Characterization of emissions from a pilot-scale combustor operating on coal blended with woody biomass.

Emissions generated from the combustion of coal have been a subject of regulation by the United States Environmental Protection Agency (U.S. EPA) and State agencies for years, as they have been associated with adverse effects on human health and the environment. Over the past several decades, regulations on these facility emissions have become more stringent and have therefore caused industry to look toward new pre- and post-combustion control technologies. In more recent years, there has been a "push" toward renewable and cleaner burning alternative fuels as replacements for traditional fossil fuels. Part of this "push" has been accomplished by States and Regions offering incentives and options for renewable portfolios, which over half of the states now have in some form. The current study investigates the potential changes in both gaseous and particulate emissions from the use of a variety of woody biomass materials as a drop-in replacement for coal as compared to use of 100% bituminous coal. Four different biomass materials are blended individually with coal at 20% and 40% by mass for testing on the U.S. EPA's Multi-Pollutant Control Research Facility, a pilot-scale coal-fired facility located in Research Triangle Park, North Carolina. Emissions are calculated based on measurements from the flue gas to characterize gaseous species (CO, CO2, NOX, SO2, other acid gases, and several organic hazardous air pollutants) as well as fine and ultrafine particulate (mass, size distribution, number count, elemental carbon, organic carbon, and black carbon) and compared among each combination of fuels and 100% bituminous coal.

Comparison of gaseous and particulate emissions from a pilot-scale combustor using three varieties of coal.

Gaseous and particulate emissions generated from the combustion of coal have been associated with adverse effects on human health and the environment, and have therefore been the subject of regulation by federal and state government agencies. Detailed emission characterizations are needed to better understand the impacts of pre- and post-combustion controls on a variety of coals found in the United States (U.S.). While the U.S. Environmental Protection Agency (EPA) requires industry reporting of emissions for criteria and several hazardous air pollutants (HAPs), many of the methods for monitoring and measuring these gaseous and particulate emissions rely on time-integrated sampling techniques. Though these emissions reports provide an overall representation of day-to-day operations, they represent well-controlled operations and do not encompass real combustion events that occur sporadically. The current study not only characterizes emissions from three coals (bituminous, sub-bituminous, and lignite), but also investigates the use of instrumentation for improved measurement and monitoring techniques that provide real-time, continuous emissions data. Testing was completed using the U.S. EPA's Multi-Pollutant Control Research Facility, a pilot-scale coal-fired combustor using industry-standard emission control technologies, in Research Triangle Park, North Carolina. Emissions were calculated based on measurements from the flue gas (pre- and post-electrostatic precipitator), to characterize gaseous species (CO, CO2, O2, NOX, SO2, other acid gases, and several organic HAPs) as well as fine and ultrafine particulate (mass, size distribution, number count, elemental carbon, organic carbon, and black carbon). Comparisons of traditional EPA methods to those made via Fourier Transfer Infrared (FTIR) Spectroscopy for CO, NOX, and SO2 are also reported.

Behavior of mercury emissions from a commercial coal-fired power plant: the relationship between stack speciation and near-field plume measurements.

The reduction of divalent gaseous mercury (Hg(II)) to elemental gaseous mercury (Hg(0)) in a commercial coal-fired power plant (CFPP) exhaust plume was investigated by simultaneous measurement in-stack and in-plume as part of a collaborative study among the U.S. EPA, EPRI, EERC, and Southern Company. In-stack continuous emission monitoring data were used to establish the CFPP's real-time mercury speciation and plume dilution tracer species (SO2, NOX) emission rates, and an airship was utilized as an airborne sampling platform to maintain static position with respect to the exhaust plume centerline for semicontinuous measurement of target species. Varying levels of Hg(II) concentration (2.39-3.90 µg m(-3)) and percent abundance (∼ 87-99%) in flue gas and in-plume reduction were observed. The existence and magnitude of Hg(II) reduction to Hg(0) (0-55%) observed varied with respect to the types and relative amounts of coals combusted, suggesting that exhaust plume reduction occurring downwind of the CFPP is influenced by coal chemical composition and characteristics.

Characterization of PFAS air emissions from thermal application of fluoropolymer dispersions on fabrics.

During thermal processes utilized in affixing fluoropolymer coatings dispersion to fibers and fabrics, coating components are vaporized. It is suspected that per- and polyfluoroalkyl substances (PFAS) from the dispersions may undergo chemical transformations at the temperatures used, leading to additional emitted PFAS thermal byproducts. It is important to characterize these emissions to support evaluation of the resulting environmental and health impacts. In this study, a bench-scale system was built to simulate this industrial process via thermal application of dispersions to fiberglass utilizing relevant temperatures and residence times in sequential drying, baking, and sintering steps. Experiments were performed with two commercially available dispersions and a simple model mixture containing a single PFAS (6:2 fluorotelomer alcohol [6:2 FTOH]). Vapor-phase emissions were sampled and characterized by several off-line and real-time mass spectrometry techniques for targeted and nontargeted PFAS. Results indicate that multiple PFAS thermal transformation products and multiple nonhalogenated organic species were emitted from the exit of the high temperature third (sintering) furnace when 6:2 FTOH was the only PFAS present in the aqueous mixture. This finding supports the hypothesis that temperatures typical of these industrial furnaces may also induce chemical transformations within the fluorinated air emissions. Experiments using the two commercial fluoropolymer dispersions indicate air emissions of part-per-million by volume (ppmv) concentrations of heptafluoropropyl-1,2,2,2-tetrafluoroethyl ether (Fluoroether E1), as well as other PFAS at operationally relevant temperatures. We suspect that E1 is a direct thermal decomposition product (via decarboxylation) of 2,3,3,3-tetrafluoro-2-(heptafluoropropoxy)propanoic acid (commonly referred to as HFPO-DA) present in the dispersions. Other thermal decomposition products, including the monomer, tetrafluoroethene, may originate from the PFAS used to stabilize the dispersion or from the polymer particles in suspension. This study represents the first researcher-built coating application simulator to report nontargeted PFAS emission characterization, real-time analyses, and the quantification of 30 volatile target PFAS.Implications: Thermal processes used to affix fluoropolymers to fabrics are believed to be a source of PFAS air emissions. These coating operations are used by many large and small manufacturers and typically do not currently require any air emissions control. This research designed and constructed a bench-scale system that simulates these processes and used several off-line and advanced real-time mass spectroscopy techniques to characterize PFAS air emissions from two commercial fluoropolymer dispersions. Further, as the compositions of commercial dispersions are largely unknown, a model three-component solution containing a single PFAS was used to characterize emissions of multiple PFAS thermal transformation products at operationally relevant conditions. This research shows that fluoropolymer fabric coating facilities can be sources of complex mixtures of PFAS air emissions that include volatile and semivolatile PFAS present in the dispersions, as well as PFAS byproducts formed by the thermal transformation of fluorocarbon and hydrocarbon species present in these dispersions.

Combustion of C1 and C2 PFAS: Kinetic modeling and experiments.

A combustion model, originally developed to simulate the destruction of chemical warfare agents, was modified to include C1-C3 fluorinated organic reactions and kinetics compiled by the National Institute of Standards and Technology (NIST). A simplified plug flow reactor version of this model was used to predict the destruction efficiency (DE) and formation of products of incomplete combustion (PICs) for three C1 and C2 per- and poly-fluorinated alkyl substances (PFAS) (CF4, CHF3, and C2F6) and compare predicted values to Fourier Transform Infrared spectroscopy (FTIR)-based measurements made from a pilot-scale EPA research combustor (40-64 kW, natural gas-fired, 20% excess air). PFAS were introduced through the flame, and at post-flame locations along a time-temperature profile allowing for simulation of direct flame and non-flame injection, and examination of the sensitivity of PFAS destruction on temperature and free radical flame chemistry. Results indicate that CF4 is particularly difficult to destroy with DEs ranging from ~60 to 95% when introduced through the flame at increasing furnace loads. Due to the presence of lower energy C-H and C-C bonds to initiate molecular dissociation reactions, CHF3 and C2F6 were easier to destroy, exhibiting DEs >99% even when introduced post-flame. However, these lower bond energies may also lead to the formation of CF2 and CF3 radicals at thermal conditions unable to fully de-fluorinate these species and formation of fluorinated PICs. DEs determined by the model agreed well with the measurements for CHF3 and C2F6 but overpredicted DEs at high temperatures and underpredicted DEs at low temperatures for CF4. However, high DEs do not necessarily mean absence of PICs, with both model predictions and limited FTIR measurements indicating the presence of similar fluorinated PICs in the combustion emissions. The FTIR was able to provide real-time emission measurements and additional model development may improve prediction of PFAS destruction and PIC formation.Implications: The widespread use of PFAS for over 70 years has led to their presence in multiple environmental matrixes including human tissues. While the chemical and thermal stability of PFAS are related to their desirable properties, this stability means that PFAS are very slow to degrade naturally and potentially difficult to destroy completely through thermal treatment processes often used for organic waste destruction. In this applied combustion study, model PFAS compounds were introduced to a pilot-scale EPA research furnace. Real-time FTIR measurements were performed of the injected compound and trace products of incomplete combustion (PICs) at operationally relevant conditions, and the results were successfully compared to kinetic model predictions of those same PFAS destruction efficiencies and trace gas-phase PIC constituents. This study represents a significant potential enhancement in available tools to support effective management of PFAS-containing wastes.

Low Temperature Thermal Treatment of Gas-Phase Fluorotelomer Alcohols by Calcium Oxide.

Given the extent to which per- and polyfluoroalkyl substances (PFAS) are used in commercial and industrial applications, the need to evaluate treatment options that reduce environmental emissions and human and ecological exposures of PFAS is becoming more necessary. One specific chemical class of PFAS, fluorotelomer alcohols (FTOHs), have vapor pressures such that a significant fraction is expected to be present in the gas-phase even at ambient temperatures. FTOHs are used in a variety of PFAS applications, including synthesis and material coatings. Using two complementary mass spectrometric methods, the use of calcium oxide (CaO) was examined as a low temperature and potentially low-cost thermal treatment media for removal and destruction of four gas-phase FTOHs of varying molecular weights. This was accomplished by assessing the removal/destruction efficiency of the FTOHs and the formation of fluorinated byproducts as a function of treatment temperature (200 - 800 °C) in the presence of CaO compared to thermal-only destruction. During the treatment process, there is evidence that other PFAS compounds are produced at low temperatures (200 - 600 °C) as the primary FTOH partially degrades. At temperatures above 600 °C, thermal treatment with CaO prevented the formation or removed nearly all these secondary products.

On-road emissions of PCDDs and PCDFs from heavy duty diesel vehicles.

This work characterized emission factors of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDDs/Fs) from on-road sampling of three heavy duty diesel vehicles (HDDVs) under experimental conditions of city and highway driving; idling operation; high (>400 ppm) and low (<5 ppm) sulfur (S) fuels; and high mileage and rebuilt engine testing. Emission factors, homologue profiles, and isomer patterns were compared to determine whether the experimental conditions had an impact on PCDD/F emissions, or whether these conditions were uninfluential in determining a fleet-representative emission factor. For a single HDDV tested under conditions of a high mileage engine, a newly rebuilt engine, and the newly rebuilt engine with low S diesel fuel, emission factors were 0.023 (+/- 0.022), 0.008 (+/- 0.002), and 0.016 (+/- 0.013) ng toxic equivalency (TEQ)/km, respectively. These results may infer some limited condition-specific differences in PCDD/F emissions, but these differences do not appear to have a significant effect on the HDDV emission factor. An older HDDV with mechanical fuel controls resulted in a single test value of 0.164 ng TEQ/km, significantly higher than all other results. Observed differences in emission factors, homologue profiles, and TEQ-related isomer patterns from this on-vehicle sampling and others' tunnel sampling suggest limitations in our present characterization of fleet PCDD/F emissions.

Characterization of Air Toxics from an Oil-Fired Firetube Boiler.

Tests were conducted on a commercially available firetube package boiler running on #2 through #6 oils to determine the emissions levels of hazardous air pollutants from the combustion of four fuel oils (a #2 oil, a #5 oil, a low sulfur #6 oil, and a high sulfur #6 oil). Measurements of carbon monoxide, nitrogen oxides, particulate matter, and sulfur dioxide stack gas concentrations were made for each oil. Flue gases were also sampled to determine levels of volatile and semivolatile organic compounds and of metals. Analytical procedures were used to provide more detailed information regarding the emissions rates for carbonyls (aldehydes and ketones), and polycyclic aromatic hydrocarbons (PAHs) in addition to the standard analyses for volatile and semivolatile organics. Metals emissions were greater than organic emissions for all oils tested, by an order of magnitude. Carbonyls dominated the organic emissions, with emission rates more than double the remaining organics for all four oils tested. Formaldehyde made up the largest percentage of carbonyls, at roughly 50% of these emissions for three of the four oils, and approximately 30% of the carbonyl emissions from the low sulfur #6 oil. Naphthalene was found to be the largest part of the PAH emissions for three of the four oils, with phenanthrene being greatest for the #2 fuel oil. The flue gases were also sampled for polychlorinated dibenzodioxins and polychlorinated dibenzofurans; however, inconsistent levels were found between repeat tests. For the boiler tested, no single hazardous air pollutant (HAP) was emitted at a rate which would require control under Title III of the Clean Air Act Amendments of 1990. The fuel emitting the largest amount of HAPs was the high sulfur #6 oil, which had a total HAP emission rate of less than 100 lb (45 kg)/year, based on operation for a full year at a firing rate of 1.25 x 106 Btu/hr (50% load of the unit tested).

Emissions of Trace Products of Incomplete Combustion from a Pilot-Scale Incinerator Secondary Combustion Chamber.

Experiments were performed on a 73 kW rotary kiln incinerator simulator equipped with a 73 kW secondary combustion chamber (SCC) to examine emissions of products of incomplete combustion (PICs) resulting from incineration of carbon tetrachloride (CC14) and dichloromethane (CH2C12). Species were measured using an on-line gas chromatograph (GC) system capable of measuring concentrations of eight species of volatile organic compounds (VOCs) in a near-realtime fashion. Samples were taken at several points within the SCC, to generate species profiles with respect to system residence time. For the experiments, the afterburner on the SCC was operated at conditions ranging from fuel-rich to fuellean, while the kiln was operated at a constant set of conditions. Results indicate that combustion of CH2C12 produces higher levels of measured PICs than combustion of CC14, particularly 1, 2 dichlorobenzene, and to a lesser extent, monochlorobenzene. Benzene emissions were predominantly affected by the afterburner air/fuel ratio regardless of whether or not a surrogate waste was being fed.