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.     

Simultaneous removal of sulfur dioxide and polycyclic aromatic hydrocarbons from incineration flue gas using activated carbon fibers

Incineration flue gas contains polycyclic aromatic hydrocarbons (PAHs) and sulfur dioxide (SO₂). The effects of SO₂ concentration (0, 350, 750, and 1000 ppm), reaction temperature (160, 200, and 280 °C), and the type of activated carbon fibers (ACFs) on the removal of SO₂ and PAHs by ACFs were examined in this study. A fluidized bed incinerator was used to simulate practical incineration flue gas. It was found that the presence of SO₂ in the incineration flue gas could drastically decrease removal of PAHs because of competitive adsorption. The effect of rise in the reaction temperature from 160 to 280 °C on removal of PAHs was greater than that on SO₂ removal at an SO₂ concentration of 750 ppm. Among the three ACFs studied, ACF-B, with the highest microporous volume, highest O content, and the tightest structure, was the best adsorbent for removing SO₂ and PAHs when these gases coexisted in the incineration flue gas.

ImplicationsSimultaneous adsorption of sulfur dioxide (SO₂) and polycyclic aromatic hydrocarbons (PAHs) emitted from incineration flue gas onto activated carbon fibers (ACFs) meant to devise a new technique showed that the presence of SO₂ in the incineration flue gas leads to a drastic decrease in removal of PAHs because of competitive adsorption. Reaction temperature had a greater influence on PAHs removal than on SO₂ removal. ACF-B, with the highest microporous volume, highest O content, and tightest structure among the three studied ACFs, was found to be the best adsorbent for removing SO₂ and PAHs.     

Comparison of Fine Particles and the Relationship between Particle Variations and Meteorology at an Urban Site and a Remote Site in the Eastern United States

Abstract

This study compared the variations in the mass of certain particles at an urban site, Washington, DC, and at a remote site, Shenandoah National Park, VA, in the eastern United States. Seven years (1991-1997) of Interagency Monitoring of Protected Visual Environments (IMPROVE) fine particulate matter (PM_2.5), PM₁₀, coarse fraction, SO₄ ^2?, and total sulfur data were used for this study together with available meteorology/climatology data. Various statistical modeling and analysis procedures, including time series analysis, factor analysis, and regression modeling, were employed. Time series of the constituents were divided into four terms: the long-term mean, the intra-annual perturbation, the interannual perturbation, and the synoptic perturbation. PM_2.5 at the two sites made up ~72% of the total mass for PM₁₀, and the coarse fraction made up the remaining 28%, on average. Thirty-one percent of the PM_2.5 at the DC site and 42% at the Shenandoah site was SO₄ ^2?, based on average data for the entire period. At the DC site, the two main contributors to the constituent mass were the long-term mean and the synoptic perturbation terms, and at the Shenandoah site, they were the long-term mean and the intra-annual perturbation terms. This suggested that the constituent mass at the two sites was affected by very different processes. The terms that provided the principal contribution to the constituent mass at the two sites were studied in detail.

At the DC site, dew point trends, a climate variable, were the primary driver of the 7-year trends for PM_2.5, PM₁₀, the coarse fraction, and total sulfur, and SO₂ emission trends were the primary driver of the trends for SO₄ ^2?. SO₂ emission trends influenced the trends for PM_2.5 and total sulfur, appearing as the second term in the model, but only parameters dealing with climate trends had significant effects on the trends for PM₁₀ and the coarse fraction. At the Shenandoah site, only parameters dealing with climate trends affected long-term particle trends.     

A Device for Measuring Volatile Organic-Carbon Emissions from Cooling-Tower Water

A manual method for measuring reduced sulfur compounds in kraft pulp mill and sulfur recovery plant emissions was evaluated. The method involves removing SO₂ from the gas stream (if present) with a citric acid-potassium citrate buffer that passes reduced sulfur compounds; thermal oxidation of all reduced sulfur compounds to SO₂; collection of the SO₂ in H₂O₂; and a titrimetric analysis of the H₂O₂ for SO₄ ^2?. A heated filter removes alkaline particulate matter that would produce a negative interference if absorbed by the buffer. When used at kraft pulp mills, the method agrees closely with Reference Method 16, provided that nonregulated reduced sulfur compounds, such as carbonyl sulfide, are not present in the emissions. At sulfur recovery plants, nonregulated reduced sulfur compounds, such as thiophene, are likely to be present in the emissions and will produce a positive bias in the results obtained with this method. The precision of the method ranges from 1 to 7 percent relative standard deviation.     

Photochemical oxidation and dispersion of gaseous sulfur compounds from natural and anthropogenic sources around a coastal location

The photochemical oxidation and dispersion of reduced sulfur compounds (RSCs: H₂S, CH₃SH, DMS, CS₂, and DMDS) emitted from anthropogenic (A) and natural (N) sources were evaluated based on a numerical modeling approach. The anthropogenic emission concentrations of RSCs were measured from several sampling sites at the Donghae landfill (D-LF) (i.e., source type A) in South Korea during a series of field campaigns (May through December 2004). The emissions of natural RSCs in a coastal study area near the D-LF (i.e., source type N) were estimated from sea surface DMS concentrations and transfer velocity during the same study period. These emission data were then used as input to the CALPUFF dispersion model, revised with 34 chemical reactions for RSCs. A significant fraction of sulfur dioxide (SO₂) was produced photochemically during the summer (about 34% of total SO₂ concentrations) followed by fall (21%), spring (15%), and winter (5%). Photochemical production of SO₂ was dominated by H₂S (about 55% of total contributions) and DMS (24%). The largest impact of RSCs from source type A on SO₂ concentrations occurred around the D-LF during summer. The total SO₂ concentrations produced from source type N around the D-LF during the summer (a mean SO₂ concentration of 7.4 ppbv) were significantly higher than those (≤0.3 ppbv) during the other seasons. This may be because of the high RSC and SO₂ emissions and their photochemistry along with the wind convergence.     

Source and Budget of Sulfate in Precipitation From Central Alberta,Canada

Rain, hail, and snow samples collected in central Alberta have been analyzed for sulfate and chloride content using a conductometric titration method. The mean values of sulfate concentration in rain and hail collected in the region of sulfur extraction gas plants were 2.7 mg/l and 2.9 mg/l respectively. The mean value of the sulfate content of a large number of hail samples collected from one severe storm well removed from a major SO₂ source was only 0.6 mg/l. Several snow samples collected in Alberta and southern British Columbia had a mean sulfate content of less than 0.5 mg/l. These results are discussed in terms of the efficiency with which SO₂ is removed from the atmosphere by the different precipitation processes. The results strongly suggest that most of the sulfate found in central Alberta precipitation is of local industrial origin.

By comparing the sulfate deposition in precipitation around one isolated gas plant with the known SO₂ emission rate, a local atmospheric sulfur budget is derived. This budget indicates that the summertime convective storms are a very efficient mechanism for removing the SO₂ from the atmosphere, with between 32 and 46% of the sulfur emitted as SO₂ arriving at the ground as sulfate sulfur within a radius of 25 miles of the source. In contrast snow is a very inefficient removal mechanism, since in winter less than 2% of the sulfur emission is deposited in the snowfall near the source.     

A simulation of sulfur wet deposition and its dependence on the inflow of sulfur species to storms

Numerical precipitation scavenging models are used to investigate the relationship between the inflow concentrations of sulfur species to precipitation systems and the resulting sulfur wet deposition. Simulations have been made for summer and winter seasons using concentration ranges of SO₂, aerosol SO₄²⁻, H₂O₂ and O₃ appropriate for the eastern U.S. summer simulations use one-dimensional timedependent convective cloud and scavenging models; winter simulations use two-dimensional steady-state warm-frontal models. Sulfur scavenging mechanisms include nucleation scavenging of aerosol, aqueous reactions of H₂O₂, O₃ and HCHO with S(IV), and nonreactive S(IV) scavenging. Over the wide range of conditions that have been examined, the relation between sulfur inflow and sulfur wet deposition varies from nearly linear to strongly nonlinear. The degree of nonlinearity is most affected by aerosol SO₄²⁻ levels and relative levels of SO₂ vs H₂O₂. Higher aerosol SO₄²⁻ levels (as found in summer) produce a more linear relation. The greatest nonlinearity occurs when SO₂ exceeds H₂O₂. Winter simulations show more nonlinearity than summer simulations.     

Influence of ozone, relative humidity, and flow rate on the deposition and oxidation of sulfur dioxide on yellow sand

To evaluate the influences of O₃, relative humidity (RH), and flow rate on the reaction between yellow sand and SO₂, the SO₂ deposition velocity and the oxidation state of sulfur were investigated by means of exposure experiments in a cylindrical flow reactor. Early in the reaction, the deposition velocity was not influenced by the RH or the presence of O₃; as the reaction progressed, however, the deposition velocity increased in the presence of O₃ and at high humidity. The oxidation of sulfur from S(IV) to S(VI) was also enhanced under these conditions. The amount of sulfur oxidation was positively correlated with the amount of deposited O₃. Furthermore, the SO₂ deposition velocity increased with increasing flow rate. However, changes in the flow rate had no noticeable effect on the amount of SO₂ oxidation.     

Gaseous Sulfur Pollutants from Urban and Natural Sources

Major aspects of the circulation through the atmospheric environment of sulfur pollutants have been estimated, including source magnitudes, residual atmospheric concentrations, and scavenging processes. The compounds considered include SO₂ and H₂S, as well as sulfates. One-third of the sulfur reaching the atmosphere comes from pollutant sources, mainly as SO₂. Within the atmosphere there is a net transfer of sulfur from land to ocean areas. Pollutant sources annually amount to 73 × 10⁶ tons as sulfur while natural sources amount to 142 × 10⁶ tons, mainly as H₂S and sulfate sea spray. More than two thirds of the natural and pollutant sulfur emissions occur in the northern hemisphere. When only pollutant emissions are considered, 93 per cent occur in the northern hemisphere.     

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.     

Compositions of Particles from Selected Sources in Philadelphia for Receptor Modeling Applications

As a part of a receptor model study of the Philadelphia, PA atmosphere, particulate samples were collected from seven air pollution sources in the area: two oil-fired power plants, a coal-fired power plant, a fluidized catalytic cracker, a refuse incinerator, a secondary aluminum smelter and an antimony ore roaster. Samples were collected In two size fractions with a dilution source sampler connected to a modified dichotomous sampler. Masses of collected material were determined gravlmetrlcally. Samples were analyzed for elements by x-ray fluorescence followed by Instrumental neutron activation analysis of some samples. Other samples were analyzed by chemical methods for volatile and nonvolatile carbon, SO₄ ^2? and NH₄ ⁺. Data are presented for up to 46 elements and species on fine (<2.5-μm aerodynamic equivalent diameter) and coarse (2.5 μm < diam < 7-10 μm) particles from each source. Although the data were collected for use in Philadelphia, they should be of value for receptor modeling of other areas having similar sources. The most unexpected results were the large amounts of rare earth elements on particles from the catalytic cracker (e.g., 0.31 percent La In fine fraction) and the oil-fired power plants (120 and 420 ppm La in fine fraction). Substantial amounts of primary SO₄ ^2? are released from the oil-fired plants, the SO₄ ^2? concentrations accounting for 40-45 percent of the fine particulate mass.     

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.     

Removal of SO2 From Flue Gases Using Carbon at Elevated Temperatures

The interaction of a typical flue gas with active charcoal and bituminous coal char at temperatures between 600 and 800°C and atmospheric pressure has been studied. The SO₂ in the flue gas interacts with the carbon to form primarily H₂S, COS, and a carbon-sulfur surface complex. H₂S and COS break through the carbon bed much in advance of SO₂. At 800°C, sulfur retention on the bed exceeds at least 11% before SO₂ breakthrough occurs. The reaction of H₂S and COS with O₂ over active charcoal at 100–140°C to produce sulfur, which deposits on the carbon, has also been studied and found to be feasible. As a result of this study, a new process is outlined for the removal of SO₂ from flue gas, with the ultimate conversion     

Transport and transformation of sulfur compounds over East Asia during the TRACE-P and ACE-Asia campaigns

On the basis of the recently estimated emission inventory for East Asia with a resolution of 1×1°, the transport and chemical transformation of sulfur compounds over East Asia during the period of 22 February through 4 May 2001 was investigated by using the Models-3 Community Multi-scale Air Quality (CMAQ) modeling system with meteorological fields calculated by the regional atmospheric modeling system (RAMS). For evaluating the model performance simulated concentrations of sulfur dioxide (SO₂) and aerosol sulfate (SO₄²⁻) were compared with the observations on the ground level at four remote sites in Japan and on board aircraft and vessel during the transport and chemical evolution over the Pacific and Asian Pacific regional aerosol characterization experiment field campaigns, and it was found that the model reproduces many of the important features in the observations, including horizontal and vertical gradients. The SO₂ and SO₄²⁻ concentrations show pronounced variations in time and space, with SO₂ and SO₄²⁻ behaving differently due to the interplay of chemical conversion, removal and transport processes. Analysis of model results shows that emission was the dominant term in regulating the SO₂ spatial distribution, while conversion of SO₂ to SO₄²⁻ in the gas phase and the aqueous phase and wet removal were the primary factors that controlled SO₄²⁻ amounts. The gas phase and the aqueous phase have the same importance in oxidizing SO₂, and about 42% sulfur compounds (25% in SO₂) emitted in the model domain was transported out, while about 57% (35% by wet removal processes) was deposited in the domain during the study period.     

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.     

The retention of SO2 by nylon filters

The retention of SO₂ by nylon filters was determined in laboratory and field studies. Less than 4% of the SO₂ was retained by nylon filters manufactured before May 1984. A change in filter material at that time appears to have greatly increased the retention of SO₂ to values as high as 70%. Therefore, the SO₂ retention by a nylon filter preceding an SO₂ collection filter must be taken into account. Some organic sulfur compounds may also be retained on nylon filters.     

Stainless Steel Anti-Smog Mufflers—Cut Air Pollution

An automatic process gas chromatograph has been developed for use on the recovery furnace stack of a Kraft pulp mill. The instrument analyzes for widely varying concentrations of H₂S, SO₂, CH₃SH and higher order sulfur compounds. It is insensitive to the fixed gases and water vapor, and performs its analysis in approximately ten minutes. The instrument features a microcoulometric detector giving it sensitivity to H₂S as low as 0.1 ppm, and SO₂ and CH₃SH as low as 0.5 ppm. The major limit to even higher sensitivity at this stage of development lies with two problems: the background noise level in the detector and the sulfur compound absorption in the Porapak Q chromatograph column. At the reported sensitivity, a 40-ml gas sample was used. The instrument also contains a data analysis system supplementary to the usual strip chart recorder. This system is made up of a digital voltmeter, a digital translator, and a teletype and hence allows the transfer of the output data to a digital computer for processing. The processed data are usually presented in the form of ppm quantities of the component gases in the stack gas. The instrument has worked successfully on small furnace effluent for periods of 25 hr but has not been tried on recovery furnace stacks. It has also run on prepared samples for periods of up to seven days with no maintenance or attendance necessary.     

The formation of dithionate during the iron(III)-catalysed autoxidation of sulfur(IV)-oxides

The iron(III)-catalyzed autoxidation of sulfur(IV)-oxides results in the formation of two different oxidation products of sulfur(IV): dithionate, S₂O₆²⁻, and sulfate, SO₄²⁻. The yield of these reaction products depends on the experimental conditions. Under the studied conditions ([Fe(III)] : [SIV)] = 1:10, pH = 2–4) dithionate is the minor reaction product. The formation of dithionate is influenced by the initial pH but not by the initial O₂ concentration. The presence of CO²⁺, Mn²⁺, and Ni²⁺ have no influence on the yield of dithionate, whereas in the presence of Cr³⁺ less and, in the presence of Cu²⁺, no dithionate is formed.     

Spatial variability of sulfur dioxide and sulfate over complex terrain in East Tennessee,USA

In 2004 and 2005, the East Tennessee Ozone Study (ETOS) enhanced its regional measurement program with annular denuder systems to quantify sulfur dioxide (SO₂) and PM_2.5 sulfate (SO₄^2?) at five sampling sites that were representative of the complex terrain and physiographic features of East Tennessee. Intersite spatial variability was more defined for SO₂ than for SO₄^2?, which showed a fairly uniform structure in both daytime and nighttime measurements. Pollution roses indicated that two sites may have been influenced by the proximity of SO₂ emission sources. The data suggest that SO₂ is affected by nearby sources in the study area while the sources of SO₄^2? are regionally distributed.     

Retention of sulfur dioxide by nylon filters

Based on laboratory studies, recovery efficiencies of sulfur dioxide (SO₂) were determined for nylon filters. The nylon filters used in these experiments were found to retain SO₂. A relatively uniform amount (1.7%) was recoverable from each nylon filter, independent of relative humidity. An appreciable portion of SO₂ was unrecoverable, and this increased from 5 to 16% as the RH increased from 28 to 49%. This unrecoverable SO₂ may account for previous reports of a low bias for SO₂ determinations employing filter packs using nylon filters. Additional characterization of nylon filters is recommended prior to their future deployment as an integrative sampling medium for ambient air.