Characterization of products from fluidized-bed combustion of coal

The technology of fluidized-bed combustion (FBC) of coal generates byproducts that have a series of unique characteristics and potential uses in technological practice. In this study, the products of fluidized-bed combustion (FBC-P) of coal derived from Moravian heat stations, a.s. Zlin, Cinergy Global Resources, Czech Republic, were characterized. Particular attention was paid to determining the chemical composition of FBC-P, the content of polycyclic aromatic hydrocarbons (PAHs) and toxic metals in the water leachates of these FBC-P, the content of unburned carbon, the capability of FBC-P to solidify with water and form a solid matrix, and the method for discovering optimum mixing water content for FBC-P solidification. The results suggest that one of the qualitatively more important means of utilizing FBC-P could be their application during solidification/stabilization (S/S) of wastes, particularly wastewater treatment sludges.     

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.     

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.     

An Assessment of the Significance of Mercury Release from Coal Fly Ash

Abstract

Some mercury (Hg) naturally present in coal is retained in the fly ash remaining after combustion. Concern has been raised regarding the potential for release of this Hg to the environment. The exchange of Hg between fly ash and the atmosphere was measured in the laboratory and in situ at a fly ash landfill. All samples of fly ash used in the laboratory study, with the exception of that derived from lignite-type coal, acted as a sink for atmospheric Hg. Deposition rates were found to increase as air Hg concentrations increased and to decrease with incident light and increased temperature. Addition of water to fly ash samples resulted in re-emission of deposited atmospheric Hg. Deposition was the dominant flux measured in situ at a fly ash landfill. Atmospheric Hg was deposited to all samples collected as part of two demonstration projects using carbon injection for enhanced Hg capture. Hg concentrations of extracts derived using U.S. Environmental Protection Agency Method 1312 (Synthetic Precipitation Leaching Procedure) were ≤14.4 ng/L. Data developed demonstrate that fly ash, including that collected from Hg removal projects, will release little Hg to the air or water, and under certain conditions, absorbs Hg from the air.     

The Effect of Coal Combustion Flue Gas Components on Low-Level Chlorine Speciation Using EPA Method 26A

ABSTRACT

U.S. Environmental Protection Agency (EPA) Method 26A is the recommended procedure for capturing and speci-ating halogen (X₂) and hydrogen halide (HX) stack emissions from combustion sources. Previous evaluation studies of Method 26A have focused primarily on hydrogen chloride (HCl) speciation. Capture efficiency, bias, and the potential interference of Cl₂ at high levels (>20 ppm [u,g/m³]) and NH₄Cl in the flue gas stream have been investigated. It has been suggested that precise Cl₂ measurement and accuracy in quantifying HX or X₂ using Method 26A are difficult to achieve at Cl₂ concentrations <5 ppm; however, no performance data exist to support this. Coal contains low levels of Cl, in the range of 5-2000 ppmw, which results in the presence of HCl and Cl₂ in the products of combustion. HCl is the predominant Cl compound formed in the high-temperature combustion process, and it persists in the gas as the products of combustion cool. Concentrations of Cl₂ in coal combustion flue gas at stack temperatures typically do not exceed 5 ppm. For this research, bench-scale experiments using simulated combustion flue gas were designed to validate the ability of Method 26A to speci-ate low levels of Cl₂ accurately. This paper presents the results of the bench-scale tests. The effect of various flue gas components is discussed. The results indicate that SO₂ is the only component in coal combustion flue gas that has an appreciable effect on Cl₂ distribution in Method 26A impingers, and that Method 26A cannot accurately speciate HCl and Cl₂ in coal combustion flue gas without modification.     

Release of Mercury Vapor from Coal Combustion Ash

Abstract

The long-term stability of Hg in coal combustion byproducts (CCBs) was evaluated at ambient and near-ambient temperatures. Six CCB samples with atypically high levels of total Hg were selected for study assuming a greater potential for release of measurable amounts of Hg vapor. The samples selected included two fly ash samples from U.S. eastern bituminous coal, two fly ash samples from South African low-rank coal, one fly ash from Powder River Basin (PRB) subbituminous coal blended with petroleum coke, and one PRB subbituminous coal fly ash incorporated with flue gas desulfurization material.

Air scrubbed of Hg was passed through compacted 100-g aliquots of each sample at 1 mL/min and vented to a gold-coated quartz trap to collect released Hg vapor. The samples were maintained at ambient and near-ambient (37 °C) temperatures. All samples released low-picogram levels of Hg after 90 days. No pattern was evident to link the total Hg content to the rate of release of Hg vapor. An average of 0.030 pg Hg/g CCB/day was released from the samples, which equates to 2.2 x 10^-8 lb Hg/ton CCB/year. If this were applied to a coal-fired power plant production of 200,000 tons of fly ash per year, there would be a maximum potential release of 0.0044 lb, or 2.00 g, of Hg per year. Experiments are continuing to determine long-term vapor release of Hg from CCBs. All samples have been set up in duplicate at ambient temperature with an improved apparatus to reevalu-ate results reported in this article.     

Combustion Kinetics and Emission Characteristics of Polycyclic Aromatic Hydrocarbons from Polylactic Acid Combustion

Abstract

This study investigates the combustion kinetics and emission factors of 16 U.S. Environmental Protection Agency priority polycyclic aromatic hydrocarbons (PAHs) in polylactic acid (PLA) combustion. Experimentally, two reactions are involved in the PLA combustion process that potentially result in the release of lactide, acetaldehyde, and n-hexaldehyde. The products may continuously be oxidized to form carbon dioxide (CO₂) and some PAHs produced because of incomplete combustion. The analytical results indicate that the emission factors for PAHs are in the range of not detectable to 98.04 μg/g. The emission factors are much lower than those of poly(ethylene terephalate) (PET) and other combustion of plastics. Results from this work suggest that combustion is a good choice for waste PLA disposal.     

Identification of Sources Contributing to Mid-Atlantic Regional Aerosol

Abstract

Source types or source regions contributing to the concentration of atmospheric fine particles measured at Brigantine National Wildlife Refuge, NJ, were identified using a factor analysis model called Positive Matrix Factorization (PMF). Cluster analysis of backward air trajectories on days of high- and low-factor concentrations was used to link factors to potential source regions. Brigantine is a Class I visibility area with few local sources in the center of the eastern urban corridor and is therefore a good location to study Mid-Atlantic regional aerosol. Sulfate (expressed as ammonium sulfate) was the most abundant species, accounting for 49% of annual average fine mass. Organic compounds (22%; expressed as 1.4 × organic carbon) and ammonium nitrate (10%) were the next abundant species. Some evidence herein suggests that secondary organic aerosol formation is an important contributor to summertime regional aerosol.

Nine factors were identified that contributed to PM_2.5 mass concentrations: coal combustion factors (66%, summer and winter), sea salt factors (9%, fresh and aged), motor vehicle/mixed combustion (8%), diesel/Zn-Pb (6%), incinerator/industrial (5%), oil combustion (4%), and soil (2%). The aged sea salt concentrations were highest in springtime, when the land breeze-sea breeze cycle is strongest. Comparison of backward air trajectories of high- and low-concentration days suggests that Brigantine is surrounded by sources of oil combustion, motor vehicle/mixed combustion, and waste incinerator/industrial emissions that together account for 17% of PM_2.5 mass. The diesel/Zn-Pb factor was associated with sources north and west of Brigantine. Coal combustion factors were associated with coal-fired power plants west and southwest of the site. Particulate carbon was associated not only with oil combustion, motor vehicle/mixed combustion, waste incinerator/industrial, and diesel/Pb-Zn, but also with the coal combustion factors, perhaps through common transport.     

Analysis and discussion on formation and control of primary particulate matter generated from coal-fired power plants

Particulate matter (PM) has been becoming the principal urban pollutant in many major cities in China, and even all over the world. It is reported that the coal combustion process is one of the main sources of PM in the atmosphere. Therefore, an investigation of formation and emission of fine primary PM in coal combustion was conducted. First, the sources and classification of coal-fired primary PM were discussed; then their formation pathways during the coal combustion process were analyzed in detail. Accordingly, the emission control methods for fine particles generated from coal-fired power plants were put forward, and were classified as precombustion control, in-combustion control, and postcombustion control. Precombustion control refers to the processes for improving the coal quality before combustion, such as coal type selection and coal preparation. In-combustion control means to take measures for adjusting the combustion conditions and injection of additives during the combustion process to abate the formation of PM. Postcombustion control is the way that the fine PM are aggregated into larger ones by some agglomeration approaches and subsequently are removed by dust removal devices, or some high-performance modifications of conventional particle emission control devices (PECDs) can be taken for capturing fine particles. Finally, some general management suggestions are given for reducing fine PM emission in coal-fired power plants.

ImplicationsThe analysis and discussions of coal properties and its combustion process are critical to recognizing the formation and emission of the fine primary PM in combustion. The measures of precombustion, in-combustion, and postcombustion control based on the analysis and discussions are favorable for abating the PM emission. Practically, some measures of implementation do need the support of national policies, even needing to sacrifice economy to gain environmental profit, but this is the very time to execute these, and high-performance PECDs, especially novel devices, should be used for removing fine PM in flue gas.     

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

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

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.     

Combustion Characteristics of Spent Catalyst and Paper Sludge in an Internally Circulating Fluidized-Bed Combustor

Abstract

Combustion of spent vacuum residue hydrodesulfurization catalyst and incineration of paper sludge were carried out in thermo-gravimetric analyzer and an internally circulating fluidized-bed (ICFB) reactor. From the thermogravimetric analyzer-differential thermo-gravimetric curves, the pre-exponential factors and activation energies are determined at the divided temperature regions, and the thermo-gravimetric analysis patterns can be predicted by the kinetic equations. The effects of bed temperature, gas velocity in the draft tube and annulus, solid circulation rate, and waste feed rate on combustion efficiency of the wastes have been determined in an ICFB from the experiments and the model studies. The ICFB combustor exhibits uniform temperature distribution along the bed height with high combustion efficiency (>90%). The combustion efficiency increases with increasing reaction temperature, gas velocity in the annulus region, and solid circulation rate and decreases with increasing waste feed rate and gas velocity in the draft tube. The simulated data from the kinetic equation and the hydrodynamic models predict the experimental data reasonably well.     

Sulfur Dioxide and Nitrogen Oxides Emissions from U.S. Pulp and Paper Mills, 1980–2005

Abstract

Comprehensive surveys conducted at 5-yr intervals were used to estimate sulfur dioxide (SO₂) and nitrogen oxides (NO_x) 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 SO₂ emissions declined by 60% to 340,000 short tons (t) and total NO_x 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_x emissions, and improvements in kraft recovery furnace operations.     

Formation of PCDD/PCDF

One option of recycling used contaminated packaging is to recover its high energy content. This can be performed in a normal multi-fuel power plant by co-combustion of packaging-derived fuel (PDF) or refuse-derived fuel (RDF) with fossil fuels, such as coal or peat. This work includes the results of 17 co-combustion tests and an evaluation of the results by the Principal Component Analysis (PCA) and the Partial Least Squares Projections to Latent Structures (PLS). PCA and PLS calculations showed that especially Pb, but also Cr, and Cu correlated with lower chlorinated furans (PCDFs) in the fly ash. Correlation between Sn and lower chlorinated dioxins (PCDDs) in the fly ash was also noticed. CO and PAH emission in the flue gas correlated with total PCDD/Fs in the flue gas. In a real full-scale combustion process, a single parameter in fuel, flue gas or a combustion parameter did not provide a guide to PCDD/F formation or to a level of the total PCDD/F emission, but correlations between different parameters and PCDD/Fs could be found. Although PDFs and RDF had catalytic heavy metals and chlorine, the co-combustion results showed that they can be co-combusted with peat and coal in a fluidized-bed boiler at least up to 26 % with very low total PCDD and PCDF emissions.     

Source Apportionment of Ambient Total Suspended Particulates and Coarse Particulate Matter in Urban Areas of Jiaozuo,China

Abstract

Approximately 750 total suspended particulates (TSPs) and coarse particulate matter (PM₁₀) filter samples from six urban sites and a background site and >210 source samples were collected in Jiaozuo City during January 2002 to April 2003. They were analyzed for mass and abundances of 25 chemical components. Seven contributive sources were identified, and their contributions to ambient TSP/PM₁₀ levels at the seven sites in three seasons (spring, summer, and winter days) and a “whole” year were estimated by a chemical mass balance (CMB) receptor model. The spatial TSP average was high in spring and winter days at a level of approximately 530 ～g/m³ and low in summer days at 456 ～g/m³; however, the spatial PM₁₀ average exhibited little variation at a level of approximately 325 ～g/m³, and PM_10-to-TSP ratios ranged from 0.58 to 0.81, which suggested heavy particulate matter pollution existing in the urban areas. Apportionment results indicated that geological material was the largest contributor to ambient TSP/PM₁₀ concentrations, followed by dust emissions from construction activities, coal combustion, secondary aerosols, vehicle movement, and other industrial sources. In addition, paved road dust and re-entrained dust were also apportioned to the seven source types and found soil, coal combustion, and construction dust to be the major contributors.     

A New Method to Assess Mercury Emissions: A Study of Three Coal-Fired Electric-Generating Power Station Configurations

Abstract

U.S. Environmental Protection Agency (EPA) Method 7473 for the analysis of mercury (Hg) by thermal decomposition, amalgamation, and atomic absorption spectroscopy has proved successful for use in Hg assessment at coal-fired power stations. In an analysis time of ～5 min per sample, this instrumental methodology can directly analyze total Hg—with no discrete sample preparation—in the solid matrices associated with a coal-fired power plant, including coal, fly ash, bottom ash, and flue gas desulfurization (FGD) material. This analysis technique was used to investigate Hg capture by coal combustion byproducts (CCBs) in three different coal-fired power plant configurations. Hg capture and associated emissions were estimated by partial mass balance. The station equipped with an FGD system demonstrated 68% capture on FGD material and an emissions estimate of 18% (11 kg/yr) of total Hg input. The power plant equipped with low oxides of nitrogen burners and an electrostatic precipitator (ESP) retained 43% on the fly ash and emitted 57% (51 kg/yr). The station equipped with conventional burners and an ESP retained less than 1% on the fly ash, emitting an estimated 99% (88 kg/yr) of Hg. Estimated Hg emissions demonstrate good agreement with EPA data for the power stations investigated.     

From Air Repair to EM: A&WMA’s Publications through a Century of Change

Abstract

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 y _CO2max, which is equal to the maximum carbon dioxide (CO₂) content by vol ume 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.     

Strength Development of Solidified/Stabilized Organic Waste and Optimum Treatment Design

Abstract

Artificially contaminated (spiked) natural soils were solidified/stabilized using various combinations of commonly used additives, such as lime, cement, fly ash, activated carbon, and silica fume. The effectiveness of the solidification/stabilization (S/S) processes was evaluated based on experimental findings from compaction testing, unconfined compressive shear strength, and X-ray diffraction (XRD). Correlations of limited reliability between unconfined compressive strength and penetrometer and torvane measurements were derived. Results from XRD experiments indicated that certain organic contaminants (i.e., naphthalene and pyrene) might impact the S/S processes for a given combination of additives. The type and amount of organic contaminants also affected the pozzolanic reactions. Specifically, the absence or small peak intensity of pozzolanic product XRD patterns for a given combination of additives was a good indication that the type and the amount of organic contaminant present inhibited pozzolanic reactions. This phenomenon was tested and confirmed for actual field-contaminated samples.     

Comparison of Particle Size Distributions and Elemental Partitioning from the Combustion of Pulverized Coal and Residual Fuel Oil

ABSTRACT

U.S. Environmental Protection Agency (EPA) research examining the characteristics of primary PM generated by the combustion of fossil fuels is being conducted in efforts to help determine mechanisms controlling associated adverse health effects. Transition metals are of particular interest, due to the results of studies that have shown cardiopulmonary damage associated with exposure to these elements and their presence in coal and residual fuel oils. Further, elemental speciation may influence this toxicity, as some species are significantly more water-soluble, and potentially more bio-available, than others. This paper presents results of experimental efforts in which three coals and a residual fuel oil were combusted in three different systems simulating process and utility boilers. Particle size distributions (PSDs) were determined using atmospheric and low-pressure impac-tion as well as electrical mobility, time-of-flight, and light-scattering techniques. Size-classified PM samples from this study are also being utilized by colleagues for animal instillation experiments.

Experimental results on the mass and compositions of particles between 0.03 and >20 μm in aerodynamic diameter show that PM from the combustion of these fuels produces distinctive bimodal and trimodal PSDs, with a fine mode dominated by vaporization, nucleation, and growth processes. Depending on the fuel and combustion equipment, the coarse mode is composed primarily of unburned carbon char and associated inherent trace elements (fuel oil) and fragments of inorganic (largely calcium-alumino-silicate) fly ash including trace elements (coal). The three coals also produced a central mode between 0.8- and 2.0-μm aerodynamic diameter. However, the origins of these particles are less clear because vapor-to-particle growth processes are unlikely to produce particles this large.

Possible mechanisms include the liberation of micron-scale mineral inclusions during char fragmentation and burnout and indicates that refractory transition metals can contribute to PM <2.5 μm without passing through a vapor phase. When burned most efficiently, the residual fuel oil produces a PSD composed almost exclusively of an ultrafine mode (~0.1 μm). The transition metals associated with these emissions are composed of water-soluble metal sulfates. In contrast, the transition metals associated with coal combustion are not significantly enriched in PM <2.5 μm and are significantly less soluble, likely because of their association with the mineral constituents. These results may have implications regarding health effects associated with exposure to these particles.