Formation of Oxides of Nitrogen in Pulverized Coal Combustion

Nitrogen oxides are a potential atmospheric pollutant. Their formation and decomposition were studied in an experimental pulverized-coal-fired furnace. The concentration of nitrogen oxides (NO_x) was a maximum in the combustion zone and decreased as the combustion gas cooled. At a coal burning rate of 2 Ib/hr and 22% excess air, reduction of nitrogen oxides was obtained by selective secondary-air distribution. With 105% cf the stoichiometric air fed to the coal-combustion zone and 17% additional air fed just beyond the flame front, 62% reduction of NO_x occurred with good combustion efficiency. Lowering the quantity of excess air lowered the NO_x concentration, but at the expense of combustion efficiency. When 22% excess air was fed to the primary combustion zone, NO_x concentration in the effluent was 550 ppm and carbon in the fly ash 2.0%. With 5% excess air, the NO_x concentration fell to 210 ppm and carbon in the fly ash rose to 13.8%. With stoichiometric combustion the NO_x was 105 ppm a reduction of 81 %, and the carbon was 42.3%. Recirculation of combustion gas was not an effective means of lowering NO_x formation.     

NOx Reduction in a Gas Fired Utility Boiler by Combustion Modifications

Data on the effect of several combustion modifications on the formation of nitrogen oxides and on boiler efficiency were acquired and analyzed for a 110 MW gas fired utility boiler. The results from the study showed that decreasing the oxygen in the flue gas from 2.2% to 0.6% reduced the NO_x formation by 33% and also gave better boiler efficiencies. Flue gas recirculation through the bottom of the firebox was found to be ineffective. Staged combustion was found to reduce the NO_x emissions by as much as 55 % while decreasing the efficiency by about 5%. Adjustment of the burner air registers reduced the NO_x formation by about 20 ppm. The lowest NO_x emissions of 42 ppm (at about 3% O₂) in the stack was obtained for air only to one top burner and 0.5% oxygen in the flue gas.     

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.     

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.     

Removal of NOx from Flue Gas with Iron Filings Reduction Following Complex Absorption in Ferrous Chelates Aqueous Solutions

Abstract

A novel process for removal of nitrogen oxides (NO_x) from flue gases with iron filings reduction following complex absorption in iron-ethylenediaminetetraacetic acid aqueous solution is proposed. The reaction mechanism involved in the process is discussed briefly. The parameters influencing the process, including the concentration of ferrous chelates, initial pH, amount of iron filings, temperature, flow rate of the flue gas, and inlet nitric oxide concentration and oxygen content of the flue gas, are researched in detail. The optimal NO_x removal conditions are established. The regeneration and circular utilization of the absorption solution also is studied.     

Selective Reduction of Nitrogen Oxides In Combustion Flue Gases

The body of Information presented in this paper is directed to those Individuals concerned with the removal of NO_x in combustion flue gases. A catalytic process for the selective reduction of nitrogen oxides by ammonia has been investigated. Efforts were made toward the development of catalysts resistant to SO_x poisoning. Nitrogen oxides were reduced over various metal oxide catalysts in the presence or absence of SO_x(SO₂ and SO₃). Catalysts consisting of oxides of base metals (for example, Fe₂O₃) were easily poisoned by SO₃, forming sulfates of the base metals. A series of catalysts which are not susceptible to the SO_x poisoning has been developed. The catalysts possess a high activity and selectivity over a wide range of temperatures, 250—450°C. The catalysts were tested in a pilot plant which treated a flue gas containing 110-150 ppm NO_x, 660-750 ppm SO₂, and 40-90 ppm SO₃. The pilot plant was operated at 350°C and at a space velocity of 10,000 h^-1. The removal of nitrogen oxides was more than 90% for several months.

A mechanism of the NO-NH₃ reaction has also been investigated. It is found that NO reacts with NH₃ at a 1:1 mole ratio in the presence of oxygen and the reaction is completely inhibited by the absence of oxygen. The experimental data show that the NO-NH₃ reaction in the presence of oxygen is represented byNO + NH₃ + 1/4 O₂ = N₂ + 3/2 H₂O.     

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.     

Predicting Extents of Mercury Oxidation in Coal-Derived Flue Gases

Abstract

The proposed mercury (Hg) oxidation mechanism consists of a 168-step gas phase mechanism that accounts for interaction among all important flue gas species and a heterogeneous oxidation mechanism on unburned carbon (UBC) particles, similar to established chemistry for dioxin production under comparable conditions. The mechanism was incorporated into a gas cleaning system simulator to predict the proportions of elemental and oxidized Hg species in the flue gases, given relevant coal properties (C/H/O/N/S/Cl/Hg), flue gas composition (O₂, H₂O, HCl), emissions (NO_X, SO_X, CO), the recovery of fly ash, fly ash loss-on-ignition (LOI), and a thermal history. Predictions are validated without parameter adjustments against datasets from lab-scale and from pilot-scale coal furnaces at 1 and 29 MW_t. Collectively, the evaluations cover 16 coals representing ranks from sub-bituminous through high-volatile bituminous, including cases with Cl₂ and CaCl₂ injection. The predictions are, therefore, validated over virtually the entire domain of Cl-species concentrations and UBC levels of commercial interest. Additional predictions identify the most important operating conditions in the furnace and gas cleaning system, including stoichiometric ratio, NO_X, LOI, and residence time, as well as the most important coal properties, including coal-Cl.     

Emission characteristics for co-combustion of leather wastes,sewage sludge,and coal in a laboratory-scale entrained flow tube furnace

Four different mixed fuels consisted of leather waste, coal, and sewage sludge were combusted in a lab-scale entrained flow fluidized bed furnace. The influence of blending ratio on emission characteristics of SO₂, NO_x, HCl, particulate matter (PM), heavy metals, and polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) was studied. Results showed that the mixing of coal with sewage sludge had a complex effect on the emission characteristics. On the one hand, with more sewage sludge blending in the mixed fuel, the acid gas pollutant (SO₂, NO_x) decreased a lot, and the recovery of volatile heavy metals (Cd, Pb) increased at the same time. Furthermore, the leaching toxicity of Cr in the fly ash and bottom ash went down below the national standard with the adding of sewage sludge. On the other hand, the mixing of sewage sludge which consisted of more ash content resulted in the increase of the PM emission. Moreover, the high content of Cu and chlorine in the sewage sludge can promote the formation of polychlorinated dibenzo-p-dioxins and polychlorinated dibenzofurans (PCDD/Fs) when the fuel 3 and 4 were combusted. Most importantly, the concentration of toxic PCDD/Fs in the flue gas produced from fuel 3 and fuel 4 was successfully controlled down below 0.20 ng I-TEQ/Nm³ by the active carbon.

     

Effectiveness in the Use of Natural Gas for the Reduction of Atmospheric Emissions: Case Study—Industrial Sector in the Metropolitan Region of Santiago,Chile

Abstract

The purpose of this investigation was to quantify the potential of natural gas to reduce emissions from stationary combustion sources by analyzing the case study of the metropolitan region of Santiago, Chile. For such purposes, referential base scenarios have been defined that represent with and without natural gas settings. The method to be applied is an emission estimate based on emission factors. The results for this case study reveal that stationary combustion sources that replaced their fuel reduced particulate matter (PM) emissions by 61%, sulfur oxides (SO_x) by 91%, nitrogen oxides (NO_x) by 40%, and volatile organic compounds (VOC) by 10%. Carbon mon-oxide (CO) emissions were reduced by 1%. As a result of this emission reduction, in addition to reductions caused by other factors, such as a shift to cleaner fuels other than natural gas, technological improvements, and sources which are not operative, emission reduction goals set forth by the environmental authorities were broadly exceeded.     

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.     

An Intelligent Emissions Controller for Fuel Lean Gas Reburn in Coal-Fired Power Plants

ABSTRACT

The application of artificial intelligence techniques for performance optimization of the fuel lean gas reburn (FLGR) system is investigated. A multilayer, feedforward artificial neural network is applied to model static nonlinear relationships between the distribution of injected natural gas into the upper region of the furnace of a coal-fired boiler and the corresponding oxides of nitrogen (NO_x) emissions exiting the furnace. Based on this model, optimal distributions of injected gas are determined such that the largest NO_x reduction is achieved for each value of total injected gas. This optimization is accomplished through the development of a new optimization method based on neural networks. This new optimal control algorithm, which can be used as an alternative generic tool for solving multidimensional nonlinear constrained optimization problems, is described and its results are successfully validated against an off-the-shelf tool for solving mathematical programming problems. Encouraging results obtained using plant data from one of Commonwealth Edison's coal-fired electric power plants demonstrate the feasibility of the overall approach.

Preliminary results show that the use of this intelligent controller will also enable the determination of the most cost-effective operating conditions of the FLGR system by considering, along with the optimal distribution of the injected gas, the cost differential between natural gas and coal and the open-market price of NO_x emission credits. Further study, however, is necessary, including the construction of a more comprehensive database, needed to develop high-fidelity process models and to add carbon monoxide (CO) emissions to the model of the gas reburn system.     

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.     

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.     

Chemical Transformations of Nitrogen Oxides While Sampling Combustion Products

The present study reviews the sampling environments and chemical transformations of nitrogen oxides that may occur within probes and sample lines while sampling combustion products. Experimental data are presented for NO_x transformations in silica and 316 stainless steel tubing when sampling simulated combustion products in the presence of oxygen, carbon monoxide, and hydrogen. A temperature range of 25° to 400°C is explored. In the absence of CO and H₂, 316 stainless steel is observed to promote the reduction of nitrogen dioxide to nitric oxide at temperatures in excess of 300°C, and silica is found to be passive to chemical transformation. In the presence of CO, reduction of N0₂ to NO is observed in 316 stainless steel at temperatures in excess of 100°C, and reduction of NO₂ to NO in silica is observed at 400°C. In the presence of H₂, NO₂ is reduced to NO in 316 stainless steel at 200°C and NO_x is removed at temperatures exceeding 200°C. In silica, the presence of H₂ promotes the reduction of NO₂ to NO at 300°C and the removal of NO_x above 300°C.     

Controlling NOx Emissions From Steam Generators

The information presented is directed to those individuals concerned with reducing nitrogen oxides (NO _x ) emissions from gas, oil, or coal fired utility steam generators. First, this paper presents NO _x emission data obtained in the testing of tangentially fired utility boilers; second, it relates these data to the general body of information developed by other investigators in the areas of theoretical analysis and bench scale and full scale testing; and finally, it discusses current design practice in relation to NO _x emission control and the continuing R&D effort required to assure acceptable control technology.     

A New Catalytic Reactor for Nitrogen Oxides Removal

The body of information presented in this paper is directed to those individuals concerned with the catalytic NO_x removal reactor for a dirty (containing dust) flue gas. In the case of treating a dirty flue gas, the concentration of dust is the most important factor. While the dirty gas passes through the catalytic reactor, dust particles deposit and plug up the catalyst causing the reactor pressure loss to rise. As a result, the NO_x reduction efficiency decreases more and more, and continuous operation becomes impossible. A new type of NO_x removal reactor for dirty flue gas, the intermittent moving bed reactor, has been developed. The following characteristics have been evaluated: (1) method of calculating reactor pressure loss caused by dust particles, (2) static pressure distribution across the catalyst bed in the reactor, (3) method of evaluating uniform movement of catalyst and (4) reentrainment pattern of dust by catalyst movement. After carrying out various successful pilot plant tests, the information needed for construction and operation of a commercial plant has been developed.     

A Feasibility Study on the Predictive Emission Monitoring System Applied to the Hsinta Power Plant of Taiwan Power Company

Abstract

The continuous emission monitoring system (CEMS) can monitor flue gas emissions continuously and instantaneously. However, it has the disadvantages of enormous cost, easily producing errors in sampling periods of bad weather, lagging response in variable ambient environments, and missing data in daily zero and span tests and maintenance. The concept of a predictive emission monitoring system (PEMS) is to use the operating parameters of combustion equipment through thermodynamic or statistical methods to construct a mathematic model that can predict emissions by a computer program. The goal of this study is to set up a PEMS in a gas-fired combined cycle power generation unit at the Hsinta station of Taiwan Power Co. The emissions to be monitored include nitrogen oxides (NO_x) and oxygen (O₂) in flue gas. The major variables of the predictive model were determined based on the combustion theory. The data of these variables then were analyzed to establish a regression model. From the regression results, the influences of these variables are discussed and the predicted values are compared with the CEMS data for accuracy. In addition, according to the cost information, the capital and operation and maintenance costs for a PEMS can be much lower than those for a CEMS.     

Regenerative Thermal Oxidation of Airborne N,N-Dimethylformamide and Its Associated Nitrogen Oxides Formation Characteristics

Abstract

In this study, a two-bed electrically heated regenerative thermal oxidizer (RTO) was used to test the thermal destruction and oxides of nitrogen (NO_x) formation characteristics in burning airstreams that contain either N, N-dimethylformamide or dimethylformamide (DMF) mixed with methyl ethyl ketone (MEK). The RTO contained two 0.152 m × 0.14 m × 1 m (L × W times] H) beds, both packed with gravel particles with an average diameter of approximately 0.0111 m and a height of up to 1 m with a void fraction of 0.42 in the packed section. The thermal recovery efficiency (TRE) and the gas pressure drop over the beds were also studied. Experimental results reveal that, with a valve shifting time (t _s) of 1.5 min, a superficial gas velocity (U _g) of 0.39 m/sec (evaluated at an influent air temperature of around 30 °C) and preset maximum destruction temperatures (T _S) of 750–950 °C, no NO_x was present in the effluent gas from the RTO when it was loaded with DMF-free air. When only DMF was present in the influent air, the average destruction efficiencies exceeded 96%, and increased with the influent DMF concentration from 300 to 750 mg/N?m³. The “NO_x-N formation/DMF-N destruction” mass ratios were in the range 0.76–1.05, and decreased as the influent DMF concentration increased within the experimental range. When both DMF and MEK were present in the influent gas, the NO_x formation ratio was almost the same and the DMF destruction efficiency increased with the influent MEK/DMF ratio from 150/300 to 4500/300 (mg/mg) and in the preset temperature range. The NO_x formation ratios were in the range 0.75–0.96. The TRE decreased as U _g increased but was invariant with T _s. The Ergun equation was found to suffice in the estimation of the pressure drop when the gas flowed over the packing beds.     

Ultra-high adsorption of Hg0 using impregnated activated carbon by selenium

Activated carbon was one of the main adsorptions utilized in elemental mercury (Hg⁰) removal from coal combustion flue gas. However, the high cost and low physical adsorption efficiency of activated carbon injection (ACI) limited its application. In this study, an ultra-high efficiency (nearly 100%) catalyst sorbent-Se_x/Activated carbon (Se_x/AC) was synthesized and applied to remove Hg⁰ in the simulated flue gas, which exhibited 120 times outstanding adsorption performance versus the conventional activated carbon. The Se_x/AC reached 17.98 mg/g Hg⁰ adsorption capacity at 160 °C under the pure nitrogen atmosphere. Moreover, it maintained an excellent mercury adsorption tolerance, reaching the efficiency of Hg⁰ removal above 85% at the NO and SO₂ conditions in a bench-scale fixed-bed reactor. Characterized by the multiple methods, including BET, XRD, XPS, kinetic and thermodynamic analysis, and the DFT calculation, we demonstrated that the ultrahigh mercury removal performance originated from the activated Se species in Se_x/AC. Chemical adsorption plays a dominant role in Hg⁰ removal: Selenium anchored on the surface of AC would capture Hg⁰ in the flue gas to form an extremely stable substance-HgSe, avoiding subsequent Hg⁰ released. Additionally, the oxygen-containing functional groups in AC and the higher BET areas promote the conversion of Hg⁰ to HgO. This work provided a novel and highly efficient carbon-based sorbent -Se_x/AC to capture the mercury in coal combustion flue gas.

Selenium-modified porous activated carbon and the interface functional group promotes the synergistic effect of physical adsorption and chemical adsorption to promote the adsorption capacity of Hg⁰.