Pressure effect on soot formation in turbulent diffusion flames

Soot formation in a methane air turbulent jet diffusion flame is investigated numerically using a semi-empirical model. The temperature, density and species (the soot precursor C2H2) fields are calculated using detailed chemical kinetic mechanism based on the flamelet library approach. The influence of pressure on the soot formation and the behavior of the semi-empirical model in different flame situations are investigated. It is found that the flame shape and the flame temperature can be well predicted by the flamelet library approach. The calculated soot yield is mostly sensitive to the soot surface growth rate and the increase of pressure. The increase of pressure leads to the increase of soot surface growth rate and therefore to the increase of soot volume fraction. By adjusting a model constant in the soot surface growth rate, the soot emissions in both pressure p = 1 atm and p = 3 atm are properly simulated by the current semi-empirical soot model.     

Modeling aerosol formation in opposed-flow diffusion flames

The microstructures of atmospheric pressure, counter-flow, sooting, flat, laminar ethylene diffusion flames have been studied numerically by using a new kinetic model developed for hydrocarbon oxidation and pyrolysis. Modeling results are in reasonable agreement with experimental data in terms of concentration profiles of stable species and gas-phase aromatic compounds. Modeling results are used to analyze the controlling steps of aromatic formation and soot growth in counter-flow configurations. The formation of high molecular mass aromatics in diffusion controlled conditions is restricted to a narrow area close to the flame front where these species reach a molecular weight of about 1000 u. Depending on the flame configuration, soot formation is controlled by the coagulation of nanoparticles or by the addition of PAH to soot nuclei.     

Study on the effect of iron on PM10 formation and design of a particle-generating system using a cocentric diffusion burner flame

Iron pentacarbonyl was added to a cocentric diffusion burner flame burning a mixture of acetylene and ethylene in a co-flowing stream of air. Samples of aerosols and gaseous species were collected within the flames and above the flames with filters and a sampling bottle, and soot volume fraction through the flame was calculated with laser light extinction measurements. Aerosol was isokinetically collected in the inhalation chamber to measure particle concentration and size distribution. Laser extinction measurement showed that iron (Fe) gave an effect on soot formation process and scanning electron microscopy of the aerosol sample showed that soot particle size for the Fe-doped flame was relatively smaller than that of non-Fe-doped flame. Transmission electron microscopy results indicated that Fe species were separated from the soot at the downstream flame. Particles of the soot and Fe mixture could be generated continuously, and the concentration was kept constant under a given experimental condition using the cocentric diffusion flame burner. The mass loading variation for each target concentration (i.e., 100, 200, and 400 microg/m3) in the inhalation chamber was less than +/-5% during 10 hr. This particle-generating burner system could be used effectively for a bioassay test to evaluate risk     

On the prediction of concentration variations in a dispersing heavy-duty truck exhaust plume using k–ε turbulent closure

This work presents the computational fluid dynamic modeling of an exhaust plume dispersed from the exhaust pipe of a class-8 tractor truck powered by 330 hp Cummins M11 electronically controlled diesel engine. This effort utilizes an advanced CFD technique to accurately predict the variation of carbon dioxide concentration inside a turbulent plume using a k–ε eddy dissipation model. The simulation includes the “real-world” operation of a truck and its exhaust plume in a NASA, Langley aircraft testing wind tunnel, that had an effective volume of 226, 535 m³ (8,000,000 ft³). The predicted results show an excellent agreement with the experimentally measured values of CO₂ concentrations, dilution ratios, and the temperature variations inside the plume. A specific goal of this effort was to study the effect of recirculation region near the truck walls on dispersion of the plume. For this purpose, growth of the plume from the center of the exhaust pipe is also presented and discussed. This work also shows the benefits of CFD modeling in applications where dispersion correlations are not required a priori, instead the dispersion coefficients are calculated precisely by solving the turbulent kinetic energy and dissipation equations.     

Effect of Ammonia in Gaseous Fuels On Nitrogen Oxide Emissions

The effect of ammonia in the fuel on NO_x emissions was investigated through laboratory experiments and field burner tests. It was found that the degree of conversion of pm-monia to NO_x was a strong function of excess air, ammonia content in the fuel, and of the degree of mixing in the flame. In premixed laboratory flames concentrations of NO_x above the peak equilibrium amounts were produced. In furnace diffusion flames the conversion to NO_x was much less. At substoichiometric air-fuel ratios all the ammonia appears to pyrolize, forming N₂, and only very little NO_x. Several methods for burning ammonia to produce low NO_x emissions were investigated.     

Mathematical Modeling of Photochemical Smog Using the PICK Method

A new method for solving the turbulent atmospheric diffusion equation has been developed based on Lagrangian mass points, or particles moving through an Eulerian grid. The method is one of a family of Particle-/n-Cell techniques but is a unique extension to incorporate the effects of turbulent diffusion based on K-theory; thus the acronym PICK.

In the three-dimensional computer-aided model, NEXUS (Numerical EXamination of Urban Smog), this method has been applied to simulation of carbon monoxide (CO) in Los Angeles. For CO the NEXUS simulation was within 20% of observed day-averaged concentrations at 12 stations and the hour-averages were also in good agreement. This model was extended to include the effects of photochemical smog in Los Angeles. The results of the photochemical simulation were also qualitatively correct due to rapid NO to NO₂ conversion in the simulation.     

Numerical simulation of scalar dispersion downstream of a square obstacle using gradient-transport type models

We present a numerical study of scalar transport released from a line source downstream of a square obstacle to investigate the capabilities and limitations of gradient-transport modeling in predicting atmospheric dispersion. The standard k–? and k–ω models and a Reynolds Stress Transport closure are employed and compared to predict the time-averaged turbulent flow field, while a standard gradient–diffusion model is initially adopted to relate the scalar flux to mean gradients of the concentration field. The analysis of two algebraic closures for turbulent scalar fluxes based on the generalized-gradient–diffusion hypothesis and its quadratic extension is also presented. In spite of the rather simple flow setup, where both the flow and the scalar fields can be assumed homogeneous in the spanwise direction, the analysis clarifies several critical issues concerning gradient-transport type models. We established the dominant role of predicted turbulent kinetic energy on scalar dispersion when a scalar diffusivity is employed, irrespectively of the Reynolds stress closure adopted for the averaged momentum equation. Moreover, the standard gradient–diffusion hypothesis failed to predict the streamwise component of the scalar flux, which is characterized by a counter-gradient-transport mechanism. Although the resulting contribution in the averaged scalar transport equation is small in the present flow configuration, this limitation can become severe for strongly inhomogeneous flows in the presence of point sources, where the spread of the scalar plume is essentially three-dimensional. The predictive capabilities of gradient-transport type modeling are found clearly improved using algebraic closures, which appear to represent a promising tool for predicting atmospheric dispersion in complex flows when unsteady transport mechanisms are not dominant.     

Adsorption of glyphosate on resin supported by hydrated iron oxide: equilibrium and kinetic studies

Hydrated iron oxide supported on resin (D301) was prepared as a new sorbent for the removal of glyphosate from wastewater. Batch adsorption studies were performed on glyphosate aqueous solutions with different initial glyphosate concentrations and temperatures. Experimental data were analyzed using the Langmuir and Freundlich isotherms, and the adsorption data were best fit to the Langmuir isotherm model. The thermodynamic parameters AG, AH, and AS also were calculated for the adsorption processes. Adsorption rate constants were determined using the pseudo-first-order and pseudo-second-order rate equations and Kannan-Sundaram intraparticle diffusion models. Adsorption of glyphosate clearly followed the pseudo-second-order model and was controlled by both film diffusion and intraparticle diffusion.     

Mass spectrometry up to 1 million mass units for the simultaneous detection of primary soot and of soot precursors (nanoparticles) in flames

A hybrid setup consisting of low pressure burner, flow reactor and photo-ionization mass spectrometer was used for the simultaneous detection of primary soot and of flame generated nanoparticles precursing soot. The studied flames were low pressure (120-180 mbar) C2H4/O2 flames surrounded by an N2 shield. The flow reactor was not used in this study. Through variation of the burner conditions (stoichiometry, sampling height) it could be shown that nanoparticles and soot are entirely independent species. The former, in particular, are found very early in the flame and their concentration profiles do not vary very much throughout the flame. This renders the possibility that nanoparticles are emitted together with soot and consequently may constitute an additional environmental hazard. Photo-ionization mass spectrometry is well suited for the detection of these particles.     

Concentration field and turbulent fluxes during the mixing of two buoyant plumes

In this work an experimental study of mixing of two identical plumes, carried out in a turbulent neutral boundary layer generated in a wind tunnel, is presented. Measurements have been performed with fast flame ionisation detectors (FFIDs) and a two-component Laser-Doppler Anemometer system. Results allow the study of both the average and the fluctuating concentration field, including the turbulent vertical and longitudinal mass fluxes, in single plumes and during the interaction of two identical plumes. This information gives insight into the details of the mixing phase of the two plumes. Results of trajectories and additional rise (due to plume interactions) have been compared with previous measurements carried out in laminar cross-flows, showing similar behaviour. Concentration distributions in plume cross-sections in turbulent cross-flows differ from those measured in laminar cross-flows. Average vertical and longitudinal velocity measurements into the plume core show the strength of the shielding effect of the upwind plume and some details of interaction between the counter-rotating vortex pairs (CVPs). For large values of the alignment angle φ, between the line joining the stacks and the cross-flow, an average negative vertical velocity is measured in the middle of the plume even if its centre of mass is rising. This downward velocity is induced by the slow interaction of the CVPs and generates a vertical stretching of the plume and negative rise enhancement. Vertical turbulent fluxes change sign on the plume centreline and are of opposite sign with respect to the longitudinal turbulent fluxes. Results indicate a good linearity between vertical turbulent fluxes and concentration gradients, with different proportionality for the top and bottom parts of the plume (especially in the near field) indicating that dispersion could be described by a gradient-transfer model.     

An axisymmetric diffusion experiment for the determination of diffusion and sorption coefficients of rock samples

Diffusion anisotropy is a critical property in predicting migration of substances in sedimentary formations with very low permeability. The diffusion anisotropy of sedimentary rocks has been evaluated mainly from laboratory diffusion experiments, in which the directional diffusivities are separately estimated by through-diffusion experiments using different rock samples, or concurrently by in-diffusion experiments in which only the tracer profile in a rock block is measured. To estimate the diffusion anisotropy from a single rock sample, this study proposes an axisymmetric diffusion test, in which tracer diffuses between a cylindrical rock sample and a surrounding solution reservoir. The tracer diffusion between the sample and reservoir can be monitored from the reservoir tracer concentrations, and the tracer profile could also be obtained after dismantling the sample. Semi-analytical solutions are derived for tracer concentrations in both the reservoir and sample, accounting for an anisotropic diffusion tensor of rank two as well as the dilution effects from sampling and replacement of reservoir solution. The transient and steady-state analyses were examined experimentally and numerically for different experimental configurations, but without the need for tracer profiling. These experimental configurations are tested for in- and out-diffusion experiments using Koetoi and Wakkanai mudstones and Shirahama sandstone, and are scrutinized by a numerical approach to identify favorable conditions for parameter estimation. The analysis reveals the difficulty in estimating diffusion anisotropy; test configurations are proposed for enhanced identifiability of diffusion anisotropy. Moreover, it is demonstrated that the axisymmetric diffusion test is efficient in obtaining the sorption parameter from both steady-state and transient data, and in determining the effective diffusion coefficient if isotropic diffusion is assumed. Moreover, measuring reservoir concentrations in an axisymmetric diffusion experiment coupled with tracer profiling may be a promising approach to estimate of diffusion anisotropy of sedimentary rocks.     

Turbulent Schmidt numbers for CFD analysis with various types of flowfield

The application of CFD (computational fluid dynamics) using RANS (Reynolds-averaged Navier–Stokes equations) model to turbulent flows with mass transfer generally estimates the turbulent scalar flux assuming the gradient diffusion hypothesis, which requires definition of the turbulent Schmidt number, Sc_t However, no universal value of Sc_t has been established and empirical values have been used in different studies. In this paper, previous research related to the application of optimum values of Sc_t for engineering flowfields relevant to atmospheric dispersion is reviewed. The optimum values for Sc_t are widely distributed in the range of 0.2–1.3 and the specific value selected has a significant effect on the prediction results. On the basis of the present study results and since the optimum values of Sc_t largely depend on the local flow characteristics, it is recommended that Sc_t should be determined by considering the dominant flow structure in each case.     

A detailed numerical study of the evolution of soot particle size distributions in laminar premixed flames

In this work, two numerical techniques, viz. the method of moments and a discrete h-p-Galerkin method, have been applied for numerical simulation of soot formation in a laminar premixed acetylene/oxygen/argon flame. From the evolution of the PAH and the soot particle size distributions, new insight into the different processes of soot formation is provided. For this, the single submodels have been examined with respect to their influence on the PAH and the soot particle size distributions. The particle inception step was studied in detail by comparing the simulated PAH size distributions with experimental results. Additionally, an estimation of the interaction energy of layered PAH dimers was performed by quantum chemical calculations. From these results, some evidence for the particle inception model employing coalescence of PAH molecules has been found. The numerical results for the gas phase chemical species, the particle number densities and volume fractions of soot as well as for the soot particle size distributions are compared with experimental data. Thereby, the consistency of the entire model is demonstrated.     

Influence of wall roughness on the dispersion of a passive scalar in a turbulent boundary layer

Many towns and cities consist of similarly sized buildings in relatively regular arrangements with smaller scale roughness elements such as roofs, chimneys and balconies. The objective of this study is to investigate how small scale roughness elements modify the influence of the large scale organized roughness on the dispersion of a passive scalar in a turbulent boundary layer. Wind tunnel experiments were performed using a passive tracer released from a line source and concentration profiles were measured with a Flame Ionisation Detector. The measurements are compared with numerical solutions of the advection–diffusion equation.The results show that decreasing the cavity aspect ratio increases the turbulent vertical mass fluxes, and that the small scale roughness enhances these fluxes, but only in the skimming flow regime. Numerical simulations showed that outside the roughness sub-layer (RSL) the changes in surface roughness could be accounted for by a simple variation of the friction velocity, but inside the RSL the spatial variability of the flow imposed by the roughness elements has much more influence. A simple model for a spatially averaged dispersion coefficient in the RSL has been developed and is shown to agree satisfactorily with the concentrations measured in these experiments.     

Spectroscopic behavior of oxygenated combustion by-products

The oxygenated species, massively produced in the energy production plants based on combustion processes, constitute one of the most numerous categories of hazardous air pollutants. Therefore, development of real time diagnostic tools are needed in order to study their formation during combustion processes and to reveal their presence both in the exhaust and in the atmosphere. In this work, oxygenated compounds were identified inside fuel-rich premixed ethylene/air flames by means of ultraviolet fluorescence spectroscopy with the support of qualitative chemical analysis of the sampled combustion gases.

Strong band progression, typical of aldehydic functionality, were recognized in fluorescence spectra (λ_exc=355 nm) measured in the early oxidation region of premixed flames varying the equivalence ratio from 3.0 up 21.6. Downstream of the oxidation region, spectroscopic signatures of pyrolytic species were found to prevail on those peculiar of oxygenated compound. The position and the extension of the two main flame zones were found to depend on the flame conditions (C/O ratio) due to the effect of the C/O ratio on the temperature history along the flame axis. This correlation was interpreted on the basis of the measured axial temperature profiles.     

UV-visible spectroscopy of organic carbon particulate sampled from ethylene/air flames

A systematic comparison of spectra obtained with extra and in situ diagnostics in the soot preinception region of rich, premixed ethylene air flames suggests that combustion generated organic carbon (OC) particulate can be extracted from flames and isolated from other flame material for further chemical analysis. Both the trend with height above the burner and the form of UV fluorescence and absorption spectra from extra situ sampled material captured in water agree with those measured in situ. These results show that the OC particulate formed in flames is partially water soluble. However, the collection efficiency can be increased using less polar solvents, like acetonitrile and dichloromethane. The fluorescence spectra from the water samples are comprised both a naphthalene-like component and a broad band UV fluorescence component similar to that observed in situ which is attributed to flame generated OC particulate. The broad band UV fluorescence centered around 320 nm is also observed very early in flames and does not change considerably with increasing flame residence time. These results support previous hypotheses that the UV broad band fluorescence is from carbonaceous material comprised two-ring aromatics, formed earlier than soot in the flame, and is still present along with soot at higher heights or flame residence times.     

Dioxin formation in stretched flames

Numerical simulations of stretched laminar twin premixed flames are carried out in order to understand the gasphase formation of dioxins in situations analogous to the post combustor and following regions of a typical incinerator. A previously developed chemical kinetic mechanism, that describes dioxin formation in terms of some generic species, is used in the calculations. The results indicate a temperature region favorable to the gasphase production of dioxins that lies between 1100 and 1500 K, as well as a weak dependence of dioxin formation on the oxygen concentration in the flames. The effect of oxygen is better described by observing the consumption of some of the generic species. Though no measurements of dioxin concentration in idealized flows, such as those simulated, are available, the results are in qualitative accord with total measurements of dioxin concentration (due to both gas- and solid-phase processes) obtained by other investigators. The numerical predictions identify some flames that are ignited, in which dioxin consumption takes place, and others which are unignited, in which significant dioxin production occurs as the result of largely isothermal mixing. The calculations indicate that unignited flames containing no initial fuel favor dioxin formation significantly over those that contain some initial quantity of fuel. Finally, some implications regarding incinerator practice are discussed.     

Monitoring of fuel consumption and aromatics formation in a kerosene spray flame as characterized by fluorescence spectroscopy

The large presence of aromatic compounds in distillate fossil fuels should allow, in line of principle, to follow the fuel consumption and/or the presence of unburned fuel in a high temperature environment like a burner or the exhaust of combustion systems by exploiting the high fluorescence emission of aromatic fuel components. To this aim an UV-excited fluorescence source has to be used since the aromatic fuel components are strongly fluorescing in the UV region of the emission spectrum.

In this work UV-excited laser induced fluorescence (LIF) diagnostics was applied to spray flames of kerosene in order to follow the fuel consumption and the formation of aromatic species. A strong UV signal was detected in the spray region of the flame that presented a shape similar to that found in the LIF spectra preliminary measured on the cold spray and in the room-temperature fluorescence of fuel solutions.

The decrease of UV signal along the spray flame region was associated to the consumption of the fuel, but more difficult seems to be the attribution of a broad visible emission, that is present downstream of the flame.

The visible emission feature could be assigned to flame-formed PAH species contained in the high molecular weight species, hypothesizing that their fluorescence spectra are shifted toward the visible for effect of the high temperature flame environment.     

Engineering,Operation and Maintenance of Electrostatic Precipitators on Open Hearth Furnaces

The photochemical reaction of various olefins and nitrogen dioxide was studied under conditions of controlled temperature, pressure, and humidity in a 200 liter stirred glass reactor. The hydrocarbon concentration in the reactor during four and five hour irradiation periods was monitored with a flame ionization chromatograph. Reaction rate constants, based on three consecutive first order reactions, were calculated for reactor temperatures of 20, 25, 30, and 35 degrees centigrade. Activation energies for the three consecutive reactions were calculated from the Arrhenius equation. Branched and straight chain olefins were studied at initial concentrations of 5.0 to 10.0 parts per million.s     

Numerical calculation of flow and stack-gas concentration fluctuation around a cubical building

A numerical simulation model was developed to predict the instantaneous concentration fluctuation of a plume and applied to stack-gas diffusion around a cubical building. The flow field, including an instantaneous velocity component, was predicted using the large eddy simulation (LES) method in the developed numerical model. Then, the instantaneous concentration fluctuation was predicted using the obtained unsteady flow field. Concentration was calculated using the finite difference method, in which the LES is expanded for concentration, and the puff method, in which small volumes of the tracer gas are divided and combined according to the calculation mesh sizes. In order to avoid numerical viscous effects, a puff method and finite difference method were applied separately in the regions near and far from the stack-gas release point, respectively. Then, the flow field around a cubical building and the diffusion of stack-gas, emitted from an elevated point source at an upstream position of the building, were calculated using the model mentioned above. Numerical calculation results were compared with those obtained in wind tunnel experiments in which concentration fluctuation was measured using high-response flame ionization detectors. Although there were some discrepancies in the flow field between the calculated results and those of wind tunnel experiments, e.g., the calculated windward length of a cavity region behind the building, the calculated mean velocity and turbulent intensity showed good agreement with those of the wind tunnel experiments. Furthermore, the calculated concentration fluctuation showed good agreement with that in the wind tunnel, not only regarding the features of fluctuating concentration signals, but also statistic quantities, viz., mean concentration, fluctuation intensity and high-concentration values.