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.     

The Fate and Behavior of Mercury in Coal-Fired Power Plants

Abstract

For the past 22 years in the Netherlands, the behavior of Hg in coal-fired power plants has been studied extensively. Coal from all over the world is fired in Dutch power stations. First, the Hg concentrations in these coals were measured. Second, the fate of the Hg during combustion was established by performing mass balance studies. On average, 43 ± 30% of the Hg was present in the flue gases downstream of the electrostatic precipitator (ESP; dust collector). In individual cases, this figure can vary between 1 and 100%. Important parameters are the Cl content of the fuel and the flue gas temperature in the ESP. On average, 54 ± 24% of the gaseous Hg was removed in the wet flue-gas desulfurization (FGD) systems, which are present at all Dutch coal-power stations. In individual cases, this removal can vary between 8% (outlier) and 72%.

On average, the fate of Hg entering the power station in the coal was as follows: <1% in the bottom ash, 49% in the pulverized fuel ash (ash collected in the ESP), 16.6% in the FGD gypsum, 9% in the sludge of the wastewater treatment plant, 0.04% in the effluent of the wastewater treatment plant, 0.07% in fly dust (leaving the stack), and 25% as gaseous Hg in the flue gases and emitted into the air. The distribution of Hg over the streams leaving the FGD depends strongly on the installation. On average, 75% of the Hg was removed, and the final concentration of Hg in the emitted flue gases of the Dutch power stations was only ~3 μg/m_STP ³ at 6% O₂. During co-combustion with biomass, the removal of Hg was similar to that during 100% coal firing.

Speciation of Hg is a very important factor. An oxidized form (HgCl₂) favors a high degree of removal. The conversion from Hg⁰ to HgCl₂ is positively correlated with the Cl content of the fuel. A catalytic DENOX (SCR) favors the formation of oxidized Hg, and, in combination with a wet FGD, the total removal can be as high as 90%.     

A Study of Primary Sulfate Emissions From a Coal-Fired Boiler with FGD

A study was carried out to investigate the emissions of SO₂ and primary sulfate materials (H₂SO₄ and inorganic particulate matter) from a boiler burning fossil fuel and using a wet-limestone scrubber for SO₂ removal. Experiments were designed to assess the scrubbing efficiency for SO₂ and sulfate, as well as the potential for scrubber liquor reentrainment. The boiler studied was an 820 MW cyclone-fired unit equipped with a wet, limestone scrubber, consisting of eight two-stage venturi-absorber modules designed to treat a flue gas flow rate of 2,760,000 acfm. The boiler fuel was a low-grade sub-bituminous coal with ash and sulfur contents of 25 and 5%, respectively. Multiple-sampling methods were employed concurrently on the inlet and outlet of a candidate absorber module to measure SO₂, total water-soluble sulfate, and free H₂SO₄. Samples were collected during three field experiments from September 1977 through April 1978. The average SO₂ scrubbing efficiency was 76% and was observed to decrease over the 5 day operation/maintenance cycle of the module. The total water-soluble sulfate input to the scrubber amounted to approximately 1% of the total sulfur oxides and was composed of a 5:1 ratio of H₂SO₄ to particulate sulfate. The total sulfate scrubbing efficiency, averaging about 29%, was invariant with respect to SO₂ removal. The sulfate emissions measured in the scrubber exit gas consisted of about 85 % H₂SO₄ as a fine aerosol. Mass emissions of acid and particulate sulfate were calculated as 1730 Ib/hr and 305 Ib/hr, respectively.     

Quantification of Hourly Variability in NOx Emissions for Baseload Coal-Fired Power Plants

Abstract

The objectives of this paper are to (1) quantify variability in hourly utility oxides of nitrogen (NO_x) emission factors, activity factors, and total emissions; (2) investigate the autocorrelation structure and evaluate cyclic effects at short and long scales of the time series of total hourly emissions; (3) compare emissions for the ozone (O₃) season versus the entire year to identify seasonal differences, if any; and (4) evaluate interannual variability. Continuous emissions monitoring data were analyzed for 1995 and 1998 for 32 units from nine baseload power plants in the Charlotte, NC, airshed. Unit emissions have a strong 24-hr cycle attributable primarily to the capacity factor. Typical ranges of the coefficient of variation for emissions at a given hour of the day were from 0.2 to 0.45. Little difference was found when comparing weekend emissions with the entire week or when comparing the O₃ season with the entire year. There were substantial differences in the mean and standard deviation of emissions when comparing 1995 and 1998 data, indicative of the effect of retrofits of control technology during the intervening time. The wide range of variability and its autocorrelation should be accounted for when developing probabilistic utility emission inventories for analysis of near-term future episodes.     

Mercury Mass Balances: A Case Study of Two North Dakota Power Plants

ABSTRACT

The Energy & Environmental Research Center (EERC) conducted a mercury-sampling program to provide data on the quantity and forms of Hg emitted and on the Hg removal efficiency of the existing air pollution control devices at two North Dakota power plants—Milton R. Young Station and Coal Creek Station. Minnkota Power Cooperative, Great River Energy, the North Dakota Industrial Commission, and EPRI funded the project. The primary objective was to obtain accurate measurements of Hg released from each plant, as verified by a material balance. A secondary objective was to evaluate the ability of a mercury continuous emission monitor (CEM) to measure total Hg at the stack.

At both plants, speciated Hg measurements were made at the inlets and outlets of both the electrostatic precipi-tators (ESPs) and the flue gas desulfurization (FGD) systems. A Semtech Hg 2000 (Semtech Metallurgy AB) mercury CEM was used to measure the total Hg emissions at the stack in real time. Using these measurements and plant data, the measured Hg concentrations in the coal, FGD slurries, and ESP ash, a Hg mass flow rate was calculated at each sampling location. Excellent Hg mass balances were obtained (±15%). It was also found that the Hg was mostly in the elemental phase (~90%), and the small amount of oxidized Hg that was generated was removed by the FGD systems.

Insignificant amounts of particulate-bound Hg were measured at both plants. However, 10-20% of the elemental Hg measured prior to the ESP was converted to oxidized Hg across the ESP. The data show that, at these facilities, almost all of the Hg generated is being emitted into the atmosphere as elemental Hg. Local or regional deposition of the Hg emitted from these plants is not a concern. However, the Hg does become part of the global Hg burden in the atmosphere. Also, the evidence appears to indicate that elemental Hg is more difficult to remove from flue gas than oxidized Hg is.     

The Epa Program to Assess the Public Health Significance of Diesel Emissions

The U.S. Environmental Protection Agency's program to assess the public health significance of diesel emissions is described. The reasons for the EPA concern over diesel exhaust products are discussed. Some results of EPA research efforts over the last nine months are summarized and preliminary conclusions are drawn. Finally, the planned future health experiments which will hopefully fill some remaining gaps in our knowledge are identified.     

Validation of Three New Methods for Determination of Metal Emissions Using a Modified Environmental Protection Agency Method 301

Abstract

Three new methods applicable to the determination of hazardous metal concentrations in stationary source emissions were developed and evaluated for use in U.S. Environmental Protection Agency (EPA) compliance applications. Two of the three independent methods, a continuous emissions monitor-based method (Xact) and an X-ray-based filter method (XFM), are used to measure metal emissions. The third method involves a quantitative aerosol generator (QAG), which produces a reference aerosol used to evaluate the measurement methods. A modification of EPA Method 301 was used to validate the three methods for As, Cd, Cr, Pb, and Hg, representing three hazardous waste combustor Maximum Achievable Control Technology (MACT) metal categories (low volatile, semivolatile, and volatile). The modified procedure tested the methods using more stringent criteria than EPA Method 301; these criteria included accuracy, precision, and linearity. The aerosol generation method was evaluated in the laboratory by comparing actual with theoretical aerosol concentrations. The measurement methods were evaluated at a hazardous waste combustor (HWC) by comparing measured with reference aerosol concentrations. The QAG, Xact, and XFM met the modified Method 301 validation criteria. All three of the methods demonstrated precisions and accuracies on the order of 5%. In addition, correlation coefficients for each method were on the order of 0.99, confirming the methods’ linear response and high precision over a wide range of concentrations. The measurement methods should be applicable to emissions from a wide range of sources, and the reference aerosol generator should be applicable to additional analytes. EPA recently approved an alternative monitoring petition for an HWC at Eli Lilly’s Tippecanoe site in Lafayette, IN, in which the Xact is used for demonstrating compliance with the HWC MACT metal emissions (low volatile, semivolatile, and volatile). The QAG reference aerosol generator was approved as a method for providing a quantitative reference aerosol, which is required for certification and continuing quality assurance of the Xact.     

Airborne Emissions of Mercury from Municipal Solid Waste. II: Potential Losses of Airborne Mercury before Landfill

Abstract

Waste distribution and compaction at the working face of municipal waste landfills releases mercury vapor (Hg⁰) to the atmosphere, as does the flaring of landfill gas. Waste storage and processing before its addition to the landfill also has the potential to release Hg⁰ to the air if it is initially present or formed by chemical reduction of Hg^II to Hg⁰ within collected waste. We measured the release of Hg vapor to the atmosphere during dumpster and transfer station activities and waste storage before landfilling at a municipal landfill operation in central Florida. We also quantified the potential contribution of specific Hg-bearing wastes, including mercury (Hg) thermometers and fluorescent bulbs, and searched for primary Hg sources in sorted wastes at three different landfills. Surprisingly large fluxes were estimated for Hg losses at transfer facilities (～100 mg/hr) and from dumpsters in the field (～30 mg/hr for 1,000 dumpsters), suggesting that Hg emissions occurring before landfilling may constitute a significant fraction of the total emission from the disposal/landfill cycle and a need for more measurements on these sources. Reducing conditions of landfill burial were obviously not needed to generate strong Hg⁰ signals, indicating that much of the Hg was already present in a metallic (Hg⁰) form. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. Broken fluorescent bulbs and thermometers in dumpsters emitted Hg⁰ at 10 to >100 μg/hr and continued to act as near constant sources for several days.     

Airborne Emissions of Mercury from Municipal Solid Waste. I: New Measurements from Six Operating Landfills in Florida

Abstract

Mercury-bearing material enters municipal landfills from a wide array of sources, including fluorescent lights, batteries, electrical switches, thermometers, and general waste; however, the fate of mercury (Hg) in landfills has not been widely studied. Using automated flux chambers and downwind atmospheric sampling, we quantified the primary pathways of Hg vapor releases to the atmosphere at six municipal landfill operations in Florida. These pathways included landfill gas (LFG) releases from active vent systems, passive emissions from landfill surface covers, and emissions from daily activities at each working face (WF). We spiked the WF at two sites with known Hg sources; these were readily detected downwind, and were used to test our emission modeling approaches. Gaseous elemental mercury (Hg⁰) was released to the atmosphere at readily detectable rates from all sources measured; rates ranged from ～1–10 ng m^?2 hr^?1 over aged landfill cover, from ～8–20 mg/hr from LFG flares (LFG included Hg⁰ at μg/m³ concentrations), and from ～200–400 mg/hr at the WF. These fluxes exceed our earlier published estimates. Attempts to identify specific Hg sources in excavated and sorted waste indicated few readily identifiable sources; because of effective mixing and diffusion of Hg⁰, the entire waste mass acts as a source. We estimate that atmospheric Hg releases from municipal landfill operations in the state of Florida are on the order of 10–50 kg/yr, substantially larger than our original estimates, but still a small fraction of current overall anthropogenic losses.     

Mercury Concentration in the Atmosphere in Chicago A New Ultrasensitive Method Employing Amalgamation

During the past two years, the Chicago Department of Environmental Control chemistry laboratory has developed a prototype sensor for measuring low levels of mercury found in the free or ambient atmosphere. Earlier studies of mercury in the Chicago area postulated that most of the mercury in the atmosphere should condense onto particulates and be collectable on filters. The results of the work presented here show that this may not occur. Analysis of composites of Chicago high volume particulate filters results in an average of 4 nanograms/m³ (range 2-10 nanograms/m³). This compared with a typical average of elemental mercury measurements of 22 nanograms/m³ (range 5-60 nanograms/m³). Thus, it is obvious that particulate borne mercury, at least as analyzed from a high volume filter paper, is not as significant as the total or elemental mercury existing in the metropolitan area. A direct method for collecting mercury and measuring in a flameless atomic absorption unit yields very good results.     

A Simplified Technique Used to Evaluate Atmospheric Dispersion of Emissions from Large Power Plants

A simplified method which is used by the Tennessee Valley Authority to estimate ambient concentrations of atmospheric emissions from its large power plants is presented. The technique requires the use of three nomogrdms for the rapid graphic solution of three dispersion models—coning, inversion breakup, and trapping. A discussion of the meteorological conditions that are associated with these dispersion models, supporting appendices, and a worked example are also presented.     

A Study of Wood Stove Particulate Emissions

Particulate emission factors for two wood stove models have been determined for two types of fuel and a range of operating conditions. The emission factors range from 1 g/kg (fuel) to 24 g/kg. A model is presented which represents the emission factor as a simple function of the ratio of fuel load to combustion rate, or the length of time between refueling. This model is felt to be appropriate for evaluating the impact of wood-based residential space heating on ambient air concentrations of particulate matter If certain assumptions can be made about stove operating conditions. An application of the emission factor model to a typical community suggests that the contribution of wood stoves to ambient particulate levels might reach 100 μg/m³ if the entire heating load were carried by wood.

Preliminary analyses of the particulate matter Indicate that benzene extractables range from 42% of the total particulate mass at short refuel times to 67% at longer refuel times. About 45% of the mass of benzene extractables appeared in the neutral fraction of acid base extractions. Polycyclic aromatic hydrocarbons are expected to be included in this neutral fraction.     

A Simple Field Method to Determine Mercury Volatilization from Soils (3 pp)

Background Estimations of gaseous mercury volatilization from soils are often complex, stationary and expensive. Our objective was to develop a mobile and more simple, easy to handle and more cost-effective field method allowing rapid estimates of potential Hg emissions from soils. Methods. The study site is located in Germany, about 100 kilometers south-westerly of Berlin and influenced by the river Elbe and its tributary Saale river. The site is representative for a lot of other floodplain locations at the river Elbe and highly polluted with Hg and other heavy metals. For our study we developed a system consisting of a glass chamber gas, two gold traps, a battery operated pump and a gas meter. Adsorbed total gaseous mercury (TGM) in the gold traps was determined by use of atomic absorption spectrometry (AAS). Results and Discussion. In contrast to the common used flux chambers we designed a chamber without inlet and named it gas suck up chamber (GSC). TGM fluxes determined with the GSC showed a very close linear correlation (r = 0.993) between the TGM content in the gold traps and the corresponding pumped gas volume. The TGM adsorbed, increased proportional with increasing gas volume indicating homogenous concentrations of gaseous mercury in the soil air sucked. In contrast to the commonly used dynamic flux chamber with the aim of precisely measuring actual fluxes of Hg from a defined soil area, we focused on developing of a measurement system which will allow rapid estimates of potential Hg emissions of a site. Earlier research at the study site indicated a high potential for releasing volatile Hg from the soil to the atmosphere. Indeed, due to the high Hg content of the soil significant amounts of TGM could be detected and no shortage was reached. Conclusion. Our initial measurements are still too few in number neither to generalize the achieved results nor discuss controlling factors and processes. However, we are pleased to communicate that the developed GSC is well suited to become an effective sampling set up to rapidly estimate the magnitude of Hg volatilization from soils. Outlook. Further measurements at other polluted locations are necessary to verify the GSC method. In addition the use of a mercury analyzer instead of gold traps is planned for faster risk assessments.     

大气环境影响评价点源预测模型软件系统的开发

大气环境影响评价是环境影响评价的一项重要内容,而其中最主要的部分就是计算各种大气扩散模式下的地面污染浓度,然后据此结果作出评价.为方便气象资料的整理和大气扩散的计算,因此使用Matlab软件,编制这套大气环境影响评价点源预测模型软件系统.     

Structural Diversity: A Multi-dimensional Approach to Assess Recreational Services in Urban Parks

Urban green spaces provide important recreational services for urban residents. In general, when park visitors enjoy “the green,” they are in actuality appreciating a mix of biotic, abiotic, and man-made park infrastructure elements and qualities. We argue that these three dimensions of structural diversity have an influence on how people use and value urban parks. We present a straightforward approach for assessing urban parks that combines multi-dimensional landscape mapping and questionnaire surveys. We discuss the method as well the results from its application to differently sized parks in Berlin and Salzburg.     

A Preliminary Study of Particulate Emissions from Small Wood Stoves

This paper summarizes the methodology developed to analyze alternative oxidant control strategies of the 1979 Air Quality Plan for the San Francisco Bay Area. The analysis of alternative oxidant control strategies is a complex task, particularly when a grid-based photochemical model is the primary analysis tool. To handle quantitatively spatial and temporal variations in emissions under both existing and projected future conditions, as well as to simulate the effects of a wide variety of control strategies, a system of computer-based models was assembled. The models projected and distributed a number of variables in space and time: population, employment, housing, land use, transportation, emissions, and air quality. Given time and budget constraints, an approach to maximizing the information return from a limited number of model runs was developed. The system was applied in three sequences to determine (1) what future air quality would be if no further controls were implemented, (2) the degree of hydrocarbon and NO_x emission control necessary to attain the oxidant standard, and (3) the effectiveness of alternative stationary source, mobile source, transportation and land use control strategies in contributing to attainment and maintenance of the oxidant standard.

A number of significant modeling assumptions had to be developed in order properly to interpret the modeled results in the context of the oxidant standard. In particular, a Larsen-type analysis was used to relate modeled atmospheric conditions to “worst case” conditions, and a proportional assumption was made to compensate model results for an imperfect validation. The specification of initial and boundary conditions for future year simulations was found to be a problem in need of further research.     

A Mercury Vapor Detector Based upon the Automatic Adjustment of Lamp Intensity to the Mercury Concentration

An office containing about 65 employees was found to have 8-h average CO concentrations of 18-26 ppm during a week in winter. On one Friday afternoon, 20 nonsmoking office workers had alveolar CO levels of 23 ± 3 ppm compared to levels of 8 ± 2 ppm in six nonsmoking workers in other offices in the same building. After a weekend at home, the affected office workers displayed reduced alveolar CO levels of 7 ± 2 ppm. The source of the high CO levels was attributed to a parking garage on the same level as the office. Closing fire doors and activating garage fans rectified the situation. The breath sampling method is found to require a correction factor based on the difference between the true alveolar CO and the CO level in the surrounding air. The methods and equipment employed in this study (personal air monitors, electronic data loggers, breath sampling) are recommended for screening and identifying potential CO problems in buildings with similar conditions.     

European Community Can Reduce CO2 Emissions by Sixty Percent: A Feasibility Study

Carbon dioxide (CO₂,) emissions in the European Community (EC) can be reduced by roughly 60 percent. A great many measures need to be taken to reach this reduction, with a total annual cost of ECU 55 milliard. Fossil fuel use is the main cause of CO2 emissions into the atmosphere; CO₂ emissions are to a large extent responsible for the greenhouse effect. Energy saving (conservation) and nuclear energy appear to be the least expensive methods of CO₂, abatement, directly followed by renewables. More expensive alternatives include the separation of CO₂, at the source (e.g., power plants), followed by storage in depleted gas fields, aquifers, or in the ocean. Biological options, such as reforestation and energy farming, are the most expensive abatement methods; however, they do have secondary advantages, such as avoided fallow premiums and avoided export premiums on cereals. Application of all measures together can lead to the 60 percent reduction goal.