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.     

Sulfur Gas Emissions from Flue Gas Desulfurization Sludge Ponds

This paper presents initial measurement data on the emission of volatile, reduced sulfur-containing gases from flue gas desulfurization (FGD) storage ponds. Several different types of FGD stored sludges were studied including lime, limestone, and mixtures of fly ash and lime or limestone residues, some of which had been chemically stabilized. The volatile sulfur gas emissions were cryogenically concentrated and determined by wall-coated, open-tubular capillary column gas chromatography using a flame photometric detector. Hydrogen sulfide, carbonyl sulfide, dimethyl sulfide, carbon disulfide, and an unusual, unidentified sulfur-containing compound were found in the gaseous pond flux. Benzene, toluene, and α-pinene were also identified by gas chromatography-single ion monitoring mass spectrometry. The total reduced sulfur gas emission from a 100 acre pond approximated 2.0 kg day^?1 (as sulfur).     

Biogenic Sulfur Gas Emissions from Soils in Eastern and Southeastern United States

Data are presented for the first systematic measurements of biogenic sulfur gas flux from the major soil orders within the eastern and southeastern United States. Sulfur flux samples were collected and analyzed on-site during the fall of 1977, spring and summer of 1978 and summer of 1979. A total of 27 sampling locales in 17 states were examined. Eight additional sites were visited in 1980.

At some locales, two to four soils were examined, providing an even broader sampling of the soil orders. Three of the locales were revisited two or three times during the course of the study to establish the influence of seasonal climatology upon the measured emission rates and chemical composition of the sulfur flux mixtures.

The sulfur gas enhancement of sulfur-free sweep air passing through dynamic emission flux chambers placed over selected sampling areas was determined by combined cryogenic enrichment sampling and wall-coated, open tubular, capillary column, cryogenic gas chromatography (WCOT/GC) using a sulfur selective, flame photometric detector (FPD).

Sulfur gas mixtures varied with soil order, ambient temperature, insolation, soil moisture, cultivation, and vegetative cover. Statistical analyses indicated strong temperature and soil order relationships for sulfur emissions from soils.

Fluxes ranged from 0.001 g to 1940 g of total sulfur as S/m²/yr. The calculated mean annual sulfur flux, weighted by soil order, was 0.03 g S/m²/yr for the study land area, or 110,872 metric tons (mT). The estimated annual average sulfur flux increased from 65 mT per 6400 km² for the land grids in the northernmost east-west grid tier to an average 1800 mT for the land grids in the southern Florida grid tiers.

This systematic sampling of major soils provides a much broader data base for estimating biogenic sulfur flux than previously reported for isolated intertidal sites, and presents the first sulfur flux estimates for inland soils which make up approximately 93% of the land of the eastern United States.     

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.     

Control of Claus Plant Sulfur Compound Emissions

The body of information of this paper is directed to those individuals charged with selecting a process to control atmospheric sulfur emissions from Claus plants serving refineries, gas processing installations, and chemical plants. The TGT process developed by the French Petroleum Institute (IFP) is an extension of the Claus reaction itself in the liquid phase. Mixed H₂S and SO₂ in tail gas from Claus units is fed to a packed tower in which a solution of proprietary catalyst in a high BP polyglycol circulates countercurrent to the gas flow. The mixed gases react with the catalyst to form a complex, which in turn reacts with more gases to produce elemental sulfur. Reaction temperature keeps the sulfur above its melting point. Product accumulates in the boot of the tower and is drawn off continuously through a seal leg.

The IFP TGT process is simple in design and units have simple construction, characterized by use of low carbon steel and the use of very few pieces of equipment. Of all processes used today to take effluent sulfur values down to 1000 ppm SO₂ after incineration, the IFP TGT process requires the least capital investment and the lowest operating costs. Twenty-six full scale plants are operating or under design or construction: nine each in the U.S. and Japan, five in the U.S.S.R. and Poland, two in western Europe and one in Canada. Capacities of the Claus plants served range from 45 to 800 Lt/d sulfur.     

Modeling Analyses of the Effects of Changes in Nitrogen Oxides Emissions from the Electric Power Sector on Ozone Levels in the Eastern United States

Abstract

In this paper, we examine the changes in ambient ozone concentrations simulated by the Community Multiscale Air Quality (CMAQ) model for summer 2002 under three different nitrogen oxides (NO_x) emission scenarios. Two emission scenarios represent best estimates of 2002 and 2004 emissions; they allow assessment of the impact of the NO_x emissions reductions imposed on the utility sector by the NO_x State Implementation Plan (SIP) Call. The third scenario represents a hypothetical rendering of what NO_x emissions would have been in 2002 if no emission controls had been imposed on the utility sector. Examination of the modeled median and 95th percentile daily maximum 8-hr average ozone concentrations reveals that median ozone levels estimated for the 2004 emission scenario were less than those modeled for 2002 in the region most affected by the NO_x SIP Call. Comparison of the “no-control” with the “2002” scenario revealed that ozone concentrations would have been much higher in much of the eastern United States if the utility sector had not implemented NO_x emission controls; exceptions occurred in the immediate vicinity of major point sources where increased NO titration tends to lower ozone levels.     

Determination of Nitrogen Oxides in Auto Exhaust

A new procedure for determining nitrogen oxides in automobile exhaust has been developed. The new procedure was included in a Bureau of Mines comparative study that aimed at evaluating various widely used methods for determining NO_x in auto exhaust. The methods included in the evaluation study follow: (1) Static oxidation in tank (ST method). The method involves oxidation of NO in residence with O₂ in a stainless steel tank. (2) Bureau of Mines method (BM method). The method involves application of the ST procedure in exhaust samples from which the hydrocarbons have been removed by combustion over catalyst. (3) Chevron Research method (CR method), as described in the literature. (4) Phenoldisulfonic acid method (PDS method), as described in the literature. The principal objective of this study was to generate experimental evidence which would lead to defining an optimum procedure for converting NO, present in exhaust gas, into NO₂; this conversion is desired so that the total of NO + NO₂ can be determined quantitatively in the form of NO₂. In pursuing this objective, the procedures prescribed by the foregoing methods were comparatively tested. The results indicated that all four methods are subject to error, the extent of which depends on the conditions employed. The BM method was superior from the standpoint of accuracy because it was less affected by interferences due to hydrocarbon-NO₂ reactions.     

测量试样中的氮氧化物含量不确定度评定

以实际监测数据为例，详细描述测量试样中的NOx含量不确定度评定方法，包括不确定度源的分析，A类标准不确定度评定、B类标准不确定度评定、合成标准不确定度和扩展不确定度等，对不确定度的分量作了详尽的分析和计算。     

Alternative Strategies for Control of Sulfur Dioxide Emissions

Achievement of air quality goals now more than ever requires careful consideration of alternative control strategies in view of national concerns with energy and the economy. Three strategies which might be used by coal-fired steam electric plants to achieve ambient air quality standards for sulfur dioxide have been compared, and the analysis shows that the desired objective can be achieved using the intermittent control strategy with substantially less impact on the environment, less consumption of energy, and at a much lower economic cost than using either stack gas scrubbing or low-sulfur coal.     

Abatement of Sulfur Hexafluoride Emissions from the Semiconductor Manufacturing Process by Atmospheric-Pressure Plasmas

Abstract

Sulfur hexafluoride (SF₆) is an important gas for plasma etching processes in the semiconductor industry. SF₆ intensely absorbs infrared radiation and, consequently, aggravates global warming. This study investigates SF₆ abatement by nonthermal plasma technologies under atmospheric pressure. Two kinds of nonthermal plasma processes—dielectric barrier discharge (DBD) and combined plasma catalysis (CPC)—were employed and evaluated. Experimental results indicated that as much as 91% of SF₆ was removed with DBDs at 20 kV of applied voltage and 150 Hz of discharge frequency for the gas stream containing 300 ppm SF₆, 12% oxygen (O₂), and 40% argon (Ar), with nitrogen (N₂) as the carrier gas. Four additives, including Ar, O₂, ethylene (C₂H₄), and H₂O_(g), are effective in enhancing SF₆ abatement in the range of conditions studied. DBD achieves a higher SF₆ removal efficiency than does CPC at the same operation condition. But CPC achieves a higher electrical energy utilization compared with DBD. However, poisoning of catalysts by sulfur (S)-containing species needs further investigation. SF₆ is mainly converted to SOF₂,SO₂F₄, sulfur dioxide (SO₂), oxygen difluoride (OF₂), and fluoride (F₂). They do not cause global warming and can be captured by either wet scrubbing or adsorption. This study indicates that DBD and CPC are feasible control technologies for reducing SF₆ emissions.     

Environmental Appraisal-Particulate Matter,Oxides of Sulfur,and Sulfuric Acid

The role of particulate matter and oxides of sulfur in degradation of the atmospheric environment is discussed. The Federal Air Quality Criteria for these pollutants are analyzed for their conformance with the requirement of the Clean Air Act of 1967 that they reflect the latest scientific knowledge pertinent to the indication of their effects on health and welfare. Visibility reduction by suspended particulate matter is treated and the bases for the criteria issued in the documents “Air Quality Criteria for Particulate Matter” and “Air Quality Criteria for Sulfur Oxides” are examined. The reactions between particulate matter and gaseous pollutants are discussed, along with the Impact of particulate matter on modifications of weather processes. Local effects, such as precipitation, are considered. The relationship between pollution by particulate matter and cloud formation is discussed, as are persistence of fog and the observation that certain sources of particulate pollution are also sources of ice nuclei.     

Review of Recent Studies of Sulfur Oxides as Air Pollutants

The current literature on the role of sulfur dioxide in air pollution     

Catalytic Reduction of Nitrogen Oxides in Automobile Exhaust

The catalytic reduction of oxides of nitrogen from leaded automobile exhaust has been demonstrated to be technically feasible. These studies made with copper-containing catalysts are based upon the reducing nature of exhaust caused by the carbon monoxide present. The reaction involves 2 CO + 2 NO → + N₂ + CO₂ + 178.5 Kcal.     

Considerations in Setting Standards for Oxides of Nitrogen

Since 1959 the California Department of Public Health has held responsibility for setting standards for ambient air quality and for motor vehicle emissions. The need for standards for oxides of nitrogen involves consideration both of direct effects and effects resulting from participation in photochemical smog reactions. This paper discusses the various effects of concern and describes the department’s program for establishing air quality standards which will become the basis for vehicle emission standards and serve as guides for control of other sources of oxides of nitrogen.     

Nitrogen Oxide Emissions of Boilers in Finland

This article discusses nitrogen oxide emissions from various types of boilers in Finland. The boilers have been classified into 61 classes according to their size, combustion technique, and main fuel. A specific emission coefficient (ng NO₂/J = mg NO₂/MJ) for each class has been determined, based on literature surveys and actual measurements. The total NO_X emission has been calculated for each class, using the emission coefficient and energy statistics. The effect of various techniques for emission reduction has also been investigated. The development of NO_X emissions has been estimated for both the case where no preventing actions have been taken and for four defined cases where alternative reduction measures are assumed

The total NO_X emission from energy production in Finland was 107,000 tons NO₂ in 1987. Seventy-five percent of this amount originated in boilers larger than 1 MWfuel effect (input effect), and the rest in smaller boilers and industrial processes. The most important boiler classes from the NO_X emission’s point of view were coal-fired boilers, with an emission of approximately 38,000 tons NO₂, peat-fired boilers and boilers fired with a mixture of fuels, emitting approximately 12,000 tons NO₂ each.

By 2005, the total NO_X emission from energy production would increase 50 percent to approximately 160,000 tons if left uncontrolled. The emission level would be 140,000 tons if primary reduction techniques are applied, and 110,000 tons NO₂, if catalytic NO_X reduction devices are installed in boilers larger than 300 MW.     

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.     

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.     

Formation of Oxides of Nitrogen in Pulverized Coal Combustion

Nitrogen oxides are a potential atmospheric pollutant. Their formation and decomposition were studied in an experimental pulverized-coal-fired furnace. The concentration of nitrogen oxides (NO_x) was a maximum in the combustion zone and decreased as the combustion gas cooled. At a coal burning rate of 2 Ib/hr and 22% excess air, reduction of nitrogen oxides was obtained by selective secondary-air distribution. With 105% cf the stoichiometric air fed to the coal-combustion zone and 17% additional air fed just beyond the flame front, 62% reduction of NO_x occurred with good combustion efficiency. Lowering the quantity of excess air lowered the NO_x concentration, but at the expense of combustion efficiency. When 22% excess air was fed to the primary combustion zone, NO_x concentration in the effluent was 550 ppm and carbon in the fly ash 2.0%. With 5% excess air, the NO_x concentration fell to 210 ppm and carbon in the fly ash rose to 13.8%. With stoichiometric combustion the NO_x was 105 ppm a reduction of 81 %, and the carbon was 42.3%. Recirculation of combustion gas was not an effective means of lowering NO_x formation.