Studies on the Removal of Sulfur Dioxide from Hot Flue Gases to Prevent Air Pollution

The pollution of the atmosphere by sulfur dioxide is one of the gravest of all in public nuisance problems, especially in the industrial regions. A practically applicable method in industry for the removal of sulfur dioxide has been studied. The Kiyoura-T .I .T. process utilizes the oxidation method to convert S0₂ of the flue gas to S0₃ in the presence of vanadium oxide. A limited amount of water vapor present in the flue gas reacts with S0₃ to form H₂SO₄. Ammonia is then introduced to the gaseous mixture, which is now at the suitable temperature, to form ammonium sulfate. Conditions are controlled to produce ammonium sulfate of the right size to produce aggregate that may be removed by a dry cyclone separator.     

Responses of Hybrid Poplar Trees to Sulfur Dioxide Fumigation

This paper verifies the presence of significant interclonal variation in the tolerance of hybrid poplar (Populus deltoides Bartr. cv. Angulata × P. trichocarpa Torr. and Gray) to sulfur dioxide fumigation. Rooted stem cuttings of four hybrid poplar clones were exposed to 5 ppm sulfur dioxide for 0, 3, 6, 9, or 12 hours in controlled environment chambers. Multivariate analyses were made from the shoot growth measurements recorded for 4 weeks before and after fumigation and on the data of foliar injury induced by sulfur dioxide. The following factors were statistically significant in determining growth response and foliar injury: (1) genotype; (2) duration of treatment; and (3) interaction between genotype and hours of fumigation. All partial correlations between foliar injury and subsequent shoot growth were positive and significant. Sufficient genetic variation appears to exist in this Populus hybrid to encourage selection of clones tolerant to short-term exposures of high levels of sulfur dioxide.     

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.     

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.     

Particulate and Sulfur Dioxide Concentration Measurements in Patras,Greece

Abstract

The purpose of this study was to obtain a better assessment of the Patras, Greece, air quality, in terms of the primary pollutants total suspended particulates (TSPs) and sulfur dioxide (SO₂), because limited and short-duration measurements have been conducted in the past. Installation and operation of a mobile air monitoring station at two different locations in the Patras downtown area and one location in the outskirts of the city was undertaken and covered the periods July 1, 1994-January 30, 1995; March 18-August 23, 1995; and April 19-July 27, 1996, respectively. For both pollutants measured at each location, the monthly average concentrations and typical weekly variation of daily averages, as well as the diurnal variations and frequency concentration distributions in each month of the monitoring periods, were calculated and are presented in bar diagrams. The annual and winter period medians and the annual 98th percentile were also calculated and are compared with the limit and guide values provided by the European Economic Community Council Directive 80/779/EEC. In addition, comparison of SO₂ values is made with the limit values adopted by the more recent Directive 1999/30/EC. It was found that the TSP and SO₂ levels at all locations were very low and were lower than the levels found in Thessaloniki and Athens, Greece. An attempt to explain what had been measured is also undertaken. The data presented are considered essential for future reference and comparison purposes.     

The Relationship of Carbon Dioxide Emissions with Coal Rank and Sulfur Content

Carbon dioxide emissions, on an equivalent energy basis, were calculated for 504 North American coals to explore the effects of coal rank and sulfur content on CO₂ emissions. The data set included coals ranging in rank from lignite through low-volatile bituminous from 15 U.S. states and Alberta, Canada. Carbon dioxide emissions were calculated from the carbon content and gross calorific value of each coal. The lowest CO₂ emissions are calculated for the high-volatile bituminous coals (198 to 211 lbs CO₂/MMBtu) and the highest for lignites and subbituminous coals (209 to 224 lbs CO₂/MMBtu). The lower CO₂ emissions from the high-volatile bituminous coals result in part from their generally higher sulfur content. However, even at equivalent sulfur contents the high-volatile bituminous coals give lower CO₂ emissions than the lower-rank coals. On average, the lowerrank coals produce 5 percent more CO₂ upon combustion than the highvolatile bituminous coals, on the basis of gross calorific value. This difference increases to 9 percent on the basis of estimated net calorific value. The net calorific value is better indicator of power plant energy production than the gross calorific value. The difference in CO₂ emissions resulting from the use of high-volatile bituminous coals and lower-rank coals is of the same order of magnitude as reductions expected from near-term combustion efficiency improvements. These results are useful to those interested in current and future CO₂ emissions resulting from coal combustion.     

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.     

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.     

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.     

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.     

Variable Responses of Soybeans to Mixtures of Ozone and Sulfur Dioxide

Foliar injury and shoot fresh weight responses of soybeans (Glycine max L.) ‘Lee 68’ and ‘Dare’ exposed to mixtures of ozone (O₃) and sulfur dioxide (SO₂) were greater than additive (synergistic), less than additive (antagonistic), or additive. The result depended on the concentrations of O₃ and SO₂, the exposure duration, and the amount of injury caused by each gas singly. Synergism usually occurred when injury from O₃ or SO₂ singly was slight to moderate. Antagonism usually occurred when injury from either gas singly was severe. In many cases of antagonism, the injury and fresh weight effects of the mixture were less than those from SO₂ alone, suggesting that O₃ can sometimes protect soybeans from SO₂.     

Impact of Free Calcium Oxide Content of Fly Ash on Dust and Sulfur Dioxide Emissions in a Lignite-Fired Power Plant

Abstract

Emitted pollutants from the Agios Dimitrios lignite-fired power plant in northern Greece show a very strong linear correlation with the free calcium oxide content of the lignite ash. Dust (fly ash) emissions are positively correlated to free calcium oxide content, whereas sulfur dioxide (SO₂) emissions are negatively correlated. As a result, at present, the Agios Dimitrios Power Plant operates very strictly within the legislative limits on atmospheric particulate emission. In the present study, the factors to be considered in assessing the impact of lignite combustion on the environment are presented and evaluated statistically. The ash appears to have a remarkable SO₂ natural dry scrubbing capability when the free calcium oxide content ranges between 4 and 7%. Precipitator operating problems attributable to high ash resistivity can be overcome by injecting sulfur trioxide to reduce the ash resistivity, with, of course, a probable increase in operating costs.     

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.     

Effects of Sulfur Dioxide and Nitric Oxide on Mercury Oxidation and Reduction under Homogeneous Conditions

Abstract

This paper is particularly related to elemental mercury (Hg⁰) oxidation and divalent mercury (Hg²⁺) reduction under simulated flue gas conditions in the presence of nitric oxide (NO) and sulfur dioxide (SO₂). As a powerful oxidant and chlorinating reagent, Cl₂ has the potential for Hg oxidation. However, the detailed mechanism for the interactions, especially among chlorine (Cl)-containing species, SO₂, NO, as well as H₂O, remains ambiguous. Research described in this paper therefore focused on the impacts of SO₂ and NO on Hg⁰ oxidation and Hg²⁺ reduction with the intent of unraveling unrecognized interactions among Cl species, SO₂, and NO most importantly in the presence of H₂O. The experimental results demonstrated that SO₂ and NO had pronounced inhibitory effects on Hg⁰ oxidation at high temperatures when H₂O was also present in the gas blend. Such a demonstration was further confirmed by the reduction of Hg²⁺ back into its elemental form. Data revealed that SO₂ and NO were capable of promoting homogeneous reduction of Hg²⁺ to Hg⁰ with H₂O being present. However, the above inhibition or promotion disappeared under homogeneous conditions when H₂O was removed from the gas blend.     

Modification of Sulfur Dioxide Injury to Tobacco and Tomato by Varying Nitrogen and Sulfur Nutrition

The body of information presented in this paper is directed to plant scientists who are concerned with factors which modify the susceptibility of plants to air pollutants.

Tobacco and tomato plants grown in sand-solution culture with varying levels of nitrogen or sulfur were exposed to injurious levels of sulfur dioxide. Plants of both species which were deficient in either nutrient exhibited decreased susceptibility to the gas compared with plants grown at optimal levels of each nutrient. Foliage of these plants was also found to have increased stomatal resistance as measured by a porometer and decreased total sulfur accumulations. Plants grown at optimum levels of each nutrient showed increased susceptibility over that of the deficient plants. Stomatal resistance was lower and sulfur accumulation was greater than in the deficient plants. At the supra-optimal nitrogen and sulfur levels, there were differences in susceptibility. Over-abundant nitrogen appeared to decrease susceptibility whereas over-supplies of sulfur increased it.

The response of plants with deficient or optimal supplies of either nutrient might be explained by the effects of nutrition on stomatal activity and hence on ability to absorb SO₂S from the atmosphere, mineral deficiency being known to increase stomatal resistance, and mineral sufficiency, to decrease stomatal resistance by virtue of increased efficiency of water use. The difference in response between plants overfertilized with respect to nitrogen or sulfur is explained by the fact that sulfur is both nutrient and phytotoxicant at the same time. Having already been oyersupplied with sulfur by absorption from the nutrient substrate, the high-sulfur plants were unable to withstand additional sulfur accumulation from the atmosphere and hence were more severely injured.

Increased carbohydrate accumulation in the nitrogen- and sulfur-deficient plants might play an additional role in protection from SO2-injury.     

Nitrogen Dioxide Absorption and Sulfide Oxidation in Aqueous Sulfide

ABSTRACT

Rates of nitrogen dioxide (NO₂) absorption and sulfide oxidation were measured in a highly characterized stirred cell contactor at 55 °C, with O₂ present in the gas phase. The rate constant of the reaction between NO₂ and sul-fide at 55 °C was determined to be 26.4 x10⁵ M^-1sec^-1. A reaction mechanism was proposed that is consistent with the kinetic data. NO₂ absorption initiates sulfide oxidation in the presence of oxygen. The rate of sulfide oxidation increased with sulfide and oxygen concentration and with the rate of NO₂ absorption. Furthermore, thiosulfate was an effective inhibitor of sulfide oxidation.     

Ciliary Activity and Pulmonary Retention of Inhaled Dust In Rats Exposed to Sulfur Dioxide

While the ciliary activity in the airways of rats exposed to sulfur dioxide at low concentration has been studied repeatedly, the effects of chronic exposure to realistic levels of sulfur dioxide and particulates has not been determined. This paper describes the response of white albino rats to the inhalation of low concentrations of sulfur dioxide while exposed to relatively high concentrations of an inert dust. Test results indicate that no change is found in the ciliary activity or the relative number of dust cells in the alveolar structure of rats exposed to 1 ppm of sulfur dioxide and 1 mg/m³ of a graphite dust.     

Relating Summer Ambient Particulate Sulfur,Sulfur Dioxide,and Light Scattering to Gaseous Tracer Emissions from the MOHAVE Power Project

ABSTRACT

Project MOHAVE was initiated in 1992 to examine the role of emissions from the 1580 MW coal-fired MOHAVE Power Project (MPP) on haze at the Grand Canyon National Park (GCNP), located about 130 km north-northeast of the power plant. Statistical relationships were analyzed between summertime ambient concentrations of a gaseous perfluorocarbon tracer released from MPP and ambient SO₂, particulate sulfur, and light scattering to evaluate whether MPP's emissions could be transported to the GCNP and then impact haze levels there. Spatial analyses indicated that particulate sulfur levels were strongly correlated across the monitoring network, regardless of whether the monitoring stations were upwind or downwind of MPP. This indicates that particulate sulfur levels in this region were influenced by distant regional emission sources. A significant particulate sulfur contribution from a point source such as MPP would result in a non-uniform pattern downwind. There was no suggestion of this in the data.

Furthermore, correlations between the MPP tracer and ambient particulate sulfur and light scattering at locations in the park were virtually zero for averaging times ranging from 24 hr to 1 hr. Hour-by-hour MPP tracer levels and light scattering were individually examined, and still no positive correlations were detected. Finally, agreement between tracer and particulate sulfur did not improve as a function of meteorological regime, implying that, even during cloudy monsoon days when more rapid conversion of SO₂ to par-ticulate sulfur would be expected, there was no evidence for downwind particulate sulfur impacts. Despite the fact that MPP was a large source of SO₂ and tracer, neither time series nor correlation analyses were able to detect any meaningful relationship between MPP's SO₂ and tracer emission “signals” to particulate sulfur or light scattering.     

Measurements of Rural Sulfur Dioxide and Particle Sulfate: Analysis of CASTNet Data, 1987 through 1996

ABSTRACT

The Clean Air Status and Trends Network (CASTNet) was implemented by the U.S. Environmental Protection Agency (EPA) in 1991 in response to Title IX of the Clean Air Amendments of 1990, which mandated the deployment of a national ambient air monitoring network to track progress of the implementation of emission reduction programs in terms of deposition, air quality, and changes to affected ecosystems. CASTNet evolved from the National Dry Deposition Network (NDDN). CASTNet currently consists of 45 sites in the eastern United States and 28 sites in the West. Each site measures sulfur dioxide (SO₂), nitric acid (HNO₃), particle sulfate (SO₄ ⁼), particle nitrate (NO₃ ^- ), and ozone. Nineteen sites collect precipitation samples. NDDN/CASTNet uses a uniform set of site-selection criteria which provides the data user with consistent measures to compare each site. These criteria also ensure that, to the extent possible, CASTNet sites are located away from local emission sources.

This paper presents an analysis of SO₂ and SO₄ ⁼ concentration data collected from 1987 through 1996 at rural NDDN/CASTNet sites. Annual and seasonal variability is examined. Gradients of SO₂ and SO₄ ⁼ are discussed. The variability of the atmospheric mix of SO₂ and SO₄ ⁼ is explored spatially and seasonally. Data from CASTNet are also compared to SO₂ and SO₄ ⁼ data from concurrent monitoring studies in rural areas.     

Sulfur Dioxide Emissions and Market Effects under the Clean Air Act Acid Rain Program

ABSTRACT

The Clean Air Act Amendments of 1990 (CAAA90) established a national program to control sulfur dioxide (SO₂) emissions from electricity generation. CAAA90's market-based approach includes trading and banking of Soumissions allowances. We analyzed data describing electric utility SO₂ emissions in 1995, the first year of the program's Phase I, and market effects over the 1990-1995 period. Fuel switching and flue-gas desulfurization were the dominant means used in 1995 by targeted generators to reduce emissions to 51% of 1990 levels. Flue-gas desulfur-ization costs, emissions allowance prices, low-sulfur coal prices, and average sulfur contents of coals shipped to electric utilities declined over the 1990-1995 period. Projections indicate that 13-15 million allowances will have been banked during the program's Phase I, which ends in 1999, a quantity expected to last through the first decade of the program's stricter Phase II controls. In 1995, both allowance prices and SO₂ emissions were below pre-CAAA90 expectations. The reduction of SO₂ emissions beyond pre-CAAA90 expectations, combined with lower-than-expected allowance prices and declining compliance costs, can be viewed as a success for market-based environmental controls.