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.     

A structural decomposition analysis of air pollution from fossil fuel combustion in India

During the last decade, there has been worldwide concern with global climate change, which has been induced by greenhouse gases (GHGs) due to the use of fossil fuels. The CO₂ emissions from fossil fuel combustion have been identified as the single most significant source of GHG emissions into the atmosphere. Realising the need to control and regulate emissions of pollutants, the objective of the present study estimates the trend of CO₂, SO₂ and NO_x between the periods 1991-92 and 1996-97. An input-output structural decomposition analysis approach is used to determine their sources of change. It also provides a set of alternative scenarios for the year 2001-2 and 2006-7. The sources of changes in the amount of CO₂, SO₂ and NO_x emissions are categorised into four factors: the ecoefficiency, the structure of production, the structure of demand, and the volume of demand. Results indicate that the electricity sector contributes more towards direct, as well as indirect, emission coefficients. The petroleum product sector also contributes more in this respect. The dominant role is played by the structure of demand and the volume of demand.     

Description and application of the EAP computer program for calculating life-cycle energy use and greenhouse gas emissions of household consumption items

Focusing on reduction in energy use and greenhouse gas emissions, a life-cycle-based analysis tool has been developed. The energy analysis program (EAP) is a computer program for determining energy use and greenhouse gas emissions related to household consumption items, using a hybrid calculation method. EAP consists of a number of fill-in screens corresponding to steps in the hybrid method, which in their turn correspond to different stages in life-cycles of consumer goods. The database incorporated in EAP comprises data about energy use and emissions of the main greenhouse gases (CO₂, CH₄and N₂O) concerning materials, economic sectors, means of transport, etc. The use of the program in several projects showed the applicability and usefulness of EAP in research and policy. In this article, EAP is applied to food: French beans as a metaphor for fruit and vegetables.     

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.     

VOC composition and ozone-forming potential of the exhaust gas of in-use motorcycles

The emission profile of volatile organic compounds (VOC) and the ozone-forming potential (OP) of the exhaust gas of six in-use motorcycles (four 4-stroke- and two 2-stroke-engines) were determined. The motorcycles were tested on a chassis dynamometer in a real-world driving cycle. The analysis involved the C2–C12-hydrocarbons as well as the aldehydes and ketones. Additionally, the regulated THC and NO_x emissions were measured according to the test procedure for type approval (ECE 40). Two vehicles did not fulfil the THC emission standard, whereas all vehicles met the requirements for NO_x emission. The aromatic fuel components toluene and xylene, and the combustion products ethene and propene contributed most to the OP of the VOC emission. The highest OP was found with the 2-stroke engines. The VOC profile of the emissions varied with vehicle and driving conditions. The reactivity of the exhaust gas, defined as gram ozone per gram of non-methane organic gases (NMOG), increased with vehicle speed.     

Flue Gas NOX Reduction Using Ammonia Radical Injection

A novel technique has been developed for flue gas NO_X reduction through the injection of plasma-treated ammonia and its decomposition products. Numerical investigation of the chemical kinetics shows nearly complete NO removal when ammonia radicals are injected into the flue gas. The feasibility of this new technique was experimentally explored on a small-scale laboratory combustor at Carnegie Mellon University and concurrently on a larger-scale combustor at the DOE Pittsburgh Energy Technology Center. Preliminary experimental results have shown that ammonia plasma-injection is more effective than simple ammonia-injection at low flue gas temperatures. NO_X reduction of 85 to 90 percent was achieved at a low plasma power input. This technique is expected to provide additional opportunities for inexpensive and effective NO_X reduction in stationary sources.     

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.     

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.     

Gas Cleaning Systems for the High Temperature,High Pressure Fluidized Bed Coal Combustor

The high temperature, high pressure fluidized bed coal combustor concept is intended to deliver a low dust content combustion gas at 1600°F and 11 atmospheres to a gas turbine for electricity generation. The perceived advantages of the system are 1) 15-20% increase in fuel efficiency and 2) flue gas desulfurization by adding crushed limestone to the fluidized bed combustor. A major R & D effort, supported by DOE, EPA, EPRI, and others, was undertaken to identify one or more gas cleaning systems of commercial size capable of 1) meeting EPA’s new source performance standards for coal burning power plants and 2) operating reliably under the severe environmental conditions specified. The principal gas cleaning systems that have been investigated for this service include: ceramic cleanable cloth filters, granular bed filters, rigid, porous ceramic structures, and electrostatic precipitators. Some of the fly ash collectors have been operated up to pilot scale size under realistic conditions. In spite of several years of intensive effort and many millions of dollars expended, production of a commercial unit has not been realized. A major content of this paper is a review of the accomplishments and failures of each of the fly ash collector concepts and a series of recommendations to guide future R & D efforts.     

Evaluation of Tire-Derived Fuel for Use in Nitrogen Oxide Reduction by Reburning

ABSTRACT

Tire-derived fuel (TDF) was tested in a small-scale (44 kW or 150,000 Btu/hr) combustor to determine its feasibility as a fuel for use in reburning for control of nitrogen oxide (NO). TDF was gravity-fed into upward flowing combustion gases from a primary natural gas flame doped with ammonia to simulate a high NO combustion process. Emissions of NO, oxygen, carbon dioxide, carbon monoxide, and particulate matter were measured. The tests varied the nominal primary NO level from 600 to 1,200 ppm and the primary stoichiometry from 1.1 to 1.2, and used both natural gas and TDF as reburn fuels. The reburn injection rate was varied to achieve 8–20% of the total heat input from the reburn fuel. NO emissions reductions ranged between 20 and 63% when using TDF, depending upon the rate of TDF injection, primary NO, and primary stoichiometry. NO emission reductions when using natural gas as the reburn fuel were consistently higher than those when using TDF. While additional work remains to optimize the process and evaluate costs, TDF has been shown to have the potential to be a technically viable reburning fuel.     

Low Emissions from Controlled Combustion for Automotive Rankine Cycle Engines

Rankine cycle engines have a high potential for meeting the emission levels established by the 1970 amendment to the Federal Clean Air Act for the 1975-76 automobile. This paper discusses a Solar research and development program sponsored by EPA/APCO which demonstrates a full scale 2 million Btu per hour working model of a Rankine cycle engine combustor and controls which can surpass the emission goals established.

Special features of the combustor are the unique methods of precisely controlling both the fuel and air to provide optimum flame performance at any engine power level. This paper discusses the special requirements of the Rankine cycle engine and shows why the very wide range of fuel flow required necessitates use. of special techniques in fuel atomization, fuel and air control, and aerodynamics. Sufficient discussion is included to show the design methods that are necessary, in general, to achieve low emissions in continuous flow combustion systems. Emphasis is placed on the importance of interfacing a combustion system with other engine parts if a successful low emission, wide turndown ratio combustor working model is to be achieved. Sufficient discussion on combustion kinetics is included to advise on approaches necessary to minimize NO formation in external combustion systems while maintaining high efficiency and low CO and unburned hydrocarbons.     

Organic Content of Particulate Matter In Turbine Engine Exhaust

Solid particulate matter, mainly carbon, emitted into the air from the combustion of fossil fuels contains a variety of organic species adsorbed on it. In our examination of these particulates from the combustion of kerosene type fuels in a gas turbine engine, attention was focused on polynuclear aromatic compounds, phenols, nitrosamines, and total organics. Polynuclears were determined by HPLC, GC/MS, and NMR examination. Phenols and nitrosamines were isolated and then measured by gas chromatography using a flame ionization detector and nitrogen detector. Total organics were determined by a backflush chromatographic procedure. The particulates were collected using a high capacity pumping system and 293 mm diameter teflon filters through which was passed up to 43 m³ of exhaust gas. Extraction of the organic matter was done in a Soxhlet extractor using hexane usually. The engine was operated at idle, approach, climb, and takeoff power settings with low sulfur and high sulfur (0.25%) fuels. Most of the PAH were small 3 and 4 fused ring compounds with very few, at low concentrations, of 5 and 6 fused ring species. No nitrosamines were found and except in a few cases, at low levels, no phenols. PNA and total organic levels decreased with increase in a power setting and were higher in the exhaust from low sulfur fuels. Less than 1% of the organic matter emitted by the engine was absorbed on the particulate matter. The body of information presented in the paper is directed to individuals concerned with the nature of emissions from gas turbine engines. The work was supported by a contract with the Environmental Protection Agency.     

Greenhouse Gas Dynamics of Municipal Solid Waste Alternatives

ABSTRACT

Previous greenhouse gas studies comparing landfilling with combustion of municipal solid waste (MSW) are limited to examinations of the emissions weighted by their relative radiative activity. This paper adds another dimension by analyzing the atmospheric response to these emissions. The heart of the analysis is a time-dependent model using a perturbation analysis of the IS92a results of the Intergovernmental Panel on Climate Change (IPCC). Using as inputs the emissions from the two technologies, the model calculates atmospheric concentration histories. Scenarios for a landfill and a combustor envision each accepting 1000 Mg refuse/day for a 30-year operating period followed by a 70-year postclosure period. The baseline scenario examines the basic greenhouse impact of each technology. The other scenario adds active gas collection at the landfill and energy offset credits for avoided power plant carbon emissions. For both scenarios, CH₄ and trace gases from the landfill persist in the atmosphere, and they are relatively potent at forcing IR heating. The combination of these features place the landfill much higher than previously expected on the greenhouse impact scale. For the baseline scenario, the time-integrated radiative forcing from landfilling is 115 times that of combustion, and this ratio is 45 for the second scenario.     

Local emissions trading in developing countries as a transitional strategy toward international greenhouse gas trading: a Beijing example

As is the case in most developing countries, China relies on command-and-control regulation to control air pollution. While it has instituted a modest air pollution levy system in the past 20 years for emissions in excess of standards, the effect on emission levels has been minimal. This paper focuses on how to use emissions trading as a policy instrument to achieve cost-effective reductions in air pollution in Beijing. Emissions or allowance trading has been widely applied to air pollution control in the USA during the past 25 years. Three of the most recent programmes will be examined, which provide applicable experience for possible SO₂ and NO_x trading in the Beijing region. A trading strategy for Beijing will be proposed by comparing the economic and political institutional differences between the USA and China, which could eventually facilitate acceptance of an international greenhouse gas trading system.     

Nitrogen oxides emissions from the MILD combustion with the conditions of recirculation gas

The nitrogen oxides (NO_x) reduction technology by combustion modification which has economic benefits as a method of controlling NO_x emitted in the combustion process, has recently been receiving a lot of attention. Especially, the moderate or intense low oxygen dilution (MILD) combustion which applied high temperature flue gas recirculation has been confirmed for its effectiveness with regard to solid fuel as well. MILD combustion is affected by the flue gas recirculation ratio and the composition of recirculation gas, so its NO_x reduction efficiency is determined by them. In order to investigate the influence of factors which determine the reduction efficiency of NO_x in MILD coal combustion, this study changed the flow rate and concentration of nitrogen (N₂), carbon dioxide (CO₂) and steam (H₂O) which simulate the recirculation gas during the MILD coal combustion using our lab-scale drop tube furnace and performed the combustion experiment. As a result, its influence by the composition of recirculation gas was insignificant and it was shown that flue gas recirculation ratio influences the change of NO_x concentration greatly. Implications: We investigated the influence of factors determining the nitrogen oxides (NO_x) reduction efficiency in MILD coal combustion, which applied high-temperature flue gas recirculation. Using a lab-scale drop tube furnace and simulated recirculation gas, we conducted combustion testing changing the recirculation gas conditions. We found that the flue gas recirculation ratio influences the reduction of NO_x emissions the most.     

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.     

The Effects of Liquid Water Addition In Gas Turbine Combustors

The addition of liquid water, in quantities equivalent to the mass of fuel consumed, exerts thermal and chemical effects upon the combustion process in a gas turbine engine. The thermal influence is produced by the vaporizalion and heating of the water and its vapor. The final temperature is reduced and the concentrations of NO _x , O, OH, CO are lower than standard combustion concentrations. Chemically, the additional H₂O participates in reactions producing the aforementioned species. However, the lower temperature overrides this influence. These effects have been assessed for different fuel states, i.e., for pre-mixed combustion and for liquid fuel undergoing vaporization and mixing.     

Synthetic SO2 Sorbents for Fluidized-Bed Coal Combustors

The information presented in this paper is directed to engineers who are involved with environmental emissions from coal conversion plants. Synthetic sorbents were investigated as an alternative to natural sorbents (limestone) for the removal of SO₂ from the combustion gas in a fluidized-bed coal combustor. The sulfation rate of a synthetic sorbent, CaO in α-AI₂O₃, was determined as a function of gas composition, temperature, and calcium concentration in the sorbent. The reaction was found to be diffusion-controlled above 850°C and kinetically controlled at lower temperatures. The physical characteristics of the support material have a major effect oh the sulfation kinetics. Porosity measurements indicated that supports containing large pores (>0.2 µm) produced sorbents having high sulfation rates and that pores with diameters less than 0.2 µm did not contribute significantly to the capture of SO₂. The sorbents SrO in α-AI₂O₃ and BaO in α-AI₂O₃ had lower SO₂ capture rates than did CaO in α-AI₂O₃. The alkali metal oxide sorbents K₂O and Na₂O in α-AI₂O₃ captured SO₂ much faster than did the alkaline earth metal oxides.     

Speciated Hydrocarbon Emissions from the Combustion of Single Component Fuels. I. Effect of Fuel Structure

Speciated hydrocarbon emissions data have been collected for six single-component fuels run in a laboratory pulse flame combustor (PFC). The six fuels include n-heptane, isooctane (2, 2, 4-trimethylpentane), cyclohexane, 1-hexene, toluene, and methyl-t-butyl ether (MTBE: an oxygenated fuel extender). Combustion of non-aromatic fuels in the PFC (at a fuel/air equivalence ratio of Φ = 1.02) produced low levels of unburned fuel and high yields of methane and olefins (> 75 percent combined) irrespective of the molecular structure of the fuel. In contrast, hydrocarbon emissions from toluene combustion in the PFC were comprised predominantly of unburned fuel (72 percent). With the PFC, low levels of 1, 3-butadiene (0.3-1.8 percent) were observed from all the fuels except MTBE, for which no measurable level (<0.2 percent) was detected; low levels of benzene were observed from isooctane, heptane, and 1-hexene, but significant levels (9 percent) from cyclohexane and toluene. No measurable amount of benzene (< 0.2 percent) was observed in the MTBE exhaust.

For isooctane and toluene the speciated hydrocarbon emissions from a spark-ignited (SI) single-cylinder engine were also determined. HC emissions from the SI engine contained the same species as observed from the PFC, although the relative composition was different. For the non-aromatic fuel isooctane, unburned fuel represented a larger fraction (50 percent) of the HC emissions when run in the engine. HC emissions from toluene combustion in the engine were similar to those from the PFC.