A Plug Flow Model for Chemical Reactions and Aerosol Nucleation and Growth in an Alkali-Containing Flue Gas

The paper presents a numerical model for the simulation of gas to particle conversion and the chemical changes during cooling of a flue gas from the combustion of fuels rich in volatile alkali species. For the homogeneous nucleation of alkali species the model uses the classical theory modified by the Tolman coefficient for the size dependent surface tension. A special adaptation of the theory to the nucleation of seeds of chloride salt from an equilibrium mixture of monomer and dimer chloride vapor molecules is also made. The growth of particles occurs by condensation and agglomeration. Different multicomponent growth models are treated. The local gas phase composition is determined from a gas phase chemical equilibrium calculation combined with finite reaction rate kinetics for slower reactions. The model is useful in the analysis of boiler operation with respect to the formation of particles, HCl, SO₂, and deposits.     

Hygroscopic Behavior of Aerosol Particles Emitted from Biomass Fired Grate Boilers

This study focuses on the hygroscopic properties of submicrometer aerosol particles emitted from two small-scale district heating combustion plants (1 and 1.5 MW) burning two types of biomass fuels (moist forest residue and pellets). The hygroscopic particle diameter growth factor (Gf) was measured when taken from a dehydrated to a humidified state for particle diameters between 30–350 nm (dry size) using a Hygroscopic Tandem Differential Mobility Analyzer (H-TDMA). Particles of a certain dry size all showed similar diameter growth and the Gf at RH = 90% for 110/100 nm particles was 1.68 in the 1 MW boiler, and 1.5 in the 1.5 MW boiler. These growth factors are considerably higher in comparison to other combustion aerosol particles such as diesel exhaust, and are the result of the efficient combustion and the high concentration of alkali species in the fuel. The observed water uptake could be explained using the Zdanovski-Stokes-Robinson (ZSR) mixing rule and a chemical composition of potassium salts only, taken from ion chromatography analysis of filter and impactor samples (KCl, K₂SO₄, and K₂CO₃). Agglomerated particles collapsed and became more spherical when initially exposed to a moderately high relative humidity. When diluted with hot particle-free air, the fractal-like structures remained intact until humidified in the H-TDMA. A method to estimate the fractal dimension of the agglomerated combustion aerosol and to convert the measured mobility diameter hygroscopic growth to the more useful property volume diameter growth is presented. The fractal dimension was estimated to be ～ 2.5.     

Generation of Internally Mixed Insoluble and Soluble Aerosol Particles to Investigate the Impact of Atmospheric Aging and Heterogeneous Processing on the CCN Activity of Mineral Dust Aerosol

Heterogeneous reactions of trace gases with mineral dust aerosol not only impact the chemical balance of the atmosphere but also the physicochemical properties of the dust particle and the ability of the particle to act as a cloud condensation nuclei (CCN). Recent field studies have shown that carbonate minerals are preferentially associated with nitrates whereas aluminum silicates (i.e., clay minerals) are preferentially associated with sulfates. To better understand how this association can impact the climate effects of mineral dust particles, we have measured the CCN activity of a number of pure and internal mixtures of aerosols relevant to these recent field studies. The CCN activity of CaCO ₃ -Ca(NO ₃ ) ₂ aerosol, simulating the activity of mineral dust aerosol that has been partially processed by nitrogen oxides in the atmosphere, is significantly enhanced relative to CaCO₃ aerosol of the same diameter. Similar results are obtained for a clay mineral, kaolinite, internally mixed with (NH ₄ ) ₂ SO ₄ . For example, at 0.3% supersaturation, a 200 nm particle containing a soluble nitrate or sulfate component is 2 to 4 times more active than an unreacted particle. The results presented here show that when determining the contribution of mineral dust aerosol to the overall impact of the aerosol indirect effect on radiative forcing, changes in chemical composition due to atmospheric processing cannot be ignored.     

A STUDY OF PROCESSES THAT GOVERN THE MAINTENANCE OF AEROSOLS IN THE MARINE BOUNDARY LAYER

We systematically evaluate the relative influence of sources and sinks of particles in the remote marine boundary layer (MBL) to elucidate the principal factors that govern MBL aerosol behavior. Processes considered include: (1) surface flux of dimethyl sulfide (DMS); (2) gas-phase oxidation of DMS to SO₂; (3) gas-phase oxidation of SO₂ to H₂SO₄; (4) mass transfer of SO₂ and H₂SO₄ to pre-existing particles; (5) homogenous nucleation of H₂SO₄/H₂O; (6) entrainment of air from the free troposphere; (7) deposition to the sea surface; (8) cycling of air through clouds and rain scavenging; (9) oxidation of SO₂ in sea salt aerosols and cloud droplets; and (10) sea-salt particle production at sea surface. The average aerosol number concentration is found to be quite sensitive to the rate of entrainment of aerosol-containing air from the free troposphere. The path that leads to the greatest accumulation of non-sea-salt (nss) sulfate involves SO₂ (rather than H₂SO₄) absorption into existing particles. Because of scavenging of SO₂ and H₂SO₄ by sea-salt aerosol, a considerable fraction of nss-sulfate is internally mixed with sea-salt aerosol. Under the conditions assumed in this study, MBL aerosol number concentration is dominated by free tropospheric aerosol under virtually all conditions, 89% in the base case, and even 69% at a 17 m s^-1 wind speed. Aerosol mass, on the other hand, is dominated by sea-salt particles, 62% in the base case and 98% at a wind speed of 17 m s^-1. Evaporation of cloud droplets provides 4.6% of the particle number in the base case, but 28% of the particle mass. At the high nucleation rate case considered here, there is notably little change in the overall contributions to aerosol number and mass from the base case; only about 5% of the total particle number is provided by nucleation events. Variation in precipitation frequency also has only a minor effect on the overall contributions. One concludes that the MBL aerosol is remarkably robust in the face of ever-changing conditions. Free tropospheric aerosol entrainment tends to sustain particle number concentrations, and sea-salt emissions maintain most of the aerosol mass. Cloud processing, while not a major contributor to aerosol number, does provide, except under high wind conditions, the order of 20% of the aerosol mass. Although nucleation occurs only infrequently and does not contribute appreciably to long-term average aerosol number or mass, nucleation is, nonetheless, the mechanism that replenishes aerosol number in brief, intense episodes when aerosol surface area levels are substantially reduced by precipitation.     

Single particle MS,SNMS, SIMS,XPS, and FTIR spectroscopic analysis of soot particles during the AIDA campaign

Within the framework of the AIDA soot aerosol campaign diesel soot particles, spark generated soot particles, and aerosol mixtures were characterized with respect to their chemical state using different surface sensitive analysis methods. A comparison between diesel soot and graphite spark generated soot revealed a significant difference in the chemical composition of the particle surfaces. No distinct change from external to internal mixing could be detected by single particle mass spectrometry for mixtures of diesel soot and (NH₄)₂SO₄ aerosol since the spectra of diesel soot and (NH₄)₂SO₄ aerosol were surprisingly similar due to sulfate on the surface of diesel soot particles and traces of carbon impurities on ammonium sulfate particles. In addition to the expected formation of new particles a considerable change of the soot particle surface was detected while exposing diesel soot or spark generated soot to α-pinene and ozone, indicating a surface layer formed by oxidation products of α-pinene. However, the oxygen-containing hydrocarbon fragments detected by single particle mass spectrometry were distinctly different for the two soot types, which can be explained by either the different product adsorption or ionization behavior. Depositions of α-pinene reaction products on the surface could be confirmed by QMS-SIMS and XPS for particles of both types of soot. Due to the high mass resolution of TOF-SIMS acidic derivatives were identified as reaction products of α-pinene and ozone. The analytical methods applied in this work elucidated the different properties of spark generated soot compared to diesel soot. Therefore, spark generated soot should only be used with care as a general diesel soot surrogate.     

Simulation of Aerosol Dynamics: A Comparative Review of Algorithms Used in Air Quality Models

A comparative review of algorithms currently used in air quality models to simulate aerosol dynamics is presented. This review addresses coagula tion, condensational growth, nucleation, and gas particle mass transfer. Two major approaches are used in air quality models to represent the particle size distribution: (1) the sectional approach in which the size distribution is discretized into sections and particle properties are assumed to be constant over particle size sections and (2) the modal approach in which the size distribution is approxi mated by several modes and particle properties are assumed to be uniform in each mode. The sectional approach is accurate for coagulation and can reproduce the major characteristics of the evolution of the particle size distribution for condensa tional growth with the moving-center and hybrid algorithms. For coagulation and condensational growth, the modal approach provides more accurate results when the standard deviations of the modes are allowed to vary than it does when they are fixed. Predictions of H₂SO₄ nucleation rates are highly sensitive to environ mental variables and simulation of relative rates of condensation on existing particles and nucleation is a preferable approach. Explicit treatment of mass transfer is recommended for cases where volatile species undergo different equilib rium reactions in different particle size ranges (e.g., in the presence of coarse salt particles). The results of this study provide useful information for use in selecting algorithms to simulate aerosol dynamics in air quality models and for improving the accuracy of existing algorithms.     

Aerosol Charge Neutralization by a Mixing-Type Bipolar Charger using Corona Discharge at High Pressure

An aerosol neutralizer called the Mixing-type Bipolar Charger using Corona-Discharge at High Pressure (MBCCHP) was developed. In the MBCCHP, a corona discharge (High-Pressure Corona Ionizer; HPC Ionizer) induced by high frequency voltage (>100 Hz) at high pressure (>0.2 MPa) is used to generate bipolar ions at high concentration (1–3 × 10⁹ ions/cm³) that are then mixed with aerosol particles flowing in a charging chamber where no external electric field is present. The charging performance of the MBCCHP was evaluated by comparing the measured and theoretical number ratios of positively and negatively charged particles to the total number of particles, and by comparing those of negatively charged to positively charged particles for an equilibrium charge distribution. The theoretical and measured results agreed well in the particle size range of 5–80 nm. Particle loss in the MBCCHP for the size range of 5–100 nm was less than 15%, and particle generation from the electrode due to spattering or from the carrier gas containing SO_x due to chemical reaction was either negligible or not observed. The MBCCHP can effectively provide aerosol particles in the equilibrium charge state. Advantages include (1) no selective deposition of charged particles by an electric field, (2) no generation of new particles by reactive molecules, such as atmospheric pollution gases contained in a sample aerosol by chemical reactions with active species, such as OH radicals, produced by discharge, and (3) no effect of carrier gases of the sample aerosol on the ion properties.     

The Nucleation of Aerosols in Flue Gases with a High Content of Alkali - A Laboratory Study

The formation of particles during cooling of a synthetic flue gas with vapors of sodium and potassium species is studied in a laboratory tubular reactor with laminar flow. It is shown to agree well with a theoretical model for the process. The kinetics of homogeneous nucleation of the pure chloride vapors is described by the classical nucleation theory, adapted to include the participation of stable dimer as well as monomer vapor molecules. The Tolman equation is used to describe the curvature-dependence of the surface tension of small nuclei. The values of the Tolman parameter for NaCl and KCl are determined from the measurements. The homogeneous nucleation of the pure chlorides is suppressed by even relatively small concentrations of foreign seed particles and is therefore unlikely to contribute to the creation of new particles in real flue gases. The addition of SO₂ to the chloride vapor feed, in the presence of oxygen and water vapor, increases the number concentration of effluent particles significantly and affects their composition to include sulphate in addition to chloride. The sulphate content is independent of the peak temperatures of the flue gas but increases with increasing content of oxygen and SO₂. The study proves that the alkali sulphates are formed by the sulphation of vapor phase rather than solid, alkali chloride. The sulphate vapors are formed in high supersaturation and show a pronounced tendency towards homogeneous nucleation, which is identified as the likely source of the submicron particles formed in alkali rich flue gases.     

Effects of chlorine and sulphur on particle formation in wood combustion performed in a laboratory scale reactor

Fine particle formation in wood combustion was studied in a laboratory scale laminar flow reactor at various flue gas chlorine and sulphur concentrations. Aerosol samples were quenched at around 850 °C using a porous tube diluter. Fine particle number concentrations, mass concentrations, size distributions and chemical compositions were measured. In addition, flue gas composition, including SO₂ and HCl, was monitored. Experimental results were interpreted by thermodynamic equilibrium calculations.Addition of HCl clearly raised fine particle mass concentration (PM1.0) which was because of increased release of ash-forming material to fine particles. Especially the release of K, Na, Zn and Cd to fine particles increased. These species form chlorides which apparently increases their volatilization from the fuel. When a sufficient amount of SO₂ was supplied in a chlorine rich combustion (S/Cl molar ratio from 4.7 to 7.5), most of the HCl stayed in the gas phase, release of ash-forming elements decreased and also fine particle concentrations dropped significantly. The sulphation of alkali metals is suggested to play a key role in the observed decrease in the fine particle concentration. It seems that the formation of sulphates leads to alkali metal retention in the coarse particle fraction.     

Characterization of the reactivity of limestones with SO2 in a fluidized bed reactor

The reaction between SO₂ and calcined limestone particles has been studied in a fluidized bed combustor. Measurements of sorbent reactivity with SO₂ were made for small batches of limestone injected into the combustor. Simultaneous continuous combustion of bituminous coal provided conditions like those of a boiler for study of the sulphation reaction. A semi-empirical rate model of the CaO-SO₂ reaction has been developed. External mass transfer of SO₂, diffusion within the particles and chemical reaction are taken into account. The limestone reactivity with SO₂ is characterized by two parameters which are dependent on the temperature and sorbent particle size. A model for predicting the limestone requirements in a fluidized bed boiler has been developed. Parameters from the batch experiments are included. The predictions for sulfur retention agree with the experimental results. In addition, effects of operating conditions (gas velocity, recycle, limestone particle size) on the retention of SO₂ were simulated using the model.     

Formation of alkali sulphate aerosols in biomass combustion

This paper is centred in the gaseous chemistry involved in the formation of alkali sulphate in combustion and post-combustion conditions, a matter of interest in the formation of fine particulates in biomass combustion and, most likely, also in deposit formation. Previous experimental results by the authors and other researchers on the role of sulphur oxidation in these processes are considered and compared with theoretical predictions based on several SO_x and SO_x-alkali mechanisms published recently, mostly based on ab initio calculations and theoretical estimations of the reaction kinetics. Whereas the complete Glarborg-Marshall mechanism for the alkali-SO_x interaction [Glarborg P, Marshall P. Mechanism and modelling of the formation of gaseous alkali sulfates. Combust Flame 2005;141:22-39] seems to be too slow for the conditions tested, the SO₂-SO₃ subset, complemented with a fast, irreversible reaction , is shown to adequately fit the experimental results considered. The results presented here confirm the role of sulphur oxidation as the limiting step in the formation of alkali sulphate, and the importance of the gas cooling rate on the amount of sulphate formed and, as a consequence, on the properties of fine particles.     

Effects of operational parameters on emission performance and combustion efficiency in small-scale CFBCs

A well-designed CFBC can burn coal with high efficiency and within acceptable levels of gaseous emissions. In this theoretical study effects of operational parameters on combustion efficiency and the pollutants emitted have been estimated using a developed dynamic 2D (two-dimensional) model for CFBCs. Model simulations have been carried out to examine the effect of different operational parameters such as excess air and gas inlet pressure and coal particle size on bed temperature, the overall CO, NO_x and SO₂ emissions and combustion efficiency from a small-scale CFBC. It has been observed that increasing excess air ratio causes fluidized bed temperature decrease and CO emission increase. Coal particle size has more significant effect on CO emissions than the gas inlet pressure at the entrance to fluidized bed. Increasing excess air ratio leads to decreasing SO₂ and NO_x emissions. The gas inlet pressure at the entrance to fluidized bed has a more significant effect on NO_x emission than the coal particle size. Increasing excess air causes decreasing combustion efficiency. The gas inlet pressure has more pronounced effect on combustion efficiency than the coal particle size, particularly at higher excess air ratios. The developed model is also validated in terms of combustion efficiency with experimental literature data obtained from 300 kW laboratory scale test unit. The present theoretical study also confirms that CFB combustion allows clean and efficient combustion of coal.     

Modulation of silica layer properties by varying the granulometric state of tetraethyl orthosilicate precursor aerosols during combustion chemical vapor deposition (CCVD)

Abstract

For the purpose of silica surface layer modulation, a pneumatic-controlled two-substance atomizer with inertia-based coarse droplet separation was operated at different system pressures for tetraethyl orthosilicate precursor aerosol supply during combustion chemical vapor deposition. A comprehensive testing study was performed to characterize the atomizer’s performance characteristics, initial precursor aerosols at the atomizer’s outlet, transformed aerosols before combustion, combustion aerosols and formed layers. Laser diffraction spectrometry, differential electrical mobility analyses and condensation particle counting were used for aerosol characterization with regard to particle size and particle production quantities. Layers were characterized by scanning electron microscopy, atomic force microscopy, spectral ellipsometry, water contact angle measurements and light transmission concerning geometric properties (thickness, surface structure and roughness) and physical behaviors (i.e., optical behaviors, hydrophobicity). Results show a quasi-linear relationship of the ejection mass flow of the pneumatic-controlled atomizer and geometric layer properties which again show a direct relationship to the physical properties. No correlation was found between the aerosols before combustion and the combustion aerosols since the majority of combustion aerosol particles are synthesized solely from the gas phase based on evaporated precursor material.

Copyright © 2020 American Association for Aerosol Research     

NOx reduction performance of lean NOx catalyst and lean NOx adsorber using DME as reducing agent

The deactivation of a commercial Selective Catalytic Reduction (SCR) catalyst, of V₂O₅−WO₃/TiO₂ type, has been studied through comparisons with results from a full-scale biomass combustion plant to that with laboratory experiments. In the latter, the catalyst was exposed to KCl and K₂SO₄ by both wet impregnation with diluted salt solutions and deposition of generated submicrometer aerosol particles by means of an electrostatic field. The reactivity of fresh and deactivated samples was examined in the SCR reaction. Chemical and physical characterizations were focusing on internal structures and chemical composition. Deposition of submicrometer sized particles on the monolithic SCR catalyst was shown to induce deactivation with characteristics resembling those obtained in a commercial biomass combustion plant.     

Conditions for Cloud Settling and Rayleigh-Taylor Instability

Most aerosol motion can be analyzed by individual particle motion or by the motion of the suspending gas. There are, however, two related situations in which an aerosol can exhibit bulk motion: cloud settling and Rayleigh-Taylor instability. In both cases, the aerosol particles move faster as a cloud than they do as individual particles. In the case of cloud settling, the aerosol is usually a spheroidal cloud surrounded by clean air. Rayleigh-Taylor instability occurs when a dense aerosol layer overlies a layer of clean air. This instability is characterized by abrupt breakthrough of the aerosol layer into the clean air layer at multiple points. High-concentration, submicrometer test aerosols were generated in two experimental systems that permitted observation of the transition from particle-dominated motion to cloud, or bulk, dominated motion and measurement of cloud settling velocities and characteristics. In both systems aerosol concentration could be controlled over two orders of magnitude. One system used commercial ventilation smoke tubes to release a dense stream of aerosol into a low velocity wind tunnel. The other used diluted mainstream cigarette smoke from a smoking machine in an aerosol centrifuge. Based on these experiments, theoretical equations for cloud settling predict cloud settling velocity within an order of magnitude. The transition from individual particle motion to observable bulk motion occurs when predicted cloud settling velocity is from 0.01 to 0.05 m/s. Cloud settling appears to be initiated from an aerosol stream or layer by Rayleigh-Taylor instability. The ratio of cloud settling velocity to particle settling velocity does not appear to be a reliable predictor of the transition from particle to bulk motion.     

Computational Modeling of Silicon Nanoparticle Synthesis: I. A General Two-Dimensional Model

A two-dimensional model has been developed for silicon nanoparticle synthesis by silane thermal decomposition driven by laser heating in a tubular reactor. This fully coupled model includes fluid dynamics, laser heating, gas phase and surface phase chemical reactions, and aerosol dynamics which includes particle transport and evolution by convection, diffusion, thermophoresis, nucleation, surface growth, and coagulation processes. A moment method, based upon a lognormal particle size distribution, and a sectional method are used to model the aerosol dynamics. The simulation results obtained by the two methods are compared. The sectional method is capable of capturing the bimodal behavior that occurs locally during the process, while the moment method is computationally more efficient. The effect of operating parameters, such as precursor concentration, gas phase composition, inlet gas velocity and laser power input, on the characteristics of the particles produced are investigated. Higher temperature generates more large particles with higher precursor conversion. Shorter residence time, from high inlet velocity, produces more small particles at the cost of lower precursor conversion. Increasing H₂ concentration suppresses particle formation by reducing the rates of gas phase and surface reactions, leading to fewer and smaller particles. In addition, the relative importance of the interconnected mechanisms involved in the particle formation is considered. The results make clear that spatial variations in reaction conditions are the primary source of size polydispersity and generation of non lognormal overall size distributions in a laser-driven process like that considered here.     

Morphological and Elemental Classification of Freshly Emitted Soot Particles and Atmospheric Ultrafine Particles using the TEM/EDS

The Transmission Electron Microscopy (TEM) and Energy Dispersive Spectroscopy (EDS) were used to determine morphology and elemental composition of a variety of freshly emitted soot particles (acetylene flame, candle flame, kerosene flame, diesel exhaust, electric arc, plastic burning, styrofoam burning, wood burning [white oak and pine bark], and rice straw burning), which can be possible candidate soot in the ambient atmosphere, and ultrafine particles sampled in urban, industrial, and coastal sites during ultrafine particle formation events (combustion and photochemical events). By using mobility-classified non-refractory ((NH ₄ ) ₂ SO ₄ ) and refractory (Polystyrene latex (PSL) and salt (NaCl)) particles, limitation of the TEM was tested. Data showed that the TEM method can be used to examine shapes of both volatile particles such as (NH ₄ ) ₂ SO ₄ (100 nm) at low, but not high magnification (refer to low and high beam intensity, respectively), and non-volatile particles like NaCl (100 nm) and PSL (84 nm) at either low or high magnification. Distinct differences in morphological properties such as primary particle diameter, fractal dimension, and microstructure were observed among the different types of fresh soot particles. The atmospheric ultrafine particles were classified as agglomerates, sulfate mixtures (spherical), metallic oxides (spherical and polygonal), C-rich refractory (not agglomerated), C-rich non-refractory (not agglomerated), Si-rich (spherical), Na-rich (porous), or P-containing (non-spherical) particles. At the urban Gwangju site, a higher fraction of fresh and aged agglomerates was observed than at other sites. The C-rich non-refractory and sulfate mixtures were often observed in the photochemical event. The C-rich refractory particles were abundant at the Gwangju and Yeosu sites. The coastal Taean site had few agglomerates due to limited anthropogenic combustion source.     

Formation and Emission of Submicron Particles in Pulverized Olive Residue (Orujillo) Combustion

The particle formation and emission in the combustion of pulverized olive residue (orujillo) is studied in this work. The fuel has been burned in controlled combustion conditions in an entrained flow reactor. A bimodal distribution with mode peaks at 155 nm and 110 μm is found for fly ashes. Coarse particles have been characterized by laser diffractometry and SEM, while fines have been analyzed by low-pressure impaction, DMA, SEM, and X-ray diffraction. Particles with Dp < 1 μm are composed of only K₂SO₄ and KCl in the same mass proportion, and possibly K₃PO₄ (less than 7% in mass). The use of a new particle sampling probe and a TEM allowed a detailed study of the formation of these particles when flue gases cool down. K₂SO₄ is experimentally found to start nucleation over 900°C, while KCl is not observed at this temperature. Condensation of KCl on these nuclei is observed in a sample taken at 560°C. These “formation steps” are in good agreement with both theoretical calculations by other authors and a simple equilibrium schema shown here.     

Removal of fine particles in wet flue gas desulfurization system by heterogeneous condensation

A novel process to remove fine particles with high efficiency by heterogeneous condensation in a wet flue gas desulfurization (WFGD) system is presented. A supersaturated vapor phase, necessary for condensational growth of fine particles, was achieved in the SO₂ absorption zone and at the top of the wet FGD scrubber by adding steam in the gas inlet and above the scrubbing liquid inlet of the scrubber, respectively. The condensational grown droplets were then removed by the scrubbing liquid and a high-efficiency demister. The results show that the effectiveness of the WFGD system for removal of fine particles is related to the SO₂ absorbent employed. When using CaCO₃ and NH₃·H₂O to remove SO₂ from flue gas, the fine particle removal efficiencies are lower than those for Na₂CO₃ and water, and the morphology and elemental composition of fine particles are changed. This effect can be attributed to the formation of aerosol particles in the limestone and ammonia-based FGD processes. The performance of the WFGD system for removal of fine particles can be significantly improved for both steam addition cases, for which the removal efficiency increases with increasing amount of added steam. A high liquid to gas ratio is beneficial for efficient removal of fine particles by heterogeneous condensation of water vapor.