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.     

Investigation of selective catalytic reduction impact on mercury speciation under simulated NOx emission control conditions

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NOx) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NOx reduction, promote the formation of oxidized mercury (Hg2+). The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg0) oxidation. Bench-scale experiments were conducted to investigate Hg0 oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO2) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO2 in the flue gases on Hg0 oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg0 to Hg2+ under SCR reaction conditions. The importance of HCl for Hg0 oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg0 oxidation occurring across the SCR reactors in the field.     

Investigation of Selective Catalytic Reduction Impact on Mercury Speciation under Simulated NOx Emission Control Conditions

Abstract

Selective catalytic reduction (SCR) technology increasingly is being applied for controlling emissions of nitrogen oxides (NO_x) from coal-fired boilers. Some recent field and pilot studies suggest that the operation of SCR could affect the chemical form of mercury (Hg) in coal combustion flue gases. The speciation of Hg is an important factor influencing the control and environmental fate of Hg emissions from coal combustion. The vanadium and titanium oxides, used commonly in the vanadia-titania SCR catalyst for catalytic NO_x reduction, promote the formation of oxidized mercury (Hg²⁺).

The work reported in this paper focuses on the impact of SCR on elemental mercury (Hg⁰) oxidation. Bench-scale experiments were conducted to investigate Hg⁰ oxidation in the presence of simulated coal combustion flue gases and under SCR reaction conditions. Flue gas mixtures with different concentrations of hydrogen chloride (HCl) and sulfur dioxide (SO₂) for simulating the combustion of bituminous coals and subbituminous coals were tested in these experiments. The effects of HCl and SO₂ in the flue gases on Hg⁰ oxidation under SCR reaction conditions were studied. It was observed that HCl is the most critical flue gas component that causes conversion of Hg⁰ to Hg²⁺ under SCR reaction conditions. The importance of HCl for Hg⁰ oxidation found in the present study provides the scientific basis for the apparent coal-type dependence observed for Hg⁰ oxidation occurring across the SCR reactors in the field.     

Mercury oxidation promoted by a selective catalytic reduction catalyst under simulated Powder River Basin coal combustion conditions

A bench-scale reactor consisting of a natural gas burner and an electrically heated reactor housing a selective catalytic reduction (SCR) catalyst was constructed for studying elemental mercury (Hg(o)) oxidation under SCR conditions. A low sulfur Powder River Basin (PRB) subbituminous coal combustion fly ash was injected into the entrained-flow reactor along with sulfur dioxide (SO2), nitrogen oxides (NOx), hydrogen chloride (HCl), and trace Hg(o). Concentrations of Hg(o) and total mercury (Hg) upstream and downstream of the SCR catalyst were measured using a Hg monitor. The effects of HCl concentration, SCR operating temperature, catalyst space velocity, and feed rate of PRB fly ash on Hg(o) oxidation were evaluated. It was observed that HCl provides the source of chlorine for Hg(o) oxidation under simulated PRB coal-fired SCR conditions. The decrease in Hg mass balance closure across the catalyst with decreasing HCl concentration suggests that transient Hg capture on the SCR catalyst occurred during the short test exposure periods and that the outlet speciation observed may not be representative of steady-state operation at longer exposure times. Increasing the space velocity and operating temperature of the SCR led to less Hg(o) oxidized. Introduction of PRB coal fly ash resulted in slightly decreased outlet oxidized mercury (Hg2+) as a percentage of total inlet Hg and correspondingly resulted in an incremental increase in Hg capture. The injection of ammonia (NH3) for NOx reduction by SCR was found to have a strong effect to decrease Hg oxidation. The observations suggest that Hg(o) oxidation may occur near the exit region of commercial SCR reactors. Passage of flue gas through SCR systems without NH3 injection, such as during the low-ozone season, may also impact Hg speciation and capture in the flue gas.     

Nitrogen oxides emission control options for coal-fired electric utility boilers

Recent regulations have required reductions in emissions of nitrogen oxides (NOx) from electric utility boilers. To comply with these regulatory requirements, it is increasingly important to implement state-of-the-art NOx control technologies on coal-fired utility boilers. This paper reviews NOx control options for these boilers. It discusses the established commercial primary and secondary control technologies and examines what is being done to use them more effectively. Furthermore, the paper discusses recent developments in NOx controls. The popular primary control technologies in use in the United States are low-NOx burners and overfire air. Data reflect that average NOx reductions for specific primary controls have ranged from 35% to 63% from 1995 emissions levels. The secondary NOx control technologies applied on U.S. coal-fired utility boilers include reburning, selective noncatalytic reduction (SNCR), and selective catalytic reduction (SCR). Thirty-six U.S. coal-fired utility boilers have installed SNCR, and reported NOx reductions achieved at these applications ranged from 15% to 66%. Recently, SCR has been installed at >150 U.S. coal-fired utility boilers. Data on the performance of 20 SCR systems operating in the United States with low-NOx emissions reflect that in 2003, these units achieved NOx emission rates between 0.04 and 0.07 lb/10(6) Btu.     

Control strategies of atmospheric mercury emissions from coal-fired power plants in China

Atmospheric mercury (Hg) emission from coal is one of the primary sources of anthropogenic discharge and pollution. China is one of the few countries in the world whose coal consumption constitutes about 70% of total primary energy, and over half of coals are burned directly for electricity generation. Atmospheric emissions of Hg and its speciation from coal-fired power plants are of great concern owing to their negative impacts on regional human health and ecosystem risks, as well as long-distance transport. In this paper, recent trends of atmospheric Hg emissions and its species split from coal-fired power plants in China during the period of 2000-2007 are evaluated, by integrating each plant's coal consumption and emission factors, which are classified by different subcategories of boilers, particulate matter (PM) and sulfur dioxide (SO2) control devices. Our results show that the total Hg emissions from coal-fired power plants have begun to decrease from the peak value of 139.19 t in 2005 to 134.55 t in 2007, though coal consumption growing steadily from 1213.8 to 1532.4 Mt, which can be mainly attributed to the co-benefit Hg reduction by electrostatic precipitators/fabric filters (ESPs/FFs) and wet flue gas desulfurization (WFGD), especially the sharp growth in installation of WFGD both in the new and existing power plants since 2005. In the coming 12th five-year-plan, more and more plants will be mandated to install De-NO(x) (nitrogen oxides) systems (mainly selective catalytic reduction [SCR] and selective noncatalytic reduction [SNCR]) for minimizing NO(x) emission, thus the specific Hg emission rate per ton of coal will decline further owing to the much higher co-benefit removal efficiency by the combination of SCR + ESPs/FFs + WFGD systems. Consequently, SCR + ESPs/FFs + WFGD configuration will be the main path to abate Hg discharge from coal-fired power plants in China in the near future. However advanced specific Hg removal technologies are necessary for further reduction of elemental Hg discharge in the long-term.     

Pilot-scale study of the effect of selective catalytic reduction catalyst on mercury speciation in Illinois and Powder River Basin coal combustion flue gases

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NOx) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg0), decreasing the percentage of Hg0 at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg0 by the SCR catalyst, with the percentage of Hg0 decreasing from approximately 96% at the inlet of the reactor to approximately 80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Nitrogen Oxides Emission Control Options for Coal-Fired Electric Utility Boilers

Abstract

Recent regulations have required reductions in emissions of nitrogen oxides (NO_x) from electric utility boilers. To comply with these regulatory requirements, it is increasingly important to implement state-of-the-art NO_x control technologies on coal-fired utility boilers. This paper reviews NO_x control options for these boilers. It discusses the established commercial primary and secondary control technologies and examines what is being done to use them more effectively. Furthermore, the paper discusses recent developments in NO_x controls. The popular primary control technologies in use in the United States are low-NO_x burners and overfire air. Data reflect that average NO_x reductions for specific primary controls have ranged from 35% to 63% from 1995 emissions levels. The secondary NO_x control technologies applied on U.S. coal-fired utility boilers include reburning, selective noncatalytic reduction (SNCR), and selective catalytic reduction (SCR). Thirty-six U.S. coal-fired utility boilers have installed SNCR, and reported NO_x reductions achieved at these applications ranged from 15% to 66%. Recently, SCR has been installed at >150 U.S. coal-fired utility boilers. Data on the performance of 20 SCR systems operating in the United States with low-NO_x emissions reflect that in 2003, these units achieved NO_x emission rates between 0.04 and 0.07 lb/10⁶ Btu.     

Sulfur dioxide and nitrogen oxides emissions from U.S. pulp and paper mills, 1980-2005

Comprehensive surveys conducted at 5-yr intervals were used to estimate sulfur dioxide (SO,) and nitrogen oxides (NO.) emissions from U.S. pulp and paper mills for 1980, 1985, 1990, 1995, 2000, and 2005. Over the 25-yr period, paper production increased by 50%, whereas total SO, emissions declined by 60% to 340,000 short tons (t) and total NO, emissions decreased approximately 15% to 230,000 t. The downward emission trends resulted from a combination of factors, including reductions in oil and coal use, steadily declining fuel sulfur content, lower pulp and paper production in recent years, increased use of flue gas desulfurization systems on boilers, growing use of combustion modifications and add-on control systems to reduce boiler and gas turbine NO, emissions, and improvements in kraft recovery furnace operations.     

Problems of Meeting Multiple Air Quality Objectives for Coal-Fired Utility Boilers

Gaseous wastes and particulate emissions are produced in the process of burning coal to produce electrical energy. In attempting to control these gaseous wastes, changes in the operation efficiency of boilers and secondary equipment are likely to result, and in addition liquid and solid waste streams are produced. The interrelationships among the various forms of wastes and the effects of air quality control on process efficiency are often overlooked in studies of environmental quality management.

The study was undertaken to evaluate the technical alternatives for handling gaseous and particulate emissions from coal-fired boilers and to determine the feasibility of meeting several standards simultaneously. The gaseous emissions of major importance in the combustion of coal are parti culates, oxides of sulfur, and oxides of nitrogen. Particulates can be controlled by a tradeoff among further preparation at the mine (for additional ash removal), type of boiler, use of dust control equipment and high stacks for dispersion of residual emissions, if ambient air standards are considered. Oxides of sulfur reduction depends currently on fuel substitution, limestone additives in the boiler and some form of contact process such as wet scrubbing, or the use of high stacks. Oxides of nitrogen control in coal fired boilers is restricted to small reductions by either changes in boiler operation, such as lower excess air levels, adsorption during wet scrubbing or by dispersion from high stacks.     

Natural desulfurization in coal-fired units using Greek lignite

This paper analyzes the natural desulfurization process taking place in coal-fired units using Greek lignite. The dry scrubbing capability of Greek lignite appears to be extremely high under special conditions, which can make it possible for the units to operate within the legislative limits of sulfur dioxide (SO2) emissions. According to this study on several lignite-fired power stations in northern Greece, it was found that sulfur oxide emissions depend on coal rank, sulfur content, and calorific value. On the other hand, SO2 emission is inversely proportional to the parameter gammaCO2(max), which is equal to the maximum carbon dioxide (CO2) content by volume of dry flue gas under stoichiometric combustion. The desulfurization efficiency is positively correlated to the molar ratio of decomposed calcium carbonate to sulfur and negatively correlated to the free calcium oxide content of fly ash.     

Opacity Reduction Using Dry Hydrated Lime Injection

Abstract

This investigation studied the effects of injecting dry hydrated lime into flue gas to reduce sulfur trioxide, (SO₃) concentrations and consequently stack opacity at the University of Missouri-Columbia power plant. The opacity was due to sulf uric acid mist forming at the stack from high SO₃ concentrations. As a result of light scattering by the mist, a visible plume leaves the stack. Therefore, reducing high concentrations of SO₃ reduces the sulfuric acid mist and consequently the opacity. To reduce SO₃ concentrations, dry hydrated lime is periodically injected into the flue gas upstream of a baghouse and downstream of an induced draft fan. The hydrated lime is transported downstream by the flue gas and deposited on the filter bags in the baghouse forming a filter cake. The reaction between the SO₃ and the hydrated lime takes place on the filter bags. The hydrated lime injection system has resulted in at least 95% reduction in the SO₃ concentration and has reduced the opacity to acceptable limits. Low capital equipment requirements, low operating cost, and increased bag life make the system very attractive to industries with similar problems.     

Pilot-Scale Study of the Effect of Selective Catalytic Reduction Catalyst on Mercury Speciation in Illinois and Powder River Basin Coal Combustion Flue Gases

Abstract

A study was conducted to investigate the effect of selective catalytic reduction (SCR) catalyst on mercury (Hg) speciation in bituminous and subbituminous coal combustion flue gases. Three different Illinois Basin bituminous coals (from high to low sulfur [S] and chlorine [Cl]) and one Powder River Basin (PRB) subbituminous coal with very low S and very low Cl were tested in a pilot-scale combustor equipped with an SCR reactor for controlling nitrogen oxides (NO_x) emissions. The SCR catalyst induced high oxidation of elemental Hg (Hg⁰), decreasing the percentage of Hg⁰ at the outlet of the SCR to values <12% for the three Illinois coal tests. The PRB coal test indicated a low oxidation of Hg⁰ by the SCR catalyst, with the percentage of Hg⁰ decreasing from ～96% at the inlet of the reactor to ～80% at the outlet. The low Cl content of the PRB coal and corresponding low level of available flue gas Cl species were believed to be responsible for low SCR Hg oxidation for this coal type. The test results indicated a strong effect of coal type on the extent of Hg oxidation.     

Simulation of stack plume opacity

The visual impact of primary particles emitted from stacks is regulated according to stack opacity criteria. In-stack monitoring of the flue gas opacity allows plant operators to ensure that the plant meets U.S. Environmental Protection Agency opacity regulations. However, the emission of condensable gases such as SO3 (that hydrolyzes to H2SO4), HCl, and NH3, which may lead to particle formation after their release from the stack, makes the prediction of stack plume opacity more difficult. We present here a computer simulation model that calculates the opacity due to both primary particles emitted from the stack and secondary particles formed in the atmosphere after the release of condensable gases from the stack. A comprehensive treatment of the plume rise due to buoyancy and momentum is used to calculate the location at which the condensed water plume has evaporated (i.e., where opacity regulations apply). Conversion of H2SO4 to particulate sulfate occurs through nucleation and condensation on primary particles. A thermodynamic aerosol equilibrium model is used to calculate the amount of ammonium, chloride, and water present in the particulate phase with the condensed sulfate. The model calculates the stack plume opacity due to both primary and secondary particles. Examples of model simulations are presented for three scenarios that differ by the emission control equipment installed at the power plant: (1) electrostatic precipitators (ESP), (2) ESP and flue gas desulfurization, and (3) ESP and selective catalytic reduction. The calculated opacity is most sensitive to the primary particulate emissions. For the conditions considered here, SO3 emissions showed only a small effect, except if one assumes that most H2SO4 condenses on primary particles. Condensation of NH4Cl occurs only at high NH3 emission rates (about 25 ppm stack concentration).     

An alternative to additional SO3 injection for fly ash conditioning

Small concentrations, approximately 2-10 parts per million (ppm), of injected sulfur trioxide (SO3) have improved particulate collection efficiencies of electrostatic precipitators burning lower-sulfur coal. However, the addition of extra SO3 not only incurs costs but also presents negative environmental effects. This work explored a method that could be applied to existing coal-fired power plants to convert the sulfur dioxide (SO2) already present in the flue gas to sufficient levels of SO3 for fly ash conditioning as an alternative to adding SO3 by burning elemental sulfur. During this research, a pre-mixed natural gas flame was used to promote the conversion of SO2 to SO3 in a drop-tube furnace with average non-flame, free stream gas temperatures of 450 and 1000 K. SO3 concentrations measured by wet chemistry and confirmed using elemental balances of other sulfur species measured by gas chromatography revealed that as much as 7% of SO2 was homogeneously transformed to SO3. The results also showed that at low temperatures, the rate at which SO3 is converted back to SO2 decreased, thus extending the time period during which SO3 concentrations would be sufficient for ash conditioning. An additional benefit of this technique is speculated to result from increased flue gas humidity.     

Flue gas desulfurization: the state of the art

Coal-fired electricity-generating plants may use SO2 scrubbers to meet the requirements of Phase II of the Acid Rain SO2 Reduction Program. Additionally, the use of scrubbers can result in reduction of Hg and other emissions from combustion sources. It is timely, therefore, to examine the current status of SO2 scrubbing technologies. This paper presents a comprehensive review of the state of the art in flue gas desulfurization (FGD) technologies for coal-fired boilers. Data on worldwide FGD applications reveal that wet FGD technologies, and specifically wet limestone FGD, have been predominantly selected over other FGD technologies. However, lime spray drying (LSD) is being used at the majority of the plants employing dry FGD technologies. Additional review of the U.S. FGD technology applications that began operation in 1991 through 1995 reveals that FGD processes of choice recently in the United States have been wet limestone FGD, magnesium-enhanced lime (MEL), and LSD. Further, of the wet limestone processes, limestone forced oxidation (LSFO) has been used most often in recent applications. The SO2 removal performance of scrubbers has been reviewed. Data reflect that most wet limestone and LSD installations appear to be capable of approximately 90% SO2 removal. Advanced, state-of-the-art wet scrubbers can provide SO2 removal in excess of 95%. Costs associated with state-of-the-art applications of LSFO, MEL, and LSD technologies have been analyzed with appropriate cost models. Analyses indicate that the capital cost of an LSD system is lower than those of same capacity LSFO and MEL systems, reflective of the relatively less complex hardware used in LSD. Analyses also reflect that, based on total annualized cost and SO2 removal requirements: (1) plants up to approximately 250 MWe in size and firing low- to medium-sulfur coals (i.e., coals with a sulfur content of 2% or lower) may use LSD; and (2) plants larger than 250 MWe and firing medium- to high-sulfur coals (i.e., coals with a sulfur content of 2% or higher) may use either LSFO or MEL.     

Oxidation of mercury across selective catalytic reduction catalysts in coal-fired power plants

A kinetic model for predicting the amount of mercury (Hg) oxidation across selective catalytic reduction (SCR) systems in coal-fired power plants was developed and tested. The model incorporated the effects of diffusion within the porous SCR catalyst and the competition between ammonia and Hg for active sites on the catalyst. Laboratory data on Hg oxidation in simulated flue gas and slipstream data on Hg oxidation in flue gas from power plants were modeled. The model provided good fits to the data for eight different catalysts, both plate and monolith, across a temperature range of 280-420 degrees C, with space velocities varying from 1900 to 5000 hr(-1). Space velocity, temperature, hydrochloric acid content of the flue gas, ratio of ammonia to nitric oxide, and catalyst design all affected Hg oxidation across the SCR catalyst. The model can be used to predict the impact of coal properties, catalyst design, and operating conditions on Hg oxidation across SCRs.     

Effect of NOx control processes on mercury speciation in utility flue gas

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NOx control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NOx control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH3, has been evaluated. The influence of NH3 on fly ash Hg reactions also is being investigated.     

1987 Joint EPRI/EPA Symposium on Stationary Combustion NOX Control

From March 23rd to 26th, 1987, the city of New Orleans hosted 350 attendees, including representatives from 15 foreign countries, at the 1987 Joint Symposium on Stationary Combustion NO_x Control. Cosponsored by the Electric Power Research Institute (EPRI) and the U.S. Environmental Protection Agency (EPA), the symposium provided attendees the opportunity to hear 49 papers in nine sessions covering technological and regulatory developments on NO_x control in the United States and abroad since the May 1985 symposium in Boston. Session topics included general environmental issues, low-NO_x combustion equipment (i.e., low-NO_x burners, reburning, etc.), flue gas treatment, fundamental combustion research, and special issues for cyclone coal-fueled boilers, oil- and gas-fired boilers, and industrial combustion applications.

Advances to the state-of-the-art presented at this symposium include: improved and/or newly applied combustion modifications for pulverized coal-fired boilers; further analyses of reburning, the leading combustion modification option for cyclone-equipped boilers; initial experiences with catalytic flue gas treatment in Europe; studies of NO_x control retrofit options for oil- and gas-fired utility systems; and new technology developments for coal, oil, and gas fueled utility and industrial combustors.

This paper summarizes those presentations that discussed significant changes since May 1985 in areas of potential interest to EPRI and its utility members. Where appropriate, they include our perspectives on the applicability of these newly disclosed findings to utility systems.     

Effect of NOx Control Processes on Mercury Speciation in Utility Flue Gas

Abstract

The speciation of Hg in coal-fired flue gas can be important in determining the ultimate Hg emissions as well as potential control options for the utility. The effects of NO_x control processes, such as selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR), on Hg speciation are not well understood but may impact emissions of Hg. EPRI has investigated the reactions of Hg in flue gas at conditions expected for some NO_x control processes. This paper describes the methodology used to investigate these reactions in actual flue gas at several power plants. Results have indicated that some commercial SCR catalysts are capable of oxidizing elemental Hg in flue gas obtained from the inlets of SCR or air heater units. Results are affected by various flue gas and operating parameters. The effect of flue gas composition, including the presence of NH₃, has been evaluated. The influence of NH₃ on fly ash Hg reactions also is being investigated.