Catalytic Reduction of Nitrogen Oxides in Automobile Exhaust

The catalytic reduction of oxides of nitrogen from leaded automobile exhaust has been demonstrated to be technically feasible. These studies made with copper-containing catalysts are based upon the reducing nature of exhaust caused by the carbon monoxide present. The reaction involves 2 CO + 2 NO → + N₂ + CO₂ + 178.5 Kcal.     

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.     

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

Abstract

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

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.     

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 Predictive Mechanism for Mercury Oxidation on Selective Catalytic Reduction Catalysts under Coal-Derived Flue Gas

Abstract

This paper introduces a predictive mechanism for elemental mercury (Hg⁰) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH₃)/nitric oxide (NO) ratio and concentrations of Hg⁰ and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg⁰ oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH₃ and that Hg⁰ contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg⁰ oxidation by NH₃, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH₃ adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg⁰ oxidation. But once NH₃ has been consumed, the Hg⁰ oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH₃/NO ratios, promote Hg⁰ oxidation.

This mechanism accurately interprets the reported tendencies for greater extents of Hg⁰ oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg⁰ oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg⁰ oxidation by NH₃ for NH₃/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg⁰ oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.     

Technology Innovations and Experience Curves for Nitrogen Oxides Control Technologies

Abstract

This paper reviews the regulatory history for nitrogen oxides (NO_x) pollutant emissions from stationary sources, primarily in coal-fired power plants. Nitrogen dioxide (NO₂) is one of the six criteria pollutants regulated by the 1970 Clean Air Act where National Ambient Air Quality Standards were established to protect public health and welfare. We use patent data to show that in the cases of Japan, Germany, and the United States, innovations in NO_x control technologies did not occur until stringent government regulations were in place, thus “forcing” innovation. We also demonstrate that reductions in the capital and operation and maintenance (O&M) costs of new generations of high-efficiency NO_x control technologies, selective catalytic reduction (SCR), are consistently associated with the increasing adoption of the control technology: the so-called learning-by-doing phenomena. The results show that as cumulative world coal-fired SCR capacity doubles, capital costs decline to ~86% and O&M costs to 58% of their original values. The observed changes in SCR technology reflect the impact of technological advance as well as other factors, such as market competition and economies of scale.     

Determination of Oxides of Nitrogen in Combustion Effluents with a Nitrate Ion Selective Electrode

The nitrate ion selective electrode was investigated as an alternative approach to the present colorimetric determination of nitrate resulting from oxidative absorption of nitrogen oxides from combustion effluents. The electrode offers advantages of speed and relatively simple experimental procedure. Replicate measurements of 10^?4–10^?2M nitric acid solutions using bracketing standards show that the electrode approach is capable of good precision (coefficient of variation = ±4%). Comparison of a method utilizing the nitrate electrode with the more laborious phenol disulfonic acid method for the measurement of nitrogen oxides in both oil and gas fired combustion effluents showed agreement within 4% of the mean even in the presence of high levels of SO₂. The correlation coefficient found for PDS vs nitrate electrode is 0.987.     

Deactivation of the Vanadia Catalyst in the Selective Catalytic Reduction Process

Results are summarized of a comprehensive study of the effects on the SCR process of all major possible poisons encountered in the combustion gases from U.S. coals. A general rule evolved from this study Is that the effect of the additive on the catalyst activity Is directly related to the basicity of the additive; poisoning Is caused by the basicity. Quantitative effects are presented, while a qualitative summary is given as follows: strong poisons-alkali metal oxides; weak poisons-oxides of alkaline earth metals, arsenic, lead phosphorus and chlorides of strong alkaline metals. SO₂ is a promoter due to its acidity. HCI, although acidic, reacts with both NH₃ (forming NH₄CI) and V₂O₅ (forming VCI₂ and VCI₃) and consequently strongly deactivates the SCR reaction.

A summary is also given for a theoretical and experimental study of the monolithic honeycomb reactor using both undoped and poison-doped catalysts. The results showed that the reactor performance can be predicted directly from the intrinsic catalyst activity through a model.     

Considerations in Setting Standards for Oxides of Nitrogen

Since 1959 the California Department of Public Health has held responsibility for setting standards for ambient air quality and for motor vehicle emissions. The need for standards for oxides of nitrogen involves consideration both of direct effects and effects resulting from participation in photochemical smog reactions. This paper discusses the various effects of concern and describes the department’s program for establishing air quality standards which will become the basis for vehicle emission standards and serve as guides for control of other sources of oxides of nitrogen.     

Ozone Control Strategies Based on the Ratio of Volatile Organic Compounds to Nitrogen Oxides

The 1990 Clean Air Act Amendments require states with O₃ nonattainment areas to adopt regulations to enforce reasonable available control technologies (RACT) for NO_X stationary sources by November 1992. However, if the states can demonstrate that such measures will have an adverse effect on air quality, NO_X requirements may be waived. To assist the states in making this decision, the U.S. EPA is attempting to develop guidelines for the states to use in deciding whether NO_X reductions will have a positive or negative impact on O3 air quality. Although NO_X is a precursor of O₃, at low VOC/NO_X ratios, the reduction of NO_X can result in increased peak O₃. EPA is examining existing information on VOC/NO_X ratios to develop “rules of thumb” to guide the states in their decision-making process. An examination of 6 a.m. to 9 a.m. VOC/NO_X ratios at a number of sites in the eastern U.S. indicates that the ratio is highly variable from day-to-day and there is no apparent relationship between ratios measured at different sites within the same area. In addition, statistical analysis failed to identify significant relationships between the 6 a.m. to 9 a.m. VOC/NO_X ratio and the maximum 1-hr. O₃ within a given area. Since we know from smog chamber and modeling studies that such a relationship exists, this further invalidates the assumption that a ratio measured at a single site is representative of the ratio for the entire region. Based on this Information, we conclude that having the 6 a.m. to 9 a.m. ambient VOC/NO_X ratio for a given area is insufficient information, by itself, to decide whether a VOC-alone, a NO_x-alone, or a combined VOC-NO_X reduction strategy is a viable or optimum O₃-reduction strategy.     

燃煤火力发电厂大气污染及其控制

电能是一种优质能源，它的使用方便快捷，使其在国民经济的各个领域得到广泛应用，但火力发电厂在发电过程中排放的烟尘所造成的大气污染，也给人类带来了负面影响。文中主要谈到燃煤火力发电厂，介绍了它的燃料特性和生产，以及排放的污染物和其危害，重点列出了当前可行的控制措施。     

Response of Fine Particulate Matter to Emission Changes of Oxides of Nitrogen and Anthropogenic Volatile Organic Compounds in the Eastern United States

Abstract

A three-dimensional chemical transport model (Particulate Matter Comprehensive Air Quality Model with Extensions [PMCAMx]) is used to investigate changes in fine particle (PM_2.5) concentrations in response to 50% emissions changes of oxides of nitrogen (NO_x) and anthropogenic volatile organic compounds (VOCs) during July 2001 and January 2002 in the eastern United States. The reduction of NO_x emissions by 50% during the summer results in lower average oxidant levels and lowers PM_2.5 (8% on average), mainly because of reductions of sulfate (9–11%), nitrate (45–58%), and ammonium (7–11%). The organic particulate matter (PM) slightly decreases in rural areas, whereas it increases in cities by a few percent when NO_x is reduced. Reduction of NO_x during winter causes an increase of the oxidant levels and a rather complicated response of the PM components, leading to small net changes. Sulfate increases (8–17%), nitrate decreases (18– 42%), organic PM slightly increases, and ammonium either increases or decreases a little. The reduction of VOC emissions during the summer causes on average a small increase of the oxidant levels and a marginal increase in PM_2.5. This small net change is due to increases in the inorganic components and decreases of the organic ones. Reduction of VOC emissions during winter results in a decrease of the oxidant levels and a 5–10% reduction of PM_2.5 because of reductions in nitrate (4–19%), ammonium (4–10%), organic PM (12–14%), and small reductions in sulfate. Although sulfur dioxide (SO₂) reduction is the single most effective approach for sulfate control, the coupled decrease of SO₂ and NO_x emissions in both seasons is more effective in reducing total PM_2.5 mass than the SO₂ reduction alone.     

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.     

Quantitative Determination of Gaseous Nitrogen Dioxide Concentrations over Long Path Lengths by Selective Absorption of Argon Ion Laser Emission

An argon ion laser emits several laser lines In the visible region of the optical spectrum. The absorption coefficients of N0₂ at these laser emissions were measured in a multiple pass absorption cell. A differential technique, in which the ratio of the transmitted intensities of the argon laser emissions is measured, is described to determine the concentration of N0₂ in a polluted atmosphere over path lengths of several kilometers. Measurement of ratios eliminates interferences from particle scattering and thermal index gradients. Evaluation of the data taken in the 48 meter multipass cell indicates that concentrations of N0₂ less than one part per million could be determined in a 1 km optical path.     

A Note on Comparison of Statistical and Analytical Results for Calculating Oxides of Nitrogen Concentrations

A question often asked about analytical diffusion models is “How do the analytical results for calculating pollution concentrations compare with those obtained by statistical techniques?” Miller and Holzworth (1967) have developed a simple analytical diffusion model that yields relative pollution concentrations, x/Q, as a function of afternoon mixing depth, mean transport wind speed, and city size. This analytical model may also be used in reverse to determine apparent afternoon source strengths from observed afternoon pollution concentrations. The apparent source strengths may then be used with the model on independent data to estimate pollution concentrations. It is the purpose of this note to compare results of calculating average afternoon concentrations of oxides of nitrogen (NO_x) by use of the Miller-Holzworth model with those obtained from statistical regression equations.     

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.     

Thermal and Catalytic Incinerators for the Control of VOCs

Abstract

The emission of Volatile Organic Compounds (VOCs) is attracting increasing concern both from the public and by government agencies. Among the many available control technologies for the treatment of VOC containing waste streams, incineration offers an ultimate disposal strategy rather than a means for collecting or concentrating the offending compounds. This paper describes the major, commercially available thermal and catalytic incinerator systems that are designed to treat dilute, VOC containing gas streams. Qualitative guidelines are presented whereby the technologies can be compared. In addition, an example waste stream is used to illustrate a simplified procedure for calculating the material and energy balances for each of the incinerators. The resulting parameters will be used in a companion paper to estimate the capital and operating costs associated with each design. In this manner, a first estimate can be obtained of the costs of cleaning a waste stream containing low levels of VOCs.