An evaluation of artifact SO42− formation on nylon filters under field conditions

The extent of SO₂ conversion on Membrana (Ghia) Nylasorb nylon filters under field conditions has been evaluated and found to be quite variable. The S-SO₄²⁻ loading on the nylon filters is higher at higher SO₂ concentrations, and on a long term basis approaches a saturatio limit of 2.5 μg S-SO₄²⁻ on a 47mm disc, at a dosage of 230 μg SO₂ approximately. The % conversion decreases as the SO₂ concentration increases. On a long term basis, at an SO₂ concentration range of 1.0–7.7 μg m⁻³, the conversion ranges from 8.2% to 2.1%. The dependence of SO₂ conversion on nylon filters on relative humidity displays a diurnal pattern. An expression has been derived to explain the observed % SO₂ conversion on nylon filters as a combined effect of the ambient SO₂ concentration and relative humidity.     

Simulation of Stack Plume Opacity

ABSTRACT

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO₃ (that hydrolyzes to H₂SO₄), HCl, and NH₃, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult.

We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply).

Conversion of H₂SO₄ to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO₃ emissions showed only a small effect, except if one assumes that most H₂SO₄ condenses on primary particles. Condensation of NH₄Cl occurs only at high NH₃ emission rates (about 25 ppm stack concentration).     

A Study of Sulfur Dioxide in Photochemical Smog I. Effect of SO2 and Water Vapor Concentration in the 1-Butene/NOx/SO2 System

There is an appreciable chemical interaction between SO₂ and photochemical smog which depends on the concentration of SO₂ and water vapor. The rate of decay of SO₂ concentration is greatly increased in the presence of photochemical smog. With 0.75 ppm SO₂, a light-scattering aerosol is produced in dry systems and systems at 22 and 55% relative humidity (RH). Aerosol is not observed until after the NO₂ peak has been reached and the NO concentration has fallen to a very low value. The formation of aerosol corresponds in time to the region of most rapid decrease in the SO₂ profile. In systems at 65% RH or with smaller amounts of SO₂, no light scattering is observed, but the percentage of SO₂ disappearing is greater. In relatively dry systems the presence of SO₂ results in a general slowing down of the photochemical smog reactions. In systems containing water vapor concentrations comparable to those found in the atmosphere, the inhibiting influence of SO₂ on the smog reaction is less pronounced. However, the maximum concentration of oxidant produced by the photochemical smog reactions is significantly lower when SO₂ is present.     

Rates of Conversion of Sulfur Dioxide to Sulfate in a Scrubbed Power Plant Plume

ABSTRACT

The rate of conversion of SO₂ to SO₄ ^2- was re-estimated from measurements made in the plume of the Cumberland power plant, located on the Cumberland River in north-central Tennessee, after installation of flue gas desulfurization (FGD) scrubbers for SO₂ removal in 1994. The ratio of SO₂ to NO_y emissions into the plume has been reduced to ~0.1, compared with a prescrubber value of ~2. To determine whether the SO₂ emissions reduction has correspondingly reduced plume-generated particulate SO₄ ^2- production, we have compared the rates of conversion before and after scrubber installation. The prescrubber estimates were developed from measurements made during the Tennessee Plume Study conducted in the late 1970s. The post-scrubber estimates are based upon two series of research flights in the summers of 1998 and 1999. During two of these flights, the Cumberland plume did not mix with adjacent power plant plumes, enabling rate constants for conversion to be estimated from samples taken in the plume at three downwind distances. Dry deposition losses and the fact the fact that SO₂ is no longer in large excess compared with SO₄ ^2- have been taken into account, and an upper limit for the conversion rate constant was re-estimated based on plume excess aerosol volume. The estimated upper limit values are 0.069 hr^-1 and 0.034 hr^-1 for the 1998 and 1999 data, respectively. The 1999 rate is comparable with earlier values for nonscrubbed plumes, and although the 1998 upper limit value is higher than expected, these estimates do not provide strong evidence for deviation from a linear relationship between SO₂ emissions and SO₄ ^2- formation.     

粘胶基活性炭纤维用于低浓度SO2常温脱除的实验研究

活性炭纤维（ACF）是一种新型功能性炭材料。应用粘胶基活性炭纤维（cellulose-ACF）对低浓度SO₂（571 mg/m³）进行吸附氧化实验，通过改变活性炭纤维量、SO₂浓度、氧浓度，观察cellulose-ACF脱除低浓度SO₂能力的变化规律。实验结果表明，随着活性炭纤维量、氧浓度的增加，cellulose-ACF对低浓度SO2的脱除能力增强。在此基础上展望活性炭纤维在大气环保领域的应用前景。     

Humidity effects on photochemical aerosol formation in the SO2-NO-C3H6-air system

In order to investigate the effects of humidity on the gas-phase oxidation of SO₂ in polluted air and on the subsequent aerosol formation process, photoirradiation experiments were carried out by means of a 4-m³ chamber, in which mixtures containing SO₂, NO and C₃H₆ with concentrations in the ppm range were exposed to simulated solar radiation in different relative humidity (r.h.) conditions. The total amount of oxidized SO₂ was quantified from the SO₄²⁻ yield determined by the chemical analysis of the aerosol product, and a part due to the oxidation by the OH radical was evaluated by estimating the OH concentration from the decay rate of C₃H₆. The remaining part was assigned to the oxidation by the Criegee intermediate, as it had a good correlation with the progress of the O₃ + C₃H₆ reaction. The contributions of the two oxidizing species to the total conversion and the oxidation rate of SO₂ were measured as functions of r.h. As a result, experimental evidence was obtained for the prediction of Calvert and Stockwell's (1983, Envir. Sci. Technol. 17, 428A–443A) simulation that the oxidation due to the Criegee intermediate was retarded by the increase in humidity. The OH contribution, on the other hand, was almost independent of r.h. It was observed consequently that the total oxidized amount of SO₂ considerably decreased as r.h. was higher.The humidity effect on the aerosol formation process was found to be more complicated than the effect on the gas-phase chemistry. The maximum rate of increase in the particle number concentration rose linearly with increasing r.h., but the number concentration itself measured at its maximum or at the end of the irradiation reached a ceiling value around r.h. = 30% and went down for higher r.h. The average panicle size in the final stage of the reaction showed a minimum around the same r.h. at which the number concentration was maximum. The H₂SO₄ concentration in the mist particles, however, decreased monotonically as r.h. got higher. It was suggested that these different responses against the increase in humidity resulted from the cooperation of several processes such as the H₂SO₄ monomer formation, the H₂O condensation, the particle coagulation, etc., which had different dependences on r.h.     

NOy removal from the Cumberland Power Plant Plume

Airborne measurements were performed in the plume of the Cumberland Power Plant during August 1998 using a highly sensitive SO₂ instrument. The measurements confirmed previous suggestions that NO_y species are removed from the plume at a faster rate than SO₂. The differential removal rate (the difference between loss rate of NO_y and that of SO₂) was estimated to be 0.06 h⁻¹. This value implies that the NO_y loss rate is in the range of 0.09–0.14 h⁻¹. The application of a mathematical argument, based on the convolution integral, enabled improved synchronization of the data from the SO₂ and NO_y instruments. Examination of the synchronized data revealed that the concentration ratio of SO₂ and NO_y varies across the plume. Near the source it is higher at the wings of the plume, while in the core of the plume it is similar to the ratio at the release point. Two possible explanations of the observations are discussed: conversion to non-measurable NO_y species, and in-plume loss of NO_y (as HNO₃) via dry deposition.     

旋转填料床/柠檬酸盐法吸收-解吸SO2

提出采用旋转填料床结合柠檬酸盐法脱除烟气中SO2的方法,考察了旋转填料床转子转速、液气比、初始柠檬酸根浓度和初始pH值等因素对脱硫效率的影响。结果表明,采用超重力法超重机转子转速为1 000 r/min、液气比为7L/m3、初始柠檬酸根浓度为1.5 mol/L、吸收液的初始pH值为5.0,脱硫效率稳定在99%左右。研究了水蒸气汽提法解吸SO2时初始柠檬酸根浓度、初始pH值、SO2浓度、富液流量和水蒸气流量对解吸效率的影响,得出了影响SO2解吸率的基本规律,并进行了分析。通过实验证明该方法在技术上是可行的,具有良好的应用前景。     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.     

Simultaneous Sulfur Dioxide and Nitrogen Dioxide Removal by Calcium Hydroxide and Calcium Silicate Solids

ABSTRACT

At conditions typical of a bag filter exposed to a coal-fired flue gas that has been adiabatically cooled with water, calcium hydroxide and calcium silicate solids were exposed to a dilute, humidified gas stream of nitrogen dioxide (NO₂) and sulfur dioxide (SO₂) in a packed-bed reactor. A prior study found that NO₂ reacted readily with surface water of alkaline and non-alkaline solids to produce nitrate, nitrite, and nitric oxide (NO). With SO₂ present in the gas stream, NO₂ also reacted with S(IV), a product of SO₂ removal, on the exterior of an alkaline solid. The oxidation of S(IV) to S(VI) by oxygen reduced the availability of S(IV) and lowered removal of NO₂. Subsequent acidification of the sorbent by the removal of NO₂ and SO₂ facilitated the production of NO. However, the conversion of nitrous acid to sulfur-nitrogen compounds reduced NO production and enhanced SO₂ removal. A reactor model based on empirical and semi-empirical rate expressions predicted rates of SO₂ removal, NO₂ removal, and NO production by calcium silicate solids. Rate expressions from the reactor model were inserted into a second program, which predicted the removal of SO₂ and NO_x by a continuous process, such as the collection of alkaline solids in a baghouse. The continuous process model, depending upon inlet conditions, predicted 30-40% removal for NO and 50-90% removal for SO₂. These x 2 results are relevant to dry scrubbing technology for combined SO₂ and NO_x removal that first oxidizes NO to NO₂ by the addition of methanol into the flue duct.     

Interactions of Sulfur Dioxide with Insoluble Suspended Particulate Matter

A laboratory study was conducted of the heterogeneous catalysis of sulfur dioxide at ppm concentrations in air by insoluble particles of CaCO₂, V₂O₅, Fe₂0₃, flyash from a coal-burning power plant, MnCO₂, activated carbon, and suspended particulate matter from urban air. The investigalion was performed by utilizing a new technique for aerosol stabilization which consists of depositing the aerosol on Teflon beads in a fluidized bed. The Teflon beads with deposited aerosol particles were then packed into a flow reactor. Progress of the chemical reaction of SO₂ with deposited particles was continuously monitored by determining the SO₂ concentrations in the reactor effluent with a microcoulometer.

In this investigation, CaCOg, V₂O₅, and flyash were essentially inert to SO₂ at room temperature. Fe₂O₃, activated carbon, MnO₂, and suspended particulate matter from urban air sorbed SO₂ from air streams with up to 14.4 ppm SO₂ in air. Evidence is presented which suggests that a substantial part of the sorbed SO₂ was physically adsorbed.

Bioassay procedures which utilize pulmonary flow resistance changes in guinea pigs to monitor response to inhaled SO₂-aerosol mixtures in air have indicated the weak or non-potentiating capacity of insoluble aerosols as contrasted to soluble aerosols. Potentiating response of an aerosol appears to be strongly associated with reaction of SO₂ in a water droplet containing aerosol ions and not with physically adsorbed SO₂ on an insoluble aerosol.     

Wet and dry deposition of sulfur and nitrogen compounds in Ontario

Measurements have been made of sulfur and nitrogen compounds in precipitation since 1980 and in air since 1981 in Ontario. This paper presents results of the atmospheric deposition measurement program to the end of 1985. As is to be expected from the distribution of emission sources, annual concentrations of SO₄²⁻ andNO₃⁻ in precipitation, and of SO₂,SO₄²⁻ andNO₃⁻ in air are higher in southern Ontario than in northern Ontario. The corresponding distribution pattern for deposition is similar to that of concentration. A wet SO₄²⁻ deposition rate of 20 kg ha¹⁻ y¹⁻, a value considered critical for the acidification of sensitive water bodies, is exceeded in all of central and southern Ontario. On a province-wide basis, sulfur wet deposition is about four times higher than sulfur dry deposition. For nitrogen, wet and dry deposition are more comparable, though the former is still higher. The S- and N-species display different seasonal trends in concentration and deposition reflecting a dependence on meteorological factors, and on the associated chemical transformation rates. On the other hand, year to year variations are small.     

Further Effects of Temperature and Pressure on Photochemical Oxidant Production

A procedure is described for producing a sulfur dioxide (SO₂) contaminated atmosphere within a body plethysmograph, exposing man to this atmosphere while maintaining the SO₂ concentration at a given level, and measuring the concentration with less than a oneminute lag time. A syringe is used to introduce incremental volumes of SO₂ limiting the maximum SO₂ concentration in the chamber and assuring safety of the subject. A Titrilog SO₂ analyzer with its rapid response characteristics provides quick measurement of the SO₂ concentration. The body plethysmograph used in this manner serves simultaneously as a pulmonary function measuring device and as an exposure chamber.     

The Absorption of Atmospheric Sulfur Dioxide by Water Solutions

Results of a laboratory study indicate that the rate of solution of atmospheric sulfur dioxide in distilled water, over the range of atmospheric concentrations of 0.81?8.73 mg SO₂/M³, is a function of the concentration of SO2 in the atmosphere, with saturation being reached more rapidly at the higher concentrations. This would indicate that rain water, with constantly renewed surfaces, can be very effective in the removal of atmospheric SO₂. The pH of the exposed water samples reached values of 4.0 or less, comparable to values observed in fog and cloud water near large industrial areas. Overall solubility of sulfur dioxide in distilled water did not follow the law of partial pressure. At the atmospheric concentrations used it was found that over 98.5% of the sulfite in solution was in the form of the bisulfite ion with, the remainder present as unionized sulfurous acid. Computations using the concentration of unionized sulfurous acid in the solution showed that the solubility of this portion of dissolved sulfite did follow the law of partial pressure.     

The Evolution of Particles in the Plume from a Large Coal-Fired Boiler with Flue Gas Desulfurization

ABSTRACT

Airborne measurements were made of gaseous and particulate species in the plume of a large coal-fired power plant after flue gas desulfurization (FGD) controls were installed. These measurements were compared with measurements made before the controls were installed. The light scattering and number and volume distributions of plume excess particles were determined by nephelometry and optical particle counting techniques. The plume impact based on optical techniques was much lower than that observed in earlier measurements. Indeed, plume excess volumes as a function of particle size were of the same magnitude as the variability of the background volume distribution. In situ excess plume scattering actually decreased with distance from the source, in contrast to pre-FGD conditions. The upper limit for the dry rate of SO₂-to-SO₄ ^2- conversion was estimated from plume excess volume measurements to be about 4% lir¹. This is slightly greater than the upper limit, 3.5% lir¹, estimated by earlier researchers, but the same as that estimated using the present technique with the earlier data. The cross-plume profile of volume suggests SO₂-to-SO₄ ^2- conversion is highest at the plume edges. The greatest benefit of SO₂ reduction on plume excess volume and visibility appears to occur far downwind of the source.     

Regional effects and efficiency of flue gas desulphurization in the Carpathian Basin

Although sulphur emissions (mainly as SO₂) have been continuously decreasing over the last 20 years in most western industrialized countries, localized SO₂ problems still exist in conjunction with strong local emission, meteorological, and topographical factors. In this study, the effect of supplementary installed flue gas desulphurization (FGD) units at high-capacity power plants on regional air pollution in the Carpathian Basin is investigated. The dispersion and accumulation of the SO₂ air pollutant are studied with the regional three-dimensional on-line atmosphere-chemistry model REMOTE. The changes in the SO₂ air pollution are investigated by parallel simulations in a case study, where the single modified parameter is the SO₂ emission rate. The results show that FGD units significantly reduce the horizontal and the vertical dispersion of the emitted SO₂, and its transboundary transport, too. Beside the SO₂ removal efficiency, the dispersion and accumulation also depend on the seasonal weather conditions. During winter, the dispersion and accumulation are higher than in other seasons. Due to this phenomenon, higher SO₂ removal efficiency is needed to guarantee similar air quality features like in the other seasons.     

Dissociation of Sulfur Hexafluoride Tracer Gas in the Presence of an Indoor Combustion Source

ABSTRACT

As an odorless, nontoxic, and inert compound, sulfur hexafluoride (SF₆) is one of the most widely used tracer gases in indoor air quality studies in both controlled and uncontrolled environments. This compound may be subject to reactions with water vapor under elevated temperature to form acidic inorganic compounds such as HF and H₂SO₄. Thus, in the presence of unvented combustion sources such as kerosene heaters, natural gas heaters, gas log fireplaces, candles, and lamps, the SF₆ dissociation may interfere with measurements of the emissions from these sources. Tests were conducted in a research house with a vent-free natural gas heater to investigate these potential interferences. It was observed that the heater operation caused about a 5% reduction of SF₆ concentration, which can be an error source for the ventilation rate measurement and consequently the estimated pollutant emission rates. Further analysis indicates that this error can be much greater than the observed 5% under certain test conditions because it is a function of the ventilation flow rate. Reducing the tracer gas concentration has no effect on this error. A simple theoretical model is proposed to estimate the magnitude of this error.

The second type of interference comes from the primary and secondary products of the SF₆ dissociation, mainly H₂SO₄, SO₂, HF, and fine particulate matter (PM). In the presence of ~5 ppm SF₆, the total airborne concentrations of these species increased by a factor of 4-10. The tests were performed at relatively high SF₆ concentrations, which is necessary to determine the interferences quantitatively. The second type of interference can be significantly reduced if the SF₆ concentration is kept at a low ppb level.     

Nucleation in the MSA-water vapor system

The threshold concentrations of gaseous methane sulfonic acid (MSA) required for homogeneous and heterogeneous nucleation of MSA solution droplets in the MSA-water system have been calculated as a function of environmental relative humidity. The MSA concentration required to supersaturate the atmosphere (with respect to aqueous MSA solutions) at 80% r.h. is of the order of 10⁻¹² atm (1 pptv), whereas the concentration required for spontaneous production of new MSA aerosol is of the order of 10⁻⁸ atm (10 ppbv). The calculations also show a strong dependence of the saturation curve on relative humidity. At 80 % r.h., 1 pptv MSA vapor supersaturates the atmosphere, whereas at 10 % r.h. about 5 ppbv is required to supersaturate the environment. The role which the conversion of dimethylsulfide (DMS) to MSA and H₂SO₄ might play in the formation and growth of sub-μm particles in remote oceanic regions is discussed.     

Removal of SO2 from Simulated Flue Gases Using Non-Thermal Plasma-Based Microgap Discharge

Abstract

The removal of sulfur dioxide (SO₂) from simulated flue gases streams (N₂/O₂/H₂O/SO₂) was experimentally investigated using microgap discharge. In the experiment, the thinner dielectric layers of aluminum oxide (Al₂O₃) were used to form the microgap discharge. With this physical method, a high concentration of hydroxyl (OH·) radicals were produced using the ionization of O₂ and H₂O to further the conversion of SO₂ into sulfuric acid (H₂SO₄) at 120° C in the absence of any catalysts and absorbents, which were captured with the electrostatic precipitator (ESP). As a result, the increase of discharge power and concentrations of O₂ and H₂O increased the production of OH· radicals resulting in enhanced removal of SO₂ from gas streams. With the test and analysis, a number of H₂SO₄ droplets were produced in experiment. Therefore, a new method for removal of SO₂ in semidry method without ammonia (NH₃) additive was found.     

Spatial and temporal variations of aerosol sulfate and trace elements in a sourcedominated urban environment

Time-resolved measurements of SO₂, sulfate, particulate carbon and trace metal (Pb, As, K, Mn, Fe and V) concentrations were performed simultaneously at four locations in Ljubljana, Yugoslavia, during February and April of 1985. During the winter three different SO₄²⁻ formation regimes are identified: A—morning period coinciding with maximum emissions and high humidity resulting in maximum SO₄²⁻ concentrations, with the sulfate formation during this period attributed to fast heterogeneous, aqueous oxidation of local SO₂ involving combustion products; B—late evening period with low humidity and high emissions when most SO₄²⁻ is primary; C—the remainder of the day when SO₄²⁻ appears to be of a regional origin and formed by a combination of heterogeneous and homogeneous processes. During the non-heating season, the SO₄²⁻ appears to be of regional origin.