Polycyclic Aromatic Hydrocarbon Condensation Research Articles

Experimental and numerical investigations of soot formation in propane laminar coflow flames in O2/N2 and O2/CO2 atmospheres

Oxygen-rich combustion is a new type of clean combustion technology with important application prospects. At present, there are few detailed analyses on the mechanism changes of soot formation under oxygen enrichment of propane. In this paper, the effects of oxygen-rich (O2/N2, O2/CO2) combustion on soot formation in the propane laminar flow coaxial jet diffusion flame were investigated by using the experiment and numerical simulation. The flame image was taken by a color (CCD) camera in the visible band, and the two-dimensional distribution of temperature and soot volume fraction in the flame was reconstructed. In numerical simulation, the soot production model considers a detailed description of nucleation via collisions among heavy polycyclic aromatic hydrocarbons, particle aggregation, polycyclic aromatic hydrocarbons condensation, surface growth and oxidation through the hydrogen abstraction acetylene addition mechanism. The results show that the experimental results were compared with the numerical simulation results, and the numerical simulation results predict the temperature and soot change of oxygen-rich flame well. With the increase in oxygen concentration, the peaks of soot and temperature in the two oxygen-rich atmospheres gradually increased. With the increase in oxygen concentration, the peaks of soot and temperature in the two oxygen-rich atmospheres gradually increased. Comparing the combustion mechanism changes of the two oxygen-rich combustion systems, it was found that the hydrogen abstraction acetylene addition mechanism was the main cause of soot generation. The OH oxidation is dominated near the fuel nozzle side, and O2 oxidation is dominant downstream. With the substitution of CO2 for N2, the chemical effect of CO2 reduces the flame temperature and inhibits the formation mechanism and oxidation mechanism of soot to some extent. This in turn leaded to a reduction in the amount of soot produced.

Effect of CH4 Addition on Soot Formation in C2H4 Diffusion Flame

Abstract Studying the effect of co-combustion of multiple fuels on soot formation has become a hot spot in the investigation of soot particles. In this paper, the influence of methane blending on soot formation in ethylene flame combustion is studied experimentally and numerically. The visible spectrum of flame image processing technology was used for the in situ measurement of laminar flame temperature and carbon smoke volume points in the experiment. The effects of different methane blending ratios on particle nucleation, coalescence, surface growth, and oxidation process of soot were analyzed based on the piecewise particle dynamics soot model of polycyclic aromatic hydrocarbons (PAHs) using CoFlame Code. Results indicate that the synergistic effect promoted the increasing rate of nucleation and addition reaction of hydrogen extraction at a low methane blending ratio, and the increase in the total mass of soot was mainly due to the PAH condensation rate. The total amount of soot generation gradually decreases with increasing blending ratio. The overall trend of condensation, surface growth rate, and soot nucleation in the flame decreases with increasing blending ratio. And the nucleation rate gradually shifts from a single peak to a double peak and increases slightly at the initial stage of the flame combustion reaction. It is worth mentioning that the change of three PAH precursors (secondary benzo(a)pyrenyl, benzo(a)pyrene, and benzo(ghi)fluoranthene) and the temperature explains the change of nucleation rate from unimodal to bimodal.

On the mechanisms affecting soot production in oxygen-depleted buoyant flames

The objective of this article is to apply a detailed polycyclic aromatic hydrocarbons (PAH)-based soot production model to investigate the effects of oxygen depletion on the overall soot production processes in laminar coflow ethylene diffusion flames. This task is accomplished by simulating the flames, studied experimentally by Sun et al. (Combust. Flame 211:96–111, 2020), burning under oxygen concentration in the oxidizer down to 16.8% and characterized by a constant volumetric stoichiometric air to fuel ratio to keep the residence time unchanged. This configuration allows isolating the effects of reducing oxygen on both soot formation and oxidation processes and avoiding the complex interactions between soot production and turbulence. Model predictions are in reasonable agreement with the experiments in terms of temperature, soot volume fraction, and primary particle diameter and capture quantitatively the effects of oxygen depletion on soot production. In all the flames, both the H-abstraction and acetylene addition (HACA) and PAH condensation contribute significantly to the soot mass growth, with the HACA slightly dominating the overall process. Reducing the oxygen concentration affects similarly all the formation and oxidation processes with a reduction in the range 30–40% from 21.0% to 18.9% and in the range from 60 to 70% as it is further reduced to 16.8%. Among the formation processes, the PAH condensation and surface growth by HACA have a similar sensitivity to oxygen depletion, followed by soot inception.

Development of a practical soot model for diesel surrogate fuels and oxygenated fuels with specific soot precursor tracking and uniform model structure

Soot formation and oxidation involve several complex processes, which are driven by gas-phase chemistry and soot particle dynamics. An effective soot model for diesel surrogate and practical oxygenated fuels is necessary for predicting the soot emissions to meet the emission regulations in engines. To develop a practical and universal soot model for various fuels without tuning any model parameters under wide operating conditions, it is important to reproduce the soot behaviors for different fuels with distinct molecular structures. In this work, a practical soot model was developed to describe the soot behaviors for diesel surrogate fuels comprising large n-alkane, isoalkane, cycloparaffin, and aromatic hydrocarbon, as well as oxygenated fuels including alcohol and ether. The influence of the fuel molecular structures on the soot behaviors was emphasized by utilizing the specific reaction pathways of polycyclic aromatic hydrocarbon (PAH) production and the specific reaction channels of the soot formation including soot nucleation and PAH condensation for different fuels. An efficient method named the moment projection method (MPM) was employed to describe the soot particle dynamics by directly solving the moment transport equations and track the number of soot particles. By coupling a reduced chemical reaction model for describing the fuel oxidation chemistry and PAH formation, it is found that the soot volume fraction and number density are well predicted for iso-octane, n-heptane, toluene, methanol, n-butanol, dimethyl ether, their mixtures, and diesel surrogate in shock tubes and laminar premixed flames without tuning any model parameters. The effects of equivalence ratio, temperature, and fuel type on soot production are analyzed through the rates of soot nucleation, surface growth, PAH condensation, and oxidation. The computational results indicate that the present model can satisfactorily reproduce the soot characteristics of different fuels with distinct soot formation and oxidation processes.

Physicochemical characteristics of polycyclic aromatic hydrocarbons in condensable particulate matter from coal-fired power plants: A laboratory simulation

The objective of this study was to examine the physicochemical characteristics of polycyclic aromatic hydrocarbons (PAHs) in condensable particulate matter (CPM) during fast condensation (within several seconds). The concentration of PAHs increased as the condensation temperature decreased, indicating that the conversion of gaseous PAHs to CPM would be enhanced at low temperatures. PAH concentrations increased in relation to the number of rings in the fragment, with the high-ring (4-,5- and 6-ring) PAHs accounting for 89.70–92.30% and 99.78–99.80% of the total concentration and total toxic equivalent of PAHs. In addition, particulate-phase PAHs (0.1–1.0 μm), developed through the synergistic effect of PAHs and fine particles, were difficult to collect by fast condensation. Inorganic fine particles could be formed when ammonia-rich conditions prevail, reducing PAH condensation further. Furthermore, CPM was morphologically and chemically characterized. During the experiment, fine and well-aggregated CPMs were detected on the membrane, and the diameter of CPMs was further enhanced by the addition of 16 PAHs. Most of the C element was collected in the rinse fluid, thus indicating that PAHs in CPM were collected through condensation. Based on these findings, basic guidelines can be provided for the control of PAHs in flue gas from coal-fired power plants.

Numerical Study of PAHs and Soot Emissions from Gasoline–Methanol, Gasoline–Ethanol, and Gasoline–n-Butanol Blend Surrogates

Soot formation is an intricate phenomenon, and soot propensity of a fuel is interwoven with the fuel composition, physical and chemical properties, and combustion environment. The present study examines the hypothesis that in addition to the chemical composition of the fuel, the sooting nature of the fuel is closely coupled with its chemical property known as octane sensitivity (S). With this motivation, the present study numerically investigates the effects of gasoline surrogate composition and its property, octane sensitivity (S), on polycyclic aromatic hydrocarbons (PAHs) and soot emissions. Four-component toluene primary reference fuel (TPRF)–alcohol blends, comprising iso-octane, n-heptane, toluene, and one of the three different alcohols- methanol, ethanol, and n-butanol, are used as gasoline surrogates. A total of 320 TPRF–alcohol mixtures, with S in the range of 1–10, are examined under laminar counterflow diffusion flame conditions. A detailed chemical mechanism coupled with a comprehensive soot model, which includes reactions for soot inception, surface growth, PAH condensation, and oxidation, is adopted. The analysis indicates that the toluene content in the fuel mixture has a prominent effect, while the alcohol content and octane sensitivity of the fuel have a weak correlation with the PAHs and soot. Thus, it is not clear if any of these three variables, namely, toluene content in the fuel, alcohol content in the fuel, and S, are individually sufficient to characterize the PAHs and soot across various blends. For this reason, a new variable (XCHO) based on the elemental composition of the fuel mixture is identified and it is shown that XCHO along with S of the fuel characterize soot emissions satisfactorily. Further, a reaction path analysis indicates that the efficacy of alcohols in reducing soot emissions follows the order: methanol > ethanol > n-butanol.

Modeling soot particles as stable radicals: a chemical kinetic study on formation and oxidation. Part I. Soot formation in ethylene laminar premixed and counterflow diffusion flames

Based on recent theoretical and experimental evidences, this work proposes a detailed discrete sectional soot model considering particles and aggregates behaving as stable radicals, paving the way for the implementation of a game-changing assumption in soot kinetic models. The concentration of large closed-shell and open-shell polycyclic aromatic hydrocarbons (PAHs) levels out with the increase of their aromatic structure and, contrary to conventional assumptions in existing soot models, their reactivity approaches that of persistent radical species. These findings were implemented in the model here proposed to describe soot formation (Part I) and oxidation (Part II). While the number of lumped pseudo-species involved is significantly reduced compared to previous discrete sectional soot models since no distinction between the kinetics of closed-shell and open-shell particles is taken into account, the physical meaning and consistency with recent evidences improves together with model performances. Rate parameters of gas-phase reactions involving resonantly stabilized radical PAHs were used as a reference for soot particle kinetics. The model was validated against 65 target ethylene laminar premixed flames and counterflow diffusion flames, with a general good agreement between experimental data and numerical simulations at different pressures (P = 1–8 atm), maximum flame temperatures (Tmax∼1500–2400 K) and soot yields (fv∼0.01 to ∼170 ppm). Parity diagrams allow to identify systematic deviations of the present model from the experiments, while the comparison between all the flames included in the database highlights the relative contribution to soot formation and growth of the main reaction classes constituting the soot model, spotting analogies and peculiarities of the two flame configurations considered. Similar kinetic patterns characterize most of the flames within the database, independently of flame configuration and sooting tendency of the specific case. Large PAH condensation dominates the formation of the first soot nuclei, while the condensation of smaller PAHs up to four aromatic rings is primarily responsible for the growth of larger soot particles and aggregates. Finally, the contribution of the different fluid dynamics in premixed and counterflow flames to particle evolution, resulting in a higher hydrogenation level of soot particles in the latter, is discussed.

Molecular Dynamics Study on the Condensation of PAH Molecules on Quasi Soot Surfaces.

In this paper, the condensation efficiency of polycyclic aromatic hydrocarbon (PAH) molecules up to coronene, from 500 to 2000 K, is calculated based on hundreds of collisions between a PAH molecule and the quasi soot surface, which is composed of stacked coronene molecules with periodic boundary conditions, using molecular dynamics simulations. The results show that the condensation efficiency increases with the PAH molecular mass but decreases as the temperature increases, following a Gaussian function. Meanwhile, when the presence of aliphatic chains on soot particle surfaces is considered, the condensation efficiency can be lowered by up to 40%, being affected more significantly at higher temperatures. A condensation efficiency model is thus proposed from the molecular trajectories. Finally, when this newly proposed PAH condensation efficiency model is adopted, better agreement with the experiments is achieved in predicting soot volume fractions of an ethylene/oxygen/nitrogen mixture in a tandem jet-stirred reactor and a plug-flow reactor.

Effects of soot inception and condensation PAH species and fuel preheating on soot formation modeling in laminar coflow CH4/air diffusion flames doped with n-heptane/toluene mixtures

This paper investigates the effects of soot inception and condensation polycyclic aromatic hydrocarbon (PAH) species and fuel preheating on soot prediction in 2D coflow laminar CH4/air diffusion flames doped with vaporized gasoline surrogate fuels, i.e., n-heptane/toluene mixtures. To evaluate the importance of considering multiple PAHs in soot inception and condensation and fuel pyrolysis near fuel tube outlet in the prediction of soot distribution along the flame centerline, the pyrene-based soot inception and PAH condensation model was improved by considering multi-PAH (A2, A2R5, A3C2H, A4, BGHIF) as nucleation and condensation species. The fuel preheating effect upstream the fuel tube exit was taken into account. Inclusion of multiple PAHs in soot inception and condensation leads to greatly enhanced soot formation along the flame centerline region due to enhanced soot inception and surface growth via PAH condensation. As a result of soot inception through smaller PAH (A2), soot appears at a lower flame height above the burner exit than experiments. The fuel preheating effect causes significantly higher fuel stream temperatures in the near burner wall region and appreciable fuel pyrolysis. Soot inception is further enhanced by the fuel preheating effect and soot appears at an even lower height above the burner exit with a reduced flame height. This study demonstrated that both multi-PAH coagulation and fuel preheating strengthen soot inception and improve the predicted soot volume fractions along the flame centerline, but they are still insufficient to achieve good agreement with available experiments. Plausible ways to further improve the soot model are discussed.

Soot production modeling in a laminar coflow ethylene diffusion flame at different Oxygen Indices using a PAH-based sectional model

A numerical study is carried out to, first of all, investigate the capability of a Polycyclic Aromatic Hydrocarbon (PAH)-based sectional particle dynamics soot model in the prediction of soot production in laminar coflow ethylene diffusion flames. The effects of different oxygen mole fractions in the oxidizer stream, called Oxygen Index (OI), ranging from 17% to oxygen-enriched conditions up to 33% are investigated. Secondly, the relative importance of species responsible for the increase in both soot formation and oxidation rates with increasing the OI is analyzed. The soot production model considers a detailed description of nucleation via collisions among heavy PAHs, particle aggregation, PAH condensation, surface growth and oxidation through the hydrogen abstraction acetylene addition (HACA) mechanism, and fragmentation of soot aggregates. Model predictions are compared with previously-published experimental data and numerical predictions obtained with a semi-empirical acetylene-based soot production model [Comb. Flame 160: 786–795 (2013)]. Results indicate that the flame structure, soot volume fraction and flame cross-section integrated soot volume fraction predicted by the PAH-based sectional soot model are in good agreement with the experimental data over the entire range of OI considered. The temperature and the concentrations of soot precursors increase with the OI, leading to higher soot nucleation, condensation, surface growth, and oxidation rates. Results show that the PAH-based sectional soot model represents a significant improvement over the semi-empirical acetylene based two-equation soot model studied earlier, especially in conditions far from the normal air conditions (21% of O2). With increasing the OI, the non-dimensional zone of influence does not change for the flame cross-section integrated soot formation rates but increases for the integrated soot oxidation rate. Nucleation occurs just above the burner rim and displays the largest increase in its rate with increasing the OI. Nucleation and condensation are mainly dependent on the concentrations of BGHIF and BAPYR. Condensation is also affected by the increase in the number of aggregates available for collision. Soot formation is mainly dominated by surface growth, through HACA, with a significant influence of soot condensation closer to the burner surface, regardless of the level of OI. The surface growth through HACA is mainly controlled not only by the acetylene concentration and the associated kinetic rate, but also by the specific soot surface area. Oxidation by O2 is found to dominate at the top of the flame, while oxidation by OH is dominant at the middle height of the flame. The oxidation rate by O2 increases more rapidly with increasing the OI than that by OH.

Soot formation characteristics of ethylene premixed burner-stabilized stagnation flame with dimethyl ether addition

Effect of dimethyl ether (DME) addition on PAH and soot formation mechanisms as well as particle-size distribution function (PSDF) behavior of C2H4 premixed burner-stabilized stagnation (BSS) flame was studied. A wide range of DME addition from pure C2H4 to pure DME was considered. The sectional aerosol dynamics model with detailed gas- and particle-phase kinetic mechanism was employed for the simulations. The results indicate that soot growth rate by nucleation, and especially the H-abstractionC2H2addition (HACA) mechanism and polycyclic aromatic hydrocarbons (PAH) condensation increased significantly inside the stagnation boundary layer, due to strong flame-wall interaction. The PSDF curve in the post-flame region was unimodal, while that in the stagnation boundary layer was bimodal. The first peak of the PSDF curve in the stagnation boundary was resulted from the enhanced nucleation rate, and the second peak was due to the intensified soot surface growth by HACA reaction and PAH condensation. The rich premixed C2H4 BSS flame did not exhibit the synergistic effect of DME addition on PAH and soot formations. Soot formation rate decreased monotonously with DME addition for the C2H4 premixed BSS flame. Topology of soot PSDF behavior of the C2H4 premixed BSS flame changed significantly when DME addition exceeded above 20%.

Numerical simulations of microgravity ethylene/air laminar boundary layer diffusion flames

Microgravity ethylene/air laminar boundary layer diffusion flames were studied numerically. Two oxidizer velocities of 250 and 300 mm/s and three fuel injection velocities of 3, 4, and 5 mm/s were considered. A detailed gas-phase reaction mechanism, which includes aromatic chemistry up to four rings, was used. Soot kinetics was modeled by using a pyrene-based model including the mechanisms of nucleation, heterogeneous surface growth and oxidation following the hydrogen-abstraction acetylene-addition (HACA) mechanism, polycyclic aromatic hydrocarbon (PAH) surface condensation and soot particle coagulation. Radiative heat transfer from CO, CO2, H2O and soot was calculated using the discrete ordinate method (DOM) coupled to a wide-band correlated-k model. Model predictions are in quantitative agreement with the available experimental data. Model results show that H and OH radicals, responsible for the dehydrogenation of sites in the HACA process, and pyrene, responsible for soot nucleation and PAH condensation, are located in a thin region that follows the stand-off distance. Soot is produced in this region and, then, is transported inside the boundary layer by convection and thermophoresis. The combustion efficiency is significantly lower than 1 and is reduced as the flow residence time increasing, confirming that these sooting micro-gravity diffusion flames are characterized by radiative quenching at the flame trailing edge. In particular, this quenching phenomenon explains the increase in flame length with the oxidizer velocity observed in previous experimental studies. The effects of using approximate radiative-property models, namely the optically-thin approximation and gray approximations for soot and combustion gases, were assessed. It was found that the re-absorption and the spectral dependence of combustion gases and soot must be taken into account to predict accurately temperature, soot volume fraction, flame geometry and flame quenching.

Application of PAH-condensation reversibility in modeling soot growth in laminar premixed and nonpremixed flames

A new model for condensation of polycyclic aromatic hydrocarbons (PAHs) on the surface of soot particles is developed based on the reversibility of the process. Statistical mechanics has been integrated with a novel PAH condensation concept to estimate the PAH evaporation rate. This estimation has been used to develop a condensation efficiency model which is easy to implement, computationally efficient, and relies on physical parameters which can be evaluated. The new condensation model, combined with a reversible nucleation model (Eaves et al., 2015), is validated for predicting soot formation in both premixed and nonpremixed flames. The validations are followed by an extensive sensitivity analysis to evaluate the role of dominant soot processes as well as PAH chemistry on soot formation and particle size distribution (PSD). Simulations include a set of burner stabilized stagnation premixed flames and a coflow ethylene/air diffusion flame. This work is the first study which successfully utilizes a single soot model to quantitatively predict soot formation in both flame configurations.

Dynamics simulation and reaction pathway analysis of characteristics of soot particles in ethylene oxidation at high temperature

Soot particles characteristics were investigated numerically for high temperature oxidation of C2H4/O2/N2 (C/O ratio of 2.2) in a closed jet-stirred/plug-flow reactor (JSR/PFR) system. Based on the growth mechanism of polycyclic aromatic hydrocarbons (PAHs), two mechanisms were used to explore the formation pathways of soot precursors and soot. Numerical results were compared with the experimental and reference data. The simulation results show that the value predicted for small molecule intermediates within A1 gives a strong regularity, consistent trend with reference data. However, with the hydrogen-abstraction-carbon-addition (HACA) growth mechanism, the predicted value for beyond-A1 PAH macromolecules and soot volume fraction are smaller than the experimental data. The results also show that the predicted soot volume fraction is in good agreement with experimental data when a combination of the HACA and PAHs condensation (HACA + PAH-PAH) growth mechanisms is used. Analyses of the A1 sensitivity and reaction pathway elucidated that A1 are mainly formed from C2H3, C2H2, C3H3, C6H5OH, A1C2H and A1-. The reaction 2C3H3 → A1 is the dominant route of benzene formation. The prediction results and an analysis of the A3 reaction pathway indicate that the growth process from benzene to larger aromatic hydrocarbons (beyond two-ring polycyclic aromatic hydrocarbons [PAHs]) goes by two pathways, i.e., HACA combined with the PAH-PAH radical recombination and addition reaction growth mechanisms.

The Effect of Conjugate Heat Transfer on Soot Formation Modeling at Elevated Pressures

Previous attempts to model elevated-pressure coflow laminar flames have been hindered by neglecting the preheating within the burner, caused by downward heat transfer to the burner. In the present work, the computational domain is extended below the exit plane of the fuel tube to account for the flame preheating effect. Conjugate heat transfer (CHT) is implemented by the harmonic mean method to model the heat transfer between the fluid streams and solid fuel tube. This extension of the domain allows for solutions to a high pressure ethane/air data set from 2 to 33 atm, which is an improvement over previous attempts where only pressures below 15 atm could be modeled. The extended model more accurately predicts centerline soot formation than the truncated model due to capturing fuel pyrolysis that occurs below the exit plane of the fuel tube. This increased fuel pyrolysis increases the contribution by polycyclic aromatic hydrocarbon (PAH) condensation to computed soot volume fractions. For pressures above 20 atm, the extended model predicts that PAH condensation is the dominant mechanism on the wings—a location where surface growth was thought to be heavily dominant regardless of flame characteristics. It is determined that the choice of fuel tube wall treatment does significantly affect numerical predictions, with the best experimental agreement obtained using a CHT model as oppose to an isothermal or adiabatic walls. The extended model with CHT is the only model that displays quantitative accuracy and is a significant advancement over previous qualitatively accurate models. [Supplementary materials are available for this article. Go to the publisher's online edition of Combustion Science and Technology for the following free supplemental resource: Numerical details.]

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.

Experimental and computational study of soot evolution in a turbulent nonpremixed bluff body ethylene flame

A turbulent nonpremixed bluff body ethylene flame is studied both experimentally and computationally. Experimentally, the soot volume fraction is measured using laser-induced incandescence (LII). Three distinct regions are observed in the flame: a low-strain recirculation zone, a downstream jet-like region, and a high-strain neck region connecting these two regions. The maximum soot volume fraction is found in the recirculation zone, but most of the soot volume is contained in the larger jet-like region further downstream. In the neck region between these two zones, soot cannot form due to large strain rates, and the small amounts of soot in this region indicate that soot rarely escapes the recirculation zone before being oxidized. The recirculation zone is characterized by a low soot intermittency, in contrast to the downstream jet-like region and previously investigated jet flames in which the soot intermittency is high. Large Eddy Simulation (LES) is used to further investigate this distinctly different evolution of soot in the recirculation zone. The LES model is found to predict the soot volume fraction profiles quite accurately, albeit with significant sensitivity to the inflow profiles of the fuel jet and air coflow. Soot is formed near the inner shear layer between the fuel jet and recirculation zone where the mixture fraction is sufficiently large to support Polycyclic Aromatic Hydrocarbon (PAH) formation. A portion of this soot is entrained into the interior of the recirculation zone where the soot growth rates are relatively low, despite the rich mixture fraction in this region. The circulation vortex then transports the soot from the interior of the recirculation zone toward less rich mixture fractions near the flame, which is situated in the outer shear layer between the air coflow and the recirculation zone. Here, the majority of soot growth occurs due to surface growth, that is, mass addition due to surface reactions with acetylene. The dominance of acetylene-based surface growth in the recirculation zone contrasts findings in previous simulations of turbulent jet flames that do not exhibit a recirculation zone, in which nucleation and PAH condensation were found to overwhelm acetylene-based surface growth.

Fractionated extraction of polycyclic aromatic hydrocarbons (PAHs) from polluted soils: estimation of the PAH fraction degradable through bioremediation

SummaryChemical extractions were tested to estimate the fraction of 15 polycyclic aromatic hydrocarbons (PAHs) in polluted soils degradable through bioremediation. Of 30 soil samples, differing in PAH concentrations, from 10 long‐term polluted sites, four were used in screening tests conducted with 14 different extractants. PAH extractability increased in the order salt solutions < surfactant solutions < organic solvents and organic solvent–water mixtures. Closest correlations (r = 0.73–0.91) and ratios of c. 1:1 of the extracted to the degradable PAH concentrations were found with aqueous solutions of two surfactants (Genapol UDD 88, Synperonic LF/RA 30).The PAH extractability by surfactant solutions increased with surfactant concentration (0–50 mg ml−1) and with decreasing degree of PAH condensation (6–2 rings). Kinetic behaviour of PAH solubilization by surfactants resembled the kinetics of PAH degradation (r = 0.84–0.99). With repeated extractions, a finite fraction of PAHs was extracted, which is thought to be the mobile and mobilizable PAH fraction, the latter being controlled by back‐diffusion from intra‐ and inter‐particle sites.Experiments with all 30 soil samples and a priori testing with an additional 10 soil samples confirmed that single extractions with surfactant solutions (5 mg ml−1; soil:solution ratio 1:20) were suitable for estimating the degradable fraction of PAHs in soil. With separate linear regression equations for PAHs grouped according to their degree of condensation, the extracted concentrations described the degradable concentrations with correlation coefficients (r) ranging from 0.62 to 0.80 (P < 0.001). PAH extractions with the surfactant solutions can be used to assess the prospects of bioremediation of PAH‐polluted sites.

Investigating the role of methane on the growth of aromatic hydrocarbons and soot in fundamental combustion processes

Experimental results are presented on the effect of methane content in a non-aromatic fuel mixture on the formation of aromatic hydrocarbons and soot in various fundamental combustion configurations. The systems considered consist of a laminar flow reactor, a laminar co-flow diffusion flame burner, and a laminar, premixed flame burner, all of which operate at atmospheric pressure. In the flow reactor, the experiments are performed at 1430 K, constant C-atom flow rates, 98% nitrogen dilution, C/O ratio = 2, and with fuel mixtures consisting of ethylene and methane. The diffusion flames are performed with fuel mixtures of methane and ethylene diluted in nitrogen to maintain a constant adiabatic flame temperature. The premixed flame experiments are performed with n-heptane and methane mixtures at a C/O ratio = 0.67 with nitrogen-impoverished air. The results show the existence of synergistic chemical effects between methane and other alkanes in the production of aromatics, despite reduced acetylene concentrations. This effect is attributable to the ability of methane to enhance the production of methyl radicals that will then promote production channels of aromatics that rely on odd-carbon-numbered species. Benzene, naphthalene, and pyrene show the strongest sensitivity to the presence of added methane. This synergy on aromatics trickles down to soot via enhanced inception and surface growth rates by polycyclic aromatic hydrocarbon condensation, but the overall effects on soot volume-fraction are smaller due to a compensating reduction in surface growth from acetylene. These results are observed under the very fuel-rich environments existing in the flow reactor and diffusion flames. In the premixed flames, however, instabilities did not permit investigation of conditions with sufficiently high equivalence ratios to perturb the aromatic and soot-growth regions.

Silicon carbide and the origin of interstellar carbon grains

THE mechanisms of interstellar grain formation are not well understood. Such grains are complex1,2, with components that include silicates, ices and carbonaceous material. Several forms have been proposed for interstellar carbon, including graphite3, amorphous carbon4, polycyclic aromatic hydrocarbons (PAHs)5, diamond6, fullerenes7 and bacteria8. The stellar winds of carbon-rich red-giant stars are the dominant source of interstellar carbon grains9–11. However, the processes leading to the formation of grains are usually discussed only in the general terms of thermodynamics and classical nucleation theory12,13. One possibility9 is that PAH condensation initiates the formation of grains, similar to the formation of soot in hydrocarbon pyrolysis and combustion. Our recent computational study14 demonstrates by detailed chemical kinetics modelling that PAHs can, under certain conditions, form in carbon-star molecular envelopes within a 900–1,100-K temperature regime. Although homogeneous gas-phase condensation of PAHs might lead to the formation of grains, we suggest instead that SiC nucleates at higher temperatures and provides a surface for subsequent carbon condensation. Here we present experimental evidence in support of this idea.