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     

Investigation of soot by two-colour four-wave mixing

A novel technique has been used for the temporally resolved investigation of the interaction of laser radiation and soot in a flame. Based on established soot vaporisation models we developed a framework to calculate the two-colour four-wave mixing signal obtained in an acetylene/air diffusion flame at atmospheric pressure. The signal comprises a contribution due to soot and, depending on the wavelength of the probe laser, a contribution because of C2, which is generated by vaporising soot. For both parts of the signal we found a good agreement between measured and calculated power dependency. Furthermore, we measured spatial profiles of the signal in a Wolfhard-Parker slot burner. By analysing the different signal contributions we found that depending on the location within the flame there are particles with different C2 yield.     

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.     

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.     

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.     

Suppression of Soot by Metal Additives During the Combustion of Polystyrene

This paper describes an experimental study on the suppression of soot by metal additives during the combustion of polystyrene (PS). A two-dimensional flame generated by using a Wolfhard-Parker type diffusion flame burner was used to simulate practical combustion situations. The PS was continuously fed to the burner and, by controlling the feed rate, the combustion was maintained at a steady state. The additives tested were the salts of Li, Na, K, Mg, Ca, Sr, and Ba, and the combinations of the salts of K and Ca, Sr, or Ba. These additives were added to the flame in the form of small drops of their aqueous solutions generated by an ultrasonic atomizer. Since the flow rate of the carrier gas (air) is very small, this addition causes no noticeable disturbance to the flame. The effectiveness of the alkali metals follows the order of their ease of ionization, i.e., K > Na > Li, and that of the alkaline-earth metals: Ba > Sr > Ca > Mg. At low addition rates, the effectiveness increases with increasing addition rate but becomes unaffected at high addition rates and the maximum percentage of soot suppressed is approximately 50 percent. The combinations of the two metals (i.e., K and Ca, Sr, or Ba) are much more effective than each single metal at the same addition rates and the maximum percentage of soot suppressed reaches approximately 90 percent. It is proposed that the alkaline-earth metals catalyze the ionization of the alkali metals, thus significantly enhancing the effect on soot suppression.     

Evidence for the contribution of methane in the formation of aromatics and soot in fuel-rich pre-mixed combustion

Experimental results from an isothermal laminar flow reactor at atmospheric pressure are presented on the chemical composition in the post-oxidative region of two sooting fuel-rich pre-mixed mixtures diluted in nitrogen. A base case composed of n-heptane and O2 in N2 at 1425 K with a C/O of 2.85 was perturbed by substituting 10% of the carbon in n-heptane with carbon as CH4. While these changes would intuitively reduce aromatics and soot formation by increasing H2 and decreasing C2H2 concentrations, we observe the opposite. The concentrations of individual aromatic species are observed to actually increase by up to 50% and the soot yield increases by 80%.     

Soot Control During the Combustion of Polystyrene

This paper describes an experimental study on the control of soot formation during the combustion of polystyrene (PS). A stable, twodimensional flame generated by using a Wolfhard-Parker type diffusion flame burner was used to simulate practical combustion situations. The combustion characteristics, effects of operating conditions on soot formation, and the effectiveness of various metallic additives as soot suppressants were investigated. It was found that soot yield could not be significantly reduced by controlling the oxidizer (air) flow rate. Increasing the O₂ mole fraction of the oxidlzer increased soot yield under typical operating conditions. However, soot yield could be greatly reduced by adding small amounts of air into the pyrolysis zone of the flame. The additional air would probably increase the combustion reaction rate while decreasing the soot precursor formation rate, thereby causing the observed effect. It was thus suggested that effective soot control could be accomplished by improving mixing between air and the PS devolatilizatlon products In practical combustion situations. The metallic additives tested in this study were the salts of Na, K, Ca, and Ba. Among these salts, Ca was the least effective in reducing soot, and K and Na were nearly equally effective. Ba was much more effective than all the others, and Its effectiveness was strongly dependent on its addition rate.     

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.     

Heterogeneous reaction of NO2 with soot at different relative humidity

The influences of relative humidity (RH) on the heterogeneous reaction of NO₂ with soot were investigated by a coated wall flow tube reactor at ambient pressure. The initial uptake coefficient (γ _initial) of NO₂ showed a significant decrease with increasing RH from 7 to 70%. The γ _initial on “fuel-rich” and “fuel-lean” soot at RH = 7% was (2.59 ± 0.20) × 10^?5 and (5.92 ± 0.34) × 10^?6, respectively, and it decreased to (5.49 ± 0.83) × 10^?6 and (7.16 ± 0.73) × 10^?7 at RH = 70%, respectively. Nevertheless, the HONO yields were almost independent of RH, with average values of (72 ± 3)% for the fuel-rich soot and (60 ± 2)% for the fuel-lean soot. The Langmuir-Hinshelwood mechanism was used to demonstrate the negative role of RH in the heterogeneous uptake of NO₂ on soot. The species containing nitrogen formed on soot can undergo hydrolysis to produce carboxylic species or alcohols at high RH, accompanied by the release of little gas-phase HONO and NO.

     

Kinetics of the reactions of soot surface-bound polycyclic aromatic hydrocarbons with the OH radicals

The kinetics of the heterogeneous reaction of OH radicals with 15 polycyclic aromatic hydrocarbons (PAHs) present in laboratory generated simulated kerosene combustion soot was studied at T = 290 K in a low pressure discharge-flow reactor combined with an electron-impact mass spectrometer. The kinetics of soot-bound PAH consumption in reaction with OH were monitored using off-line HPLC measurements of their concentrations in soot samples as a function of time of exposure to OH. Concentration of OH radicals in the gas phase was measured by mass spectrometry. The first-order rate constants measured for the individual PAH at T = 290 K ranged from 0.02 to 0.04 s^?1 and were found to be independent of the OH concentration ([OH] = (0.34–2.5) × 10¹² molecule cm^?3) and of the molecular structure of the PAH. In addition, the uptake coefficient of OH on soot surface and the diffusion coefficient of OH in He were measured to be 0.19 ± 0.03 (calculated with geometric surface area) and (615 ± 80) Torr cm² s^?1, respectively. Comparison of the results on the PAH + OH reaction to those from previous studies carried out on different carbonaceous substrates, indicates probable dependence of the heterogeneous reactivity of PAH toward OH on the substrate nature. Rapid reaction with OH can be an important potential pathway of the atmospheric degradation of non-volatile PAH present mainly in the particulate phase in the atmosphere.     

A modeling evaluation of the effect of chlorine on the formation of particulate matter in combustion

The effect of chlorine on the fuel-rich oxidation of hydrocarbons and on the molecular weight growth of aromatics is analyzed by simulating experiments featuring a model chlorinated additive CH3Cl in a jet-stirred/plug-flow reactor and premixed flames. The kinetic model used in this work emphasizes the role of resonantly stabilized radicals in the formation and growth of aromatics, and considers soot inception as the net effect of molecular weight growth and graphitization of aromatic structures. Chlorinated hydrocarbons decompose at temperatures significantly lower than hydrocarbons, producing reactive Cl-atoms, which have a strong tendency to go to HCl. The HCI, tying up the H-atoms, inhibits hydrocarbon oxidation. The model is able to predict not only the levels but the shape of the experiments quite well and also the surprising finding of an increased soot formation associated with lower PAH levels found in rich flames with significant levels of chlorine. Based on reaction kinetic analysis, chlorine addition to the fuel enhances soot formation by promoting the formation of aromatic-ring compounds and accelerating the abstraction of aromatic H-atoms from stable PAH molecules. This process activates the transformation of aromatics to soot.     

PAH and soot emissions from burning components of medical waste: examination/surgical gloves and cotton pads

This is a laboratory investigation on the emissions from batch combustion of representative infectious ("red bag") medical waste components, such as medical examination latex gloves and sterile cotton pads. Plastics and cloth account for the majority of the red bag wastes by mass and, certainly, by volume. An electrically heated, horizontal muffle furnace was used for batch combustion of small quantities of shredded fuels (0.5-1.5 g) at a gas temperature of approximately 1000 degrees C. The residence time of the post-combustion gases in the furnace was approximately 1 s. At the exit of the furnace, the following emissions were measured: CO, CO2, NOx, particulates and polynuclear aromatic compounds (PACs). The first three gaseous emissions were measured with continuous gas analyzers. Soot and PAC emissions were simultaneously measured by passing the furnace effluent through a filter (to collect condensed-phase PACs) and a bed of XAD-4 adsorbent (to capture gaseous-phase PACs). Analysis involved soxhlet extraction, followed by gas chromatography-mass spectrometry (GC-MS). Results were contrasted with previously measured emissions from batch combustion of pulverized coal and tire-derived fuel (TDF) under similar conditions. Results showed that the particulate soot) and cumulative PAC emissions from batch combustion of latex gloves were more than an order of magnitude higher than those from cotton pads. The following values are indicative of the relative trends (but not necessarily absolute values) in emission yields: 26% of the mass of the latex was converted to soot, 11% of which was condensed PAC. Only 2% of the mass of cotton pads was converted to soot, and only 3% of the weight of that soot was condensed PAC. The PAC yields from latex were comparable to those from TDF. The PAC yields from cotton were higher than those from coal. A notable exception to this trend was that the three-ring gas-phase PAC yields from cotton were more significant than those from latex. Emission yields of CO and CO2 from batch combustion of cotton were, respectively, comparable and higher than those from latex, despite the fact that the carbon content of cotton was half that of latex. This is indicative of the more effective combustion of cotton. Nearly all of the mass of carbon of cotton gasified to CO and CO2 while only small fractions of the carbon in latex were converted to CO2 and CO (20% and 10%, respectively). Yields of NOx from batch combustions of latex and cotton accounted for 15% and 12%, respectively, of the mass of fuel nitrogen indicating that more fuel nitrogen was converted to NOx in the former case, possibly due to higher flame temperatures. No SO2 emissions were detected, indicating that during the fuel-rich combustion of latex, its sulfur content was converted to other compounds (such as H2S) or remained in the soot.     

Black carbon particulate matter emission factors for buoyancy-driven associated gas flares

Flaring is a technique used extensively in the oil and gas industry to burn unwanted flammable gases. Oxidation of the gas can preclude emissions of methane (a potent greenhouse gas); however, flaring creates other pollutant emissions such as particulate matter (PM) in the form of soot or black carbon (BC). Currently available PM emissionfactors for flares were reviewed and found to be questionably accurate, or based on measurements not directly relevant to open-atmosphere flares. In addition, most previous studies of soot emissions from turbulent diffusion flames considered alkene or alkyne based gaseous fuels, and few considered mixed fuels in detail and/or lower sooting propensity fuels such as methane, which is the predominant constituent of gas flared in the upstream oil and gas industry. Quantitative emission measurements were performed on laboratory-scale flares for a range of burner diameters, exit velocities, and fuel compositions. Drawing from established standards, a sampling protocol was developed that employed both gravimetric analysis of filter samples and real-time measurements of soot volume fraction using a laser-induced incandescence (LII) system. For the full range of conditions tested (burner inner diameter [ID] of 12.7-76.2 mm, exit velocity 0.1-2.2 m/sec, 4- and 6-component methane-based fuel mixtures representative of associated gas in the upstream oil industry), measured soot emission factors were less than 0.84 kg soot/10(3) m3 fuel. A simple empirical relationship is presented to estimate the PM emission factor as a function of the fuel heating value for a range of conditions, which, although still limited, is an improvement over currently available emission factors.     

Detection of combustion formed nanoparticles

UV–visible extinction and scattering and two extra situ sampling techniques: atomic force microscopy (AFM) and differential mobility analysis (DMA) are used to follow the evolution of the particles formed in flames. These particle sizing techniques were chosen because of their sensitivity to detect inception particles, which have diameters, d<5 nm, too small to be observed with typical particle measurement instrumentation. The size of the particles determined by AFM and DMA compares well with the size determined by in situ optical measurements, indicating that the interpretation of the UV–visible optical signal is quite good, and strongly showing the presence of d=2–4 nm particles. UV–visible extinction measurements are also used to determine the concentration of d=2–4 nm particles at the exhausts of practical combustion systems. A numerical model, able to reproduce the experimentally observed low coagulation rate of nanoparticles with respect to soot particles, is used to investigate the operating conditions in the combustion chamber and exhaust system for which 2–4 nm particles survive the exhaust or grow to larger sizes. Combustion generated nanoparticles are suspected to affect human and environmental health because of their affinity for water, small size, low rate of coagulation, and large surface area/weight ratio. The ability to isolate nanoparticles from soot particles in hydrosols collected from combustion may be useful for future analysis by a variety of techniques and toxicological assays.     

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.     

Development of a measuring technique for simultaneous in situ detection of nanoscaled particle size distributions and gas temperatures

Point measurements of time-resolved LII signals have been performed in sooting premixed low pressure flames. Soot particle size distribution and gas temperature in these flames are known from independent measurements. This data is used to validate parameters of an improved LII model, where special emphasis is taken on the accurate modelling of mass and heat transfer rates. Using this model particle size distributions and gas temperatures can be estimated from time-resolved LII signals using non-linear regression. Standard numerical methods are applied. An experimental setup is presented, which allows measuring one-dimensional maps of particle size distribution and gas temperature. The technique is based on the one-dimensional and time-resolved detection of LII signals using a Streak camera.     

Pore structure of soot deposits from several combustion sources

Soot was harvested from five combustion sources: a dodecane flame, marine and bus diesel engines, a wood stove, and an oil furnace. The soots ranged from 20% to 90% carbon by weight and molar C/H ratios from 1 to 7, the latter suggesting a highly condensed aromatic structure. Total surface areas (by nitrogen adsorption using the Brunauer Emmett Teller, BET method) ranged from 1 to 85 m2 g(-1). Comparison of the surface area and meso-pore (pores 2-50 nm) surface area predicted by density functional theory (DFT) suggested that the soot was highly porous. Total meso-pore volume and surface area ranged from 0.004-0.08 cm3 g(-1) and from 0.33-6.9 m2 g(-1) respectively, accounting for up 33% of the BET surface area. The micro-pore volume (pores <2 nm) calculated from CO2 adsorption data (by DFT) ranged from 0.0009 to 0.013 cm3 g(-1) and micro-pore surface area was 3.1-41 m2 g(-1), accounting for 10-20% of the total intra-particle (meso-plus micro-pores) pore volume and 70-90% of the total intra-particle surface area. Higher pore volume and surface area values were computed using the Dubinin Radushkevich plot technique; ranging from 0.004-0.04 cm3 g(-1) to 11-102 m2 g(-1) for micro-pore volume and surface area, respectively. Comparison of the C/H ratio and the micro-pore structure showed a strong correlation, suggesting a relationship between the condensation of the skeletal structure and micro-porosity of the soot. These data contradict literature reports that soot particles are non-porous and are consistent with recent literature reports that soil organic matter has large micro-pore surface areas.     

Heterogeneous reactions of soot aerosols with nitrogen dioxide and nitric acid: atmospheric chamber and Knudsen cell studies

Heterogeneous chemical processes involving trace atmospheric gases with solid particulates, such as carbonaceous aerosol, are not well understood. In an effort to quantify some relevant carbon aerosol systems, the heterogeneous chemistry of NO₂ with both commercial and freshly prepared hexane soot was investigated in an atmospheric reaction chamber. At approximately an atmosphere of total pressure (760 Torr) and under dry conditions (relative humidities⩽1%), kinetic measurements gave an uptake coefficient of (2.4±0.6)×10⁻⁸ for n-hexane soot when referenced to the BET surface area of the sample. Commercial carbon black samples were found to yield a similar uptake coefficient. The reaction of HNO₃ with commercial carbon black was also investigated and gas phase NO₂ was detected as a reaction product. Low-pressure Knudsen cell experiments were carried out to facilitate a quantitative comparison between the two different techniques. The agreement between our current results and previously reported values of the uptake coefficient, with different soot samples and under varied pressure and surface coverage conditions, are discussed along with the possible implications for atmospheric chemistry.