Dynamics of sulfur dioxide absorption in a raindrop falling at terminal velocity

Sulfur dioxide absorption dynamics in a raindrop are studied numerically by means of a fully numerical simulation method (FNSM) in which a composite orthogonal grid system consisting of both gas- and liquid-phase is adopted. When a raindrop with fixed radius falls in association with terminal velocity, a recirculation bubble always accompanies the gas-phase flow field in the aft region of the drop. With regard to the drop internal flow structure it has a drastic variation with drop size. When the drop radius is small (e.g. r_s=200 μm), only a single vortex motion is seen inside the drop. Under such a situation, sulfur dioxide absorbed from the interface is mainly transported from the area in front of the aft stagnation point. In contrast, as the drop is relatively large, say, r_s=500 μm, it is of interest to find that a double-vortex motion, composed of a primary and a secondary vortexes, is clearly observed. As a result, the onset of SO₂ transport process occurs at the drop’s surface near where the two vortexes meet. By defining a drop mass transport number, it indicates that the mass transported via internal circulation is always much faster than that by mass diffusion and the latter is highly relevant to the drop radius. Accordingly, the SO₂ transport dynamics in a raindrop is essentially determined by drop size.     

Simulation of aerosols and gas-phase species over Europe with the Polyphemus system. Part II: Model sensitivity analysis for 2001

This paper presents a multi-pollutant sensitivity study of an air quality model over Europe with a focus on aerosols. Following the evaluation presented in the companion paper, the aim here is to study the sensitivity of the model to input data, mathematical parameterizations and numerical approximations. To that end, 30 configurations are derived from a reference configuration of the model by changing one input data set, one parameterization or one numerical approximation at a time. Each of these configurations is compared to the same reference simulation over two time periods of the year 2001, one in summer and one in winter. The sensitivity of the model to the different configurations is evaluated through a statistical comparison between the simulation results and through comparisons to available measurements. The species studied are ozone (O₃), nitrogen dioxide (NO₂), sulfur dioxide (SO₂), ammonia (NH₃), coarse and fine aerosol particles (PM_c and PM_2.5), sulfate, nitrate, ammonium, chloride and sodium.For all species, the modeled concentrations are very sensitive to the parameterization used for vertical turbulent diffusion and to the number of vertical levels. For the other configurations considered in this work, the sensitivity of the modeled concentration to configuration choice varies with the species and the period of the year. O₃ is impacted by options related to boundary conditions. PM_c is sensitive to sea-salt related options, to options influencing deposition and to options related to mass transfer between gas and particulate phases. PM_2.5 is sensitive to a larger number of options than PM_c: sea-salt, boundary conditions, heterogeneous reactions, aqueous chemistry and gas/particle mass transfer. NO₂ is strongly influenced by heterogeneous reactions. Nitrate shows the highest variability of all species studied. As with NO₂, nitrate is strongly sensitive to heterogeneous reactions but also to mass transfer, thermodynamic related options, aqueous chemistry and computation of the wet particle diameter. While SO₂ is mostly sensitive to aqueous chemistry, sulfate is also sensitive to boundary conditions and, to a lesser extent, to heterogeneous reactions. As with nitrate, ammonium is largely impacted by the different configuration choices, although the sensitivity is slightly lower than for nitrate. NH₃ is sensitive to aqueous chemistry, mass transfer and heterogeneous reactions. Chloride and sodium are impacted by sea-salt related options, by options influencing deposition and by options concerning the aqueous-phase module.     

氧化镁烟气脱硫反应特性研究

利用实验室规模的鼓泡式反应装置,对比了碳酸钙、氧化镁和氧化镁/硫酸镁脱硫剂的反应活性,证实脱硫液中高浓度硫酸镁的存在是保证镁法脱硫效率高于钙法的重要因素,并考察了硫酸镁浓度、脱硫剂(氧化镁)浓度、烟气量、SO2浓度和吸收液温度等因素对脱硫效率的影响。结果表明,脱硫反应可以根据pH分为2个不同阶段;反应过程中脱硫效率随着硫酸镁浓度的增加而显著升高;烟气量增加将会导致脱硫效率有所下降;入口SO2浓度升高,脱硫效率下降;氧化镁浓度、温度对脱硫效率影响不显著。结合实验现象进行推断,氧化镁脱硫的反应过程受SO2在气液两相界面的传质扩散和其水解产物在液相的扩散控制。     

From Air Repair to EM: A&WMA’s Publications through a Century of Change

Abstract

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO₂) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO₂ emission is inversely proportional to the parameter y _CO2max, which is equal to the maximum carbon dioxide (CO₂) content by vol ume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

The Survival of Airborne Serratia marcescens in Urban Concentrations of Sulfur Dioxide

Aerosols of Serratia marcescens ATCC 274 were suspended in a 709L rotating drum at 20 ± 1 °C and high to mid-range relative humidities. At specified times after bacterial aerosolization, sulfur dioxide was added to concentrations of 2.5, or 5 mg/m³. Viable cell decay rate constants, in control aerosols without added sulfur dioxide, increased rapidly from near 100% to 60% RH in the first hour (termed: young aerosol) of suspension, and from a minimum rate constant at 80% in the succeeding four hours (termed: old aerosol).Upon addition of sulfur dioxide to a cloud of S. marcescens, generally, viable cell decay rate constants increased further. One exception was at 80% relative humidity where maximum resistance to SO₂ accelerated death was observed for old aerosols. Cells in young aerosols were particularly sensitive to SO₂ addition at mid-range humidities, while in older aerosols the cells were insensitive to up to 5 mg SO₂/m³ introduced at high RH; but were up to 10 times more sensitive than cells in young aerosols to a given increase (from 2.5 to 5 mg/m³) in SO₂ concentration at mid-range humidities.     

Simplified Models of U.S. Acid Rain Control Costs

Simplified algorithms are presented for estimating the cost of controlling sulfur dioxide (SO₂) emissions from existing coal-fired power plants on a state-by-state basis. Results are obtained using the detailed Utility Control Strategy Model (UCSM) to calculate the Impacts of emission reductions ranging from approximately 30 percent to 90 percent of projected 1995 emissions for 18 different scenarios and 36 states. Scenarios include the use of two dry SO₂ removal technologies (lime spray dryers and LIMB) as potential options for power plant retrofit, in addition to currently available emission control options including coal switching, coal cleaning and wet flue gas desulfurization (FGD). Technical assumptions relating to FGD system performance and the upgrading of existing cold-side electrostatic precipitators (ESP) for reduced sulfur levels are also analyzed, along with the effects of interest rates, coal prices, coal choice restrictions, plant lifetime, and plant operating levels. Results are summarized in the form of a 3-term polynomial equation for each state, giving total annualized SO₂ control cost as a function of the total SO₂ emissions reduction for each scenario. Excellent statistical fits to UCSM results are obtained for these generalized equations.     

High Volume Sampling of Acid Mist

Many nonferrous metals are produced from sulfur-bearing minerals. When pyrometallurgical processes are used, sulfur dioxide gas is formed as a byproduct. In many cases, a small but significant portion of the SO₂ is oxidized further to SO₃ within the pyrometallurgical reactor system. Upon cooling of the gases, as would occur when such gases contact the atmosphere, SO₃ will absorb moisture and condense as a sulfuric acid aerosol, typically referred to as acid mist.     

Broadband UV spectroscopy system used for monitoring of SO2 and NO emissions from thermal power plants

A gas monitoring system based on broadband absorption spectroscopic techniques in the ultraviolet region is described and tested. The system was employed in real-time continuous concentration measurements of sulfur dioxide (SO₂) and nitric oxide (NO) from a 220-ton h^?1 circulating fluidized bed (CFB) boiler in Shandong province, China. The emission coefficients (per kg of coal and per kWh of electricity) and the total emission of the two pollutant gases were evaluated. The measurement results showed that the emission concentrations of SO₂ and NO from the CFB boiler fluctuated in the range of 750–1300 mg m^?3 and 100–220 mg m^?3, respectively. Compared with the specified emission standards of air pollutants from thermal power plants in China, the values were generally higher for SO₂ and lower for NO. The relatively high emission concentrations of SO₂ were found to mainly depend on the sulfur content of the fuel and the poor desulfurization efficiency. This study indicates that the broadband UV spectroscopy system is suitable for industrial emission monitoring and pollution control.     

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.     

Multi-Instrument Performance Evaluation of Conductivity-Type Sulfur Dioxide Analyzers

Three different recording analyzers for sulfur dioxide were operated in parallel under field conditions. Manual sampling for sulfur dioxide using the West-Gaeke procedure supplemented the instrumental evaluation tests. Two of the analyzers were of the continuous-flow type. These were found to give markedly higher readings for SO₂ in the atmosphere (in some cases as much as threefold) than did the other recorder which was sequential-batch or the West-Gaeke manual method.     

Sulfur processing in the marine atmospheric boundary layer: A review and critical assessment of modeling uncertainties

Sulfur is an extremely motile and vital element in the Earth's biogeochemical environment, one whose active redox chemistry maintains small reservoirs in the atmosphere and biosphere yet large fluxes through both. Essential for life, intimately linked to the climate state, and an important component of air quality, sulfur and its transport and processing in the atmosphere have been the subject of active research for several decades. This review article describes the current state of our understanding of the atmospheric sulfur cycle, focusing on the marine atmospheric boundary layer, with the aim of identifying the largest roots of uncertainty that most inhibit accurate simulation of sulfur cycling in the atmosphere. An overview of the emissions by phytoplankton and shipping, dispersion and entrainment in the marine boundary layer, and chemical processing by aerosols, clouds, and dry deposition is presented. Analysis of 20 contemporary modeling studies suggests that the greatest ambiguity in global sulfur cycling derives from (in descending order) wet deposition of aerosol sulfate, dry deposition of sulfur dioxide to the Earth's surface, and the heterogeneous oxidation of SO₂ in aerosols and clouds.     

Toxicologic Appraisal of Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

An examination of the available toxicological literature indicates that sulfur dioxide itself would be properly classified as a mild respiratory irritant, the main portion of which is absorbed in the upper respiratory tract. The reported industrial experience of symptoms of mild chronic respiratory irritation from exposures at or above 5 ppm is compatible with what would have been predicted on the basis of available toxicological data. The basic physiological response to inhalation of pure SO₂ appears to be a mild degree of bronchoconstriction reflected in a measurable increase in flow resistance. Although the response is highly variable, most individuals tested have responded to 5 ppm and levels of 5 to 10 ppm have upon occasion produced severe bronchospasm in sensitive individuals. This serves to point up the fact that experience with the industrial Threshold Limit Value (5 ppm) is not applicable as a guide for the general population. Although the majority of individuals tested have shown no detectable response to levels of 1 ppm, there are again sensitive individuals who have responded. It is not known whether these individuals would have responded to concentrations lower than this. The response of these more sensitive individuals to 1 ppm would be classified as detectable response, not as severe bronchospasm. An examination of the available toxicological literature also indicates that sulfuric acid and irritant sulfates, to the extent that the latter have been examined, are more potent irritants than sulfur dioxide. This has been demonstrated in studies using morality and lung pathology as criteria as well as in studies using alterations in pulmonary function in experimental animals and human subjects. The irritant potency of these substances is affected by particle size and by relative humidity, which factors are probably interrelated. It is unfortunate that these substances have not been as yet studied in as great detail as has the less irritant sulfur dioxide. There is evidence which cannot be ignored, even though it is based entirely on animal experiments of one investigator, indicating that the presence of particulate material capable of oxidizing sulfur dioxide to sulfuric acid caused a three to fourfold potentiation of the irritant response. The aerosols causing this potentiation were soluble salts of ferrous iron, manganese and vanadium all of which would become droplets upon inhalation. Insoluble aerosols such as carbon, iron oxide fume, triphenylphosphate or fly ash did not cause a potentiation of the irritant action of SO₂ even when used at higher concentrations. The concentrations of SO₂ used in these various experiments were in some cases as low as 0.16 ppm. The catalytic aerosols were used at concentrations of 0.7 to 1 mg/m³ which is above any reported levels of these metals in urban air. If the SO₂ present as an air pollutant remained unaltered until removed by dilution, there would be no evidence in the toxicological literature suggesting that it would be likely to have any effects on man at prevailing levels. Studies of atmospheric chemistry have shown that SO₂ does not remain unaltered in the atmosphere, especially under onditions of high humidity and in the presence of particulate material, but is converted to H₂SO₄. Such a conversion increases its irritant potency. On this basis the toxicological literature combined with the literature of atmospheric chemistry suggest that sulfur dioxide levels be controlled in terms of the potential formation of irritant particles. This means that control measures as far as feasible should be aimed at both SO₂ and particulate material and not against either alone.     

Odor Threshold Measurement by Dynamic Olfactometry: Significant Operational Variables

Abstract

Combustion flue gases of three different industrial boilers firing miscellaneous fuels were monitored for a twoweek period. Nitric oxide (NO), sulfur dioxide (SO₂), carbon monoxide (CO), carbon dioxide (CO₂), and total hydrocarbons (CxHy) were continuously measured using single-component gas analyzers in parallel with a lowresolution Fourier Transform Infrared (FTIR) gas analyzer. Hydrogen chloride (HCl) was measured continuously using the FTIR analyzer and semi-continuously using a traditional liquid-absorption technique. Nitrous oxide (N₂O), nitrogen dioxide (NO₂), and water vapor (H₂O) were continuously measured using the FTIR analyzer only. Laboratory tests were conducted prior to the field measurements to assess the detection limits of the different measurement methods for each gas component. No significant differences were found between the results of the low-resolution FTIR analyzer and the single-component analyzers or the liquid absorption method.     

Modeling of Sulfur Dioxide Emissions and Acidic Precipitation at Mesoscale Distances

A steady state mesoscale model developed to predict primary SO₂ concentrations from a single point source is presented. The model was validated with data from the Midwest Interstate Sulfur Transport and Transformation (MISTT) project, with root mean square errors of 9.69 μg m^?3 and 0.42 μg m^?3 for SO₂ and SO₄ respectively. Wet deposition (washout and rainout), eddy dispersivity, dry deposition of SO₂ and mean wind speed were found to be the most important factors controlling sulfur dioxide and sulfate concentrations. Estimation of precipitation acidity was then carried out using scavenging theory. The greatest potential acidification occurred approximately 200 km from the source along plume centerllne, which indicates a rather local effect as opposed to a long distance effect. The cross-plume influence was up to 60 km in width at a distance of 400 km from the source.     

Studies on a New Method of Simultaneously Removing Sulfur Dioxide and Oxides of Nitrogen from Combustion Gases

Simultaneous reduction of SO₂ and NO by catalyzed reaction with carbon monoxide at space rates approaching 10⁴ vol/vol/hr has been shown. The reaction of sulfur dioxide with carbon monoxide results in the formation of carbon dioxide and elemental sulfur. Nitric oxide reacts with carbon monoxide to form carbon dioxide and molecular nitrogen. Metals supported on alumina appear to be the preferred catalysts. Among the effective metals are copper, silver, and palladium. A side reaction of carbon monoxide with elemental sulfur to form carbonyl sulfide requires that the initial amount of carbon monoxide be stoichio-metric for the amount of sulfur dioxide plus nitric oxide present. A furnace employing this method would have to be operated at low excess air, near stoichiometric fuel/air, or possibly slightly on the rich side.     

碱式硫酸铝溶液吸收二氧化硫

为了探讨碱式硫酸铝对二氧化硫的吸收效果,对所需试剂硫酸铝和碳酸钙的适宜比例（碱度）,以及碱式硫酸铝能稳定存在的铝量范围等进行了研究,测定了不同铝量和碱度的碱式硫酸铝对二氧化硫的吸收量以及pH值,并分析每种吸收液的饱和吸收量,最后将其与乙二胺/磷酸溶液的吸收情况进行对比。结果表明,碱度为40%时,铝量要保持在70 g/L以下才能在加热时不产生沉淀,吸收过程pH由4.5左右一直下降到2.0左右保持稳定,饱和吸收时间控制在140~160 min为宜,较为理想的方案是铝量32 g/L,碱度35%。     

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.     

Chain Scission of Polymers by Small Concentrations (1 to 5 ppm) of Sulfur Dioxide and Nitrogen Dioxide,Respectively, in Presence of Air and Near Ultraviolet Radiation

Results are presented as to the extent of chain scission (crosslinking) suffered by various polymers exposed to 1 atm of air and near ultraviolet light (λ > 2800 Å) in presence and absence of nitrogen dioxide, sulfur dioxide, and ozone, respectively, in the concentration range of 1 to 5 ppm. Vinyl polymers are scarcely affected by SO₂ and NO₂, respectively; however, nylon and elastomers are quite sensitive toward these gases. These conclusions agree with observations, found in the literature, on tensile tests, elongations, flexibilities, and infrared measurements in presence of sulfur dioxide under similar conditions.     

用于气态零价汞转化的催化剂研究

零价汞的高效去除是燃煤烟气汞污染控制过程中的关键环节。为了促进烟气中的零价汞转化为易于去除的氧化态汞,分别考察了在有HCl存在时,几种过渡金属氧化物(Cu、Fe、Mn、Co和Zr)对零价汞氧化的催化作用,以筛选出性能较好的催化组分;为提高催化剂的抗SO2性能,分别尝试了利用几种金属元素(Sr、Ce、W和Mo)对催化剂进行掺杂改性的方法。结果表明,锰氧化物的催化作用最好,其最佳使用温度在573 K左右;SO2对零价汞的催化氧化有明显抑制作用,在无SO2及1 400 mg/m3SO2时锰催化剂对零价汞催化氧化效率分别为93%和78%。而Mo改性的锰氧化物催化剂的抗硫性能大幅提高,在1 400 mg/m3SO2存在的情况下其对零价汞的催化氧化效率可达到90%以上,较其他改性元素高。     

Emissions of Sulfur Trioxide from Coal-Fired Power Plants

Abstract

Emissions of sulfur trioxide (SO₃) are a key component of plume opacity and acid deposition. Consequently, these emissions need to be low enough to not cause opacity violations and acid deposition. Generally, a small fraction of sulfur (S) in coal is converted to SO₃ in coal-fired combustion devices such as electric utility boilers. The emissions of SO₃ from such a boiler depend on coal S content, combustion conditions, flue gas characteristics, and air pollution devices being used. It is well known that the catalyst used in the selective catalytic reduction (SCR) technology for nitrogen oxides control oxidizes a small fraction of sulfur dioxide in the flue gas to SO₃. The extent of this oxidation depends on the catalyst formulation and SCR operating conditions. Gas-phase SO₃ and sulfuric acid, on being quenched in plant equipment (e.g., air preheater and wet scrubber), result in fine acidic mist, which can cause increased plume opacity and undesirable emissions. Recently, such effects have been observed at plants firing high-S coal and equipped with SCR systems and wet scrubbers. This paper investigates the factors that affect acidic mist production in coal-fired electric utility boilers and discusses approaches for mitigating emission of this mist.