to the baseline case of the ethylene flame, the doping of 5% (by volume) propane or ethane in ethylene tends to increase the soot volume fraction and number density while keeping the average soot size almost unchanged. These results are in agreement with experimental observations. Laser light extinction/scattering as well as laser induced fluorescence techniques were used to study the effect of strain rate on soot and PAH formation in counterfl ow diffusion ames. The results showed that as strain rate increased both soot volume fraction and PAH concentrations decreased. The concentrations of larger PAH were more sensitive to strain rate compared to smaller ones. The effect of CO2 addition on soot formation was also studied using similar experimental techniques. Soot loading was reduced with CO2 dilution. Subsequent numerical modeling studies were able to reproduce the experimental trend. In addition, the chemical effect of CO2 addition was analyzed using numerical data. Critical conditions for the onset of soot were systematically studied in counterfl ow diffusion ames for various gaseous hydrocarbon fuels and at different strain rates. A sooting temperature index (STI) and a sooting sensitivity index (SSI) were proposed to present the sooting tendencies of different fuels and their sensitivities to strain rates.

The Fire Dynamics Simulator (FDS) code recently developed by the National Institute of Standards and Technology (NIST) is particularly well-suited for use by fire protection engineers for studying fire behavior. It makes use of Large Eddy Simulation (LES) techniques to directly calculate the large-scale fluid motions characteristic of buoyant turbulent diffusion flames. However, the underlying model needs further development and validation against experiment in the areas of soot formation/oxidation and radiation before it can be used to calculate flame heat transfer and predict the burning of solid or liquid fuels. WPI, Factory Mutual Research, and NIST have undertaken a project to make FDS capable of calculating the flame heat transfer taking place in fires of hazardous scale. The temperatures predicted by the FDS code were generally too high on the fuel side and too low on the oxidant side when compared to experimental data from small-scale laminar diffusion flames. For this reason, FDS was reformulated to explicitly solve the conservation of energy equation in terms of total (chemical plus sensible) enthalpy. This allowed a temperature correction to be applied by removing enthalpy from the fuel side and adding it to the oxidant side. This reformulation also has advantages when using probability density function (PDF) techniques in larger turbulent flames because the radiatively-induced nonadiabaticity is tracked locally with each fluid parcel. The divergence of the velocity field, required to obtain the flow-induced perturbation pressure, is calculated from an expression derived from the continuity equation. A new approach to soot modeling in diffusion flames was developed and added to the FDS code. The soot model postulated as part of this work differs from others because it is intended for engineering calculations of soot formation and oxidation in an arbitrary hydrocarbon fuel. Previous models contain several fuel-specific constants that generally can only be determined by calibration experiments in laminar flames. The laminar smoke point height, an empirical measure of a fuel?s sooting propensity, is used in the present model to characterize fuel-specific soot chemistry. Two separate mechanisms of soot growth are considered. The first is attributed to surface growth reactions and is dependent on the available surface area of the soot aerosol. The second is attributed to homogeneous gas-phase reactions and is independent of the available soot surface area. Soot oxidation is treated empirically in a global (fuel-independent) manner. The local soot concentration calculated by the model drives the rate of radiant emission. Calibration against detailed soot volume fraction and temperature profiles in laminar axisymmetric flames was performed. This calibration showed that the general approach postulated here is viable, yet additional work is required to enhance and simplify the model. The essential mathematics for modeling larger turbulent flames have also been developed and incorporated into the FDS code. An assumed-beta PDF is used to approximate the effect of unresolved subgrid-scale fluctuations on the grid-scale soot formation/oxidation rate. The intensity of subgrid-scale fluctuations is quantified using the principle of scale similarity. The modified FDS code was used to calculate the evolution of soot in buoyant turbulent diffusion flames. This exercise indicated that the subgrid-scale fluctuations are quantitatively important in LES of turbulent buoyant diffusion flames, although no comparison of prediction and experiment was performed for the turbulent case.

Soot prediction from combustion systems is still a major challenge in high-fidelity simulations of reactive flows, especially in turbulent conditions. Among the critical aspects, due to its slow characteristic formation times, soot sensitivity to strain rate and turbulence-chemistry interaction models for combustion closure can be found. Starting from the laminar problem, Soot Formation (SF) and Soot Formation Oxidation (SFO) counterflow flames are studied, allowing assessment of the roles of the different underlying phenomena concurring at soot formation with varying strain rates, depending on their relevance in each configuration. Attention is devoted to the inception model, which always regulates the onset of soot formation, and entirely determines the soot sensitivity to strain rate in the SF configuration through nucleation and condensation. Besides, surface growth and oxidation are analyzed in the SFO configuration, where they are predominant. The corresponding models are fine-tuned and generalized, and improved predictions are obtained in both configurations. Afterwards, a 2-points flame-controlling continuation method with soot module inclusion is developed to build a tool capable of flamelets generation inclusive of soot effects on the gas phase. The implementation is first tested discussing general features of the S-curve and verifying the consistency with previous works. The tool is finally used to compute the S-curve of ethylene pressurized sooting flames. The models and tools developed are incorporated into an OpenFOAM-based solver to perform Computational Fluid Dynamic (CFD) simulations of sooting turbulent flames. These are studied in pressurized, highly turbulent environments, to validate the soot model at a fundamental level but with practically relevant operative conditions. The numerical results are found to satisfactorily depict the soot volume fraction (SVF) formation, even though a few quantitative and qualitative discrepancies are discussed. Furthermore, soot intermittency and pressure scaling are analyzed. Finally, an alternative turbulence-chemistry interaction model for combustion closure is explored. A generalized partially-stirred reactor model is developed which accounts for all chemical times in a consistent manner. While the applicability of available models is confined to specific turbulence-chemistry interaction regimes, the incorporation of detailed chemistry description in the proposed approach improves synergistic predictions of all species and makes it suitable for systems with characteristic times very different from each other, such as soot and NOx.